TITLE

POLYMERS FOR USE IN ELECTRONIC DEVICES

CLAIM OF BENEFIT OF PRIOR APPLICATION

This application claims the benefit of U.S. Provisional Application No. 62/672,272, filed May 16, 2018, which is incorporated in its entirety herein by reference.

BACKGROUND INFORMATION

Field of the Disclosure

The present disclosure relates to novel polymeric compounds. The disclosure further relates to methods for preparing such polymeric compounds and electronic devices having at least one layer comprising these materials.

Description of the Related Art

Materials for use in electronics applications often have strict requirements in terms of their structural, optical, thermal, electronic, and other properties. As the number of commercial electronics applications continues to increase, the breadth and specificity of requisite properties demand the innovation of materials with new and/or improved properties. Polyimides represent a class of polymeric compounds that has been widely used in a variety of electronics applications. They can serve as a flexible replacement for glass in electronic display devices provided that they have suitable properties. These materials can function as a component of Liquid Crystal Displays (“LCDs”), where their modest consumption of electrical power, light weight, and layer flatness are critical properties for effective utility. Other uses in electronic display devices that place such parameters at a premium include device substrates, substrates for color filter sheets, cover films, touch screen panels, and others. A number of these components are also important in the

construction and operation of organic electronic devices having an organic light emitting diode (“OLED”). OLEDs are promising for many display applications because of their high power conversion efficiency and applicability to a wide range of end-uses. They are increasingly being used in cell phones, tablet devices, handheld / laptop computers, and other commercial products. These applications call for displays with high information content, full color, and fast video rate response time in addition to low power consumption.

Polyimide films generally possess sufficient thermal stability, high glass transition temperature, and mechanical toughness to merit consideration for such uses. Also, polyimides generally do not develop haze when subject to repeated flexing, so they are often preferred over other transparent substrates like polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) in flexible display applications.

The traditional amber color of polyimides, however, precludes their use in some display applications such as color filters and touch screen panels since a premium is placed on optical transparency. Further, polyimides are generally stiff, highly aromatic materials; and the polymer chains tend to orient in the plane of the film / coating as the film / coating is being formed. This leads to differences in refractive index in the parallel vs. perpendicular directions of the film (birefringence) which produces optical retardation that can negatively impact display performance. If polyimides are to find additional applications in the displays market, a solution is needed to maintain their desirable properties, while at the same time improving their optical transparency and reducing the amber color and birefringence that leads to optical retardation.

There is thus a continuing need for low-color materials that are suitable for use in electronic devices.

SUMMARY

There are provided imide-containing monomers for polyimides. There is further provided a diamine having Formula I

where:

R ^a represents a tetracarboxylic acid component residue;

R ^b represents a diamine residue; and

m is an integer from 1 -20.

There is further provided a polyamic acid composition which is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the diamines comprise 1 -100 mol% of a diamine having Formula I.

There is further provided an acid dianhydride having Formula IV

where:

R ^d represents a tetracarboxylic acid component residue;

R ^e represents a diamine residue; and

m is an integer from 1 -20.

There is further provided a polyamic acid composition which is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the tetracarboxylic acid components comprise 1 -100 mol% of a tetracarboxylic acid dianhydride having Formula IV.

There is further provided a composition comprising (a) either of the above polyamic acid and (b) at least one high-boiling, aprotic solvent. There is further provided a polyimide resulting from the imidization of either of the above polyamic acid.

There is further provided a polyimide film comprising the above polyimide.

There is further provided one or more methods for preparing the above polyimide film.

There is further provided a flexible replacement for glass in an electronic device wherein the flexible replacement for glass the above polyimide film.

There is further provided an electronic device having at least one layer comprising the above polyimide film.

There is further provided an organic electronic device, such as an OLED, wherein the organic electronic device contains a flexible replacement for glass as disclosed herein.

The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improve understanding of concepts as presented herein.

FIG. 1 includes an illustration of one example of a polyimide film that can act as a flexible replacement for glass.

FIG. 2 includes an illustration of one example of an electronic device that includes a flexible replacement for glass.

Skilled artisans appreciate that objects in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the objects in the figures may be exaggerated relative to other objects to help to improve understanding of embodiments.

DETAILED DESCRIPTION

Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims. The detailed description first addresses Definitions and

Clarification of Terms, followed by Imide-Containing Monomers, the Diamine Having Formula I, the Acid Dianhydride Having Formula IV, the Polyamic Acid, the Polyimide, the Methods for Preparing the Polyimide Films, the Electronic Device, and Examples.

1. Definitions and Clarification of Terms

Before addressing details of embodiments described below, some terms are defined or clarified.

As used in the“Definitions and Clarification of Terms”, R, R ^a , R ^b , R’, R” and any other variables are generic designations and may be the same as or different from those defined in the formulas.

The term“alignment layer” is intended to mean a layer of organic polymer in a liquid-crystal device (LCD) that aligns the molecules closest to each plate as a result of its being rubbed onto the LCD glass in one preferential direction during the LCD manufacturing process.

As used herein, the term“alkyl” includes branched and straight- chain saturated aliphatic hydrocarbon groups. Unless otherwise indicated, the term is also intended to include cyclic groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, tertbutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl and the like. The term“alkyl” further includes both substituted and

unsubstituted hydrocarbon groups. In some embodiments, the alkyl group may be mono-, di- and tri-substituted. One example of a substituted alkyl group is trifluoromethyl. Other substituted alkyl groups are formed from one or more of the substituents described herein. In certain embodiments alkyl groups have 1 to 20 carbon atoms. In other embodiments, the group has 1 to 6 carbon atoms. The term is intended to include heteroalkyl groups. Heteroalkyl groups may have from 1 -20 carbon atoms. The term“aprotic” refers to a class of solvents that lack an acidic hydrogen atom and are therefore incapable of acting as hydrogen donors. Common aprotic solvents include alkanes, carbon tetrachloride (CCI4), benzene, dimethyl formamide (DMF), N-methyl-2-Pyrrolidone (NMP), dimethylacetamide (DMAc), and many others.

The term“aromatic compound” is intended to mean an organic compound comprising at least one unsaturated cyclic group having 4n+2 delocalized pi electrons. The term is intended to encompass both aromatic compounds having only carbon and hydrogen atoms, and heteroaromatic compounds wherein one or more of the carbon atoms within the cyclic group has been replaced by another atom, such as nitrogen, oxygen, sulfur, or the like.

The term“aryl” or“aryl group” a moiety formed by removal of one or more hydrogen (“H”) or deuterium (“D”) from an aromatic compound. The aryl group may be a single ring (monocyclic) or have multiple rings

(bicyclic, or more) fused together or linked covalently. A“hydrocarbon aryl” has only carbon atoms in the aromatic ring(s). A“heteroaryl” has one or more heteroatoms in at least one aromatic ring. In some embodiments, hydrocarbon aryl groups have 6 to 60 ring carbon atoms; in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, heteroaryl groups have from 4-50 ring carbon atoms; in some

embodiments, 4-30 ring carbon atoms.

The term“alkoxy” is intended to mean the group -OR, where R is alkyl.

The term“aryloxy” is intended to mean the group -OR, where R is aryl.

The term“allyl” is intended to mean the group -CH2-CH=CH2.

The term“vinyl” is intended to mean the group -CH=CH2.

Unless otherwise indicated, all groups can be substituted or unsubstituted. An optionally substituted group, such as, but not limited to, alkyl or aryl, may be substituted with one or more substituents which may be the same or different. Suitable substituents include alkyl, aryl, nitro, cyano, -N(R’)(R ^” ), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -S(0)2- -C(=0)-N(R’)(R”), (R’)(R”)N-alkyl, (R’)(R”)N-alkoxyalkyl, (R’)(R”)N- alkylaryloxyalkyl, -S(0) _s -aryl (where s=0-2) or -S(0) _s -heteroaryl (where s=0-2). Each R’ and R” is independently an optionally substituted alkyl, cycloalkyl, or aryl group. R’ and R”, together with the nitrogen atom to which they are bound, can form a ring system in certain embodiments. Substituents may also be crosslinking groups.

The term“amine” is intended to mean a that contains a basic nitrogen atom with a lone pair. The term“amino” refers to the functional group -Nhte, -NHR, or -NR2, where R is the same or different at each occurrence and can be an alkyl group or an aryl group. The term

“diamine” is intended to mean a compound that contains two basic nitrogen atoms with associated lone pairs. The term“aromatic diamine” is intended to mean an aromatic compound having two amino groups. The term“bent diamine” is intended to mean a diamine wherein the two basic nitrogen atoms and associated lone pairs are asymmetrically disposed about the center of symmetry of the corresponding compound or functional group, e.g. m-phenylenediamine:

The term“aromatic diamine residue” is intended to mean the moiety bonded to the two amino groups in an aromatic diamine. The term “aromatic diisocyanate residue” is intended to mean the moiety bonded to the two isocyanate groups in an aromatic diisocyanate compound. This is further illustrated below. Diamine/Diisocyanate Residue

The term“b*” is intended to mean the b* axis in the CIELab Color Space that represents the yellow / blue opponent colors. Yellow is represented by positive b* values, and blue is represented by negative b* values. Measured b* values may be affected by solvent, particularly since solvent choice may affect color measured on materials exposed to high- temperature processing conditions. This may arise as the result of inherent properties of the solvent and/or properties associated with low levels of impurities contained in various solvents. Particular solvents are often preselected to achieve desired b* values for a particular application.

The term“birefringence” is intended to mean the difference in the refractive index in different directions in a polymer film or coating. This term usually refers to the difference between the x- or y-axis (in-plane) and the z-axis (out-of-plane) refractive indices.

The term "charge transport," when referring to a layer, material, member, or structure is intended to mean such layer, material, member, or structure facilitates migration of such charge through the thickness of such layer, material, member, or structure with relative efficiency and small loss of charge. Hole transport materials facilitate positive charge; electron transport materials facilitate negative charge. Although light-emitting materials may also have some charge transport properties, the term “charge transport layer, material, member, or structure” is not intended to include a layer, material, member, or structure whose primary function is light emission. The term“compound” is intended to mean an electrically uncharged substance made up of molecules that further include atoms, wherein the atoms cannot be separated from their corresponding molecules by physical means without breaking chemical bonds. The term is intended to include oligomers and polymers.

The term“linear coefficient of thermal expansion (CTE or a)” is intended to mean the parameter that defines the amount which a material expands or contracts as a function of temperature. It is expressed as the change in length per degree Celsius and is generally expressed in units of pm / m / °C or ppm / °C. a = (DI_ / Lo) / DT

Measured CTE values disclosed herein are made via known methods during the first or second heating scan. The understanding of the relative expansion / contraction characteristics of materials can be an important consideration in the fabrication and/or reliability of electronic devices.

The term“dopant” is intended to mean a material, within a layer including a host material, that changes the electronic characteristic(s) or the targeted wavelength(s) of radiation emission, reception, or filtering of the layer compared to the electronic characteristic(s) or the wavelength(s) of radiation emission, reception, or filtering of the layer in the absence of such material.

The term“electroactive” as it refers to a layer or a material, is intended to indicate a layer or material which electronically facilitates the operation of the device. Examples of electroactive materials include, but are not limited to, materials which conduct, inject, transport, or block a charge, where the charge can be either an electron or a hole, or materials which emit radiation or exhibit a change in concentration of electron-hole pairs when receiving radiation. Examples of inactive materials include, but are not limited to, planarization materials, insulating materials, and environmental barrier materials. The term“tensile elongation” or“tensile strain” is intended to mean the percentage increase in length that occurs in a material before it breaks under an applied tensile stress. It can be measured, for example, by ASTM Method D882.

The prefix“fluoro” is intended to indicate that one or more hydrogens in a group have been replaced with fluorine.

The term“glass transition temperature (or T _g )” is intended to mean the temperature at which a reversible change occurs in an amorphous polymer or in amorphous regions of a semi crystalline polymer where the material changes suddenly from a hard, glassy, or brittle state to one that is flexible or elastomeric. Microscopically, the glass transition occurs when normally-coiled, motionless polymer chains become free to rotate and can move past each other. T _g ’s may be measured using differential scanning calorimetry (DSC), thermo-mechanical analysis (TMA), or dynamic-mechanical analysis (DMA), or other methods.

The prefix“hetero” indicates that one or more carbon atoms have been replaced with a different atom. In some embodiments, the

heteroatom is O, N, S, or combinations thereof.

The term“high-boiling” is intended to indicate a boiling point greater than 130°C.

The term“host material” is intended to mean a material to which a dopant is added. The host material may or may not have electronic characteristic(s) or the ability to emit, receive, or filter radiation. In some embodiments, the host material is present in higher concentration.

The term“isothermal weight loss” is intended to mean a material’s property that is directly related to its thermal stability. It is generally measured at a constant temperature of interest via thermogravimetric analysis (TGA). Materials that have high thermal stability generally exhibit very low percentages of isothermal weight loss at the required use or processing temperature for the desired period of time and can therefore be used in applications at these temperatures without significant loss of strength, outgassing, and/or change in structure.

The term "liquid composition" is intended to mean a liquid medium in which a material is dissolved to form a solution, a liquid medium in which a material is dispersed to form a dispersion, or a liquid medium in which a material is suspended to form a suspension or an emulsion.

The term“matrix” is intended to mean a foundation on which one or more layers is deposited in the formation of, for example, an electronic device. Non-limiting examples include glass, silicon, and others.

The term“1 % TGA Weight Loss” is intended to mean the

temperature at which 1 % of the original polymer weight is lost due to decomposition (excluding absorbed water).

The term“optical retardation (or RTH)” is intended to mean the difference between the average in-plane refractive index and the out-of- plane refractive index (i.e. , the birefringence), this difference then being multiplied by the thickness of the film or coating. Optical retardation is typically measured for a given frequency of light, and the units are reported in nanometers. It can be measured by Metricon or Axoscan.

The term "organic electronic device" or sometimes“electronic device” is herein intended to mean a device including one or more organic semiconductor layers or materials.

The term“particle content” is intended to mean the number or count of insoluble particles that is present in a solution. Measurements of particle content can be made on the solutions themselves or on finished materials (pieces, films, etc.) prepared from those films. A variety of optical methods can be used to assess this property.

The term“photoactive” refers to a material or layer that emits light when activated by an applied voltage (such as in a light emitting diode or chemical cell), that emits light after the absorption of photons (such as in down-converting phosphor devices), or that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector or a photovoltaic cell).

The term“polyamic acid solution” refers to a solution of a polymer containing amic acid units that have the capability of intramolecular cyclization to form imide groups.

The term“polyimide” refers to condensation polymers resulting from the reaction of one or more bifunctional carboxylic acid components with one or more primary diamines or diisocyanates. They contain the imide structure -CO-NR-CO- as a linear or heterocyclic unit along the main chain of the polymer backbone.

The term“satisfactory,” when regarding a materials property or characteristic, is intended to mean that the property or characteristic fulfills all requirements / demands for the material in-use. For example, an isothermal weight loss of less than 1 % at 350 °C for 3 hours in nitrogen can be viewed as a non-limiting example of a“satisfactory” property in the context of the polyimide films disclosed herein.

The term“soft-baking” is intended to mean a process commonly used in electronics manufacture wherein spin-coated materials are heated to drive off solvents and solidify a film. Soft-baking is commonly performed on a hot plate or in exhausted oven at temperatures between 90 °C and 110 °C as a preparation step for subsequent thermal treatment of coated layers or films.

The term“substrate” refers to a base material that can be either rigid or flexible and may include one or more layers of one or more materials, which can include, but are not limited to, glass, polymer, metal or ceramic materials or combinations thereof. The substrate may or may not include electronic components, circuits, or conductive members.

The term“siloxane” refers to the group R3SiOR2Si-, where R is the same or different at each occurrence and is H, C1 -20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in an R alkyl group are replaced with Si.

The term“siloxy” refers to the group R3S1O-, where R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl.

The term“silyl” refers to the group R3S1-, where R is the same or different at each occurrence and is H, C1 -20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in an R alkyl group are replaced with Si.

The term“spin coating” is intended to mean a process used to deposit uniform thin films onto flat substrates. Generally, a small amount of coating material is applied on the center of the substrate, which is either spinning at low speed or not spinning at all. The substrate is then rotated at specified speeds in order to spread the coating material uniformly by centrifugal force.

The term“laser particle counter test” refers to a method used to assess the particle content of polyamic acid and other polymeric solutions whereby a representative sample of a test solution is spin coated onto a 5” silicon wafer and soft baked / dried. The film thus prepared is evaluated for particle content by any number of standard measurement techniques. Such techniques include laser particle detection and others known in the art.

The term“tensile modulus” is intended to mean the measure of the stiffness of a solid material that defines the initial relationship between the stress (force per unit area) and the strain (proportional deformation) in a material like a film. Commonly used units are giga pascals (GPa).

The term“tetracarboxylic acid component” is intended to mean any one or more of the following: a tetracarboxylic acid, a tetracarboxylic acid monoanhydride, a tetracarboxylic acid dianhydride, a tetracarboxylic acid monoester, and a tetracarboxylic acid diester.

The term“tetracarboxylic acid component residue” is intended to mean the moiety bonded to the four carboxy groups in a tetracarboxylic acid component. This is further illustrated below.

Tetracarboxylic acid component Residue

The term“transmittance” refers to the percentage of light of a given wavelength impinging on a film that passes through the film so as to be detectable on the other side. Light transmittance measurements in the visible region (380 nm to 800 nm) are particularly useful for characterizing film-color characteristics that are most important for understanding the properties-in-use of the polyimide films disclosed herein.

The term“yellowness index (or Yl)” refers to the magnitude of yellowness relative to a standard. A positive value of Yl indicates the presence, and magnitude, of a yellow color. Materials with a negative Yl appear bluish. It should also be noted, particularly for polymerization and/or curing processes run at high temperatures, that Yl can be solvent dependent. The magnitude of color introduced using DMAC as a solvent, for example, may be different than that introduced using NMP as a solvent. This may arise as the result of inherent properties of the solvent and/or properties associated with low levels of impurities contained in various solvents. Particular solvents are often preselected to achieve desired Yl values for a particular application. In a structure where a substituent bond passes through one or more rings as shown below,

it is meant that the substituent R may be bonded at any available position on the one or more rings.

The phrase“adjacent to,” when used to refer to layers in a device, does not necessarily mean that one layer is immediately next to another layer. On the other hand, the phrase“adjacent R groups,” is used to refer to R groups that are next to each other in a chemical formula (i.e. , R groups that are on atoms joined by a bond). Exemplary adjacent R groups are shown below:

In this specification, unless explicitly stated otherwise or indicated to the contrary by the context of usage, where an embodiment of the subject matter hereof is stated or described as comprising, including, containing, having, being composed of or being constituted by or of certain features or elements, one or more features or elements in addition to those explicitly stated or described may be present in the embodiment. An alternative embodiment of the disclosed subject matter hereof, is described as consisting essentially of certain features or elements, in which embodiment features or elements that would materially alter the principle of operation or the distinguishing characteristics of the

embodiment are not present therein. A further alternative embodiment of the described subject matter hereof is described as consisting of certain features or elements, in which embodiment, or in insubstantial variations thereof, only the features or elements specifically stated or described are present.

Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, use of“a” or“an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of the elements use the "New Notation" convention as seen in the CRC Handbook of Chemistry and Physics, 81 ^st Edition (2000-2001 ).

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specific materials, processing acts, and circuits are conventional and may be found in textbooks and other sources within the organic light-emitting diode display, photodetector, photovoltaic, and semiconductive member arts.

2. Imide-containinq Monomers

Difficulties with low reactivity, processability, and the capability to control polymer structure hinder the application of some potentially useful classes of monomers for synthesizing polyimides. Both dianhydride monomers and diamine monomers can present problems. Some monomers with low reactivity can only be polymerized under harsh reaction conditions. Such conditions can facilitate the formation of side reactions which deleteriously affect the quality of the ultimate polyimide film. Both optical and mechanical properties can be diminished.

It has been found that the imide-containing monomers described herein can be used to overcome problems with monomers having low reactivity, to control polymer structure (such as regioregularity and tacticity) in order to achieve imidization with a lower number of defects for polyimides with improved properties.

In some embodiments, the imide-containing monomers described herein can be used to provide polyimides having reduced stress.

In some embodiments, the imide-containing monomers are isolated, purified from defects and side products. Thus highly pure compounds with precisely defined oligomeric structures can be used as monomers.

In some embodiments, the imide-containing monomers are used as formed and are mixtures of preimidized compounds.

The imide-containing monomers described herein are compounds having an imidized core with reactive end groups.

In some embodiments, the imide-containing monomer is a diamine, and the reactive end groups are amino groups, -NH2.

In some embodiments, the imide-containing monomer is a diisocyanate, and the reactive end groups are isocyanate groups, -NCO.

In some embodiments, the imide-containing monomers are a tetracarboxylic acid dianhydride, and the reactive end groups are anhydrides.

In some embodiments, the imidized core contains two imide groups, hereinafter referred to as a“di-imide”.

In some embodiments, the imidized core is a polyimide oligomer having 4-20 imide groups.

Herein is disclosed a method of synthesis of precisely-defined imide-containing polymers obtained from preimidized (imide-containing) monomers. This is described below as Scheme I and Scheme II.

In Scheme I, the first step is preimidization of a first dianhydride with an excess of a first diamine. The thusly formed preimidized diamine monomer can be isolated and purified. The preimidized diamine possesses sufficient reactivity to react with one or more additional dianhydrides (which can be the same or different from the first

dianhydride) in step 2, to form an imide-containing polyamic acid. This imide-containing polymer is soluble and processible despite the presence of imide groups even in high molar ratios. Step 3 is final imidization to form the polyimide polymer using conventional imidization techniques, such as thermal curing. One embodiment of Scheme I is shown below, where the second dianhydride is different from the first.

Scheme I: one embodiment

0 0

2

and processible

imide-containing polymer

In the above scheme, Y represents the residue from the first

tetracarboxylic acid component (dianhydride), Z represents the residue from the diamine, X1 represents the residue from the second

tetracarboxylic acid component (dianhydride), n1 represents an integer of 1 -20, and n represents an integer greater than 50.

In some embodiments of Scheme I, n1 = 1 and the diamine has a single imidized core. In some embodiments of Scheme I, n1 = 2-20, and the diamine has an oligomeric imidized core. In some embodiments, n1 = 2-5; in some embodiments, 6-10; in some embodiments 11-20.

In Scheme II, the first step is preimidization of a first diamine with an excess of a dianhydride. The thusly formed preimidized dianhydride monomer possesses sufficient reactivity to react with one or more additional diamines (which can be the same or different from the first diamine) in step 2, to form an imide-containing polyamic acid. This imide- containing polymer is soluble and processible despite the presence of imide groups even in high molar ratio. Step 3 is final imidization to form the polyimide polymer using conventional imidization techniques, such as thermal curing. One embodiment of Scheme II is shown below, where the second diamine is different from the first.

Scheme II: one embodiment

In the above scheme, Y represents the residue from the tetracarboxylic acid component (dianhydride), Z represents the residue from the first diamine, X2 represents the residue from the second diamine, n1 represents an integer from 1-20, and n represents an integer greater than 50.

In some embodiments of Scheme II, n1 = 1 and the dianhydride has a single imidized core. In some embodiments of Scheme II, n1 = 2-20, and the dianhydride has an oligomeric imidized core. In some embodiments, n1 = 2-5; in some embodiments, 6-10; in some embodiments, 11-20.

Alternatively, the preimidized monomers can be used in situ without isolating and characterizing. This is described below as Scheme III and Scheme IV.

In Scheme III, the first step is preimidization of a first dianhydride with a large excess of a first diamine. The resulting mixture of preimidized diamine and excess first diamine is reacted with one or more dianhydrides and, optionally, one or more additional diamines, in step 2. The resulting imide-containing polyamic acid is imidized in step 3, using conventional imidization techniques.

In Scheme III, the preimidized diamine in made in step 1 has the formula shown below

where ml represents an integer from 1 -20. A mixture of monomers may be present having different ml values. In the polyamic acid and

polyimide, ml can be the same or different at each occurrence. In some embodiments, ml is 2-5; in some embodiments, 6-10; in some

embodiments, 11 -20. Y represents the residue from the first

tetracarboxylic acid component (dianhydride) and Z represents the residue from the first diamine.

In Scheme IV, the first step is preimidization of a first diamine with a large excess of a first dianhydride. The resulting mixture of preimidized dianhydride monomer and excess first dianhydride is reacted with one or more diamines and, optionally, one or more additional dianhydrides, in step 2. The resulting imide-containing polyamic acid is imidized in step 3, using conventional imidization techniques.

In Scheme IV, the preimidized dianhydride made in step 1 has the formula shown below

where ml represents an integer from 1 -20. A mixture of monomers may be present having different ml values. In the polyamic acid and polyimide, ml can be the same or different at each occurrence. In some embodiments, ml is 2-5; in some embodiments, 6-10; in some

embodiments, 1 1 -20. Y represents the residue from the first

tetracarboxylic acid component (dianhydride) and Z represents the residue from the first diamine. 3. Diamine Flaying Formula I

The diamine described herein has Formula I

where:

R ^a represents a tetracarboxylic acid component residue;

R ^b represents a diamine residue; and

m is an integer from 1 -20.

In some embodiments of Formula I, m = 1 .

In some embodiments of Formula I, m = 2-20.

In some embodiments of Formula I, m = 2-5.

In some embodiments of Formula I, m = 6-10.

In some embodiments of Formula m = 1 1 -20.

In some embodiments of Formula I, R ^a is aromatic.

In some embodiments of Formula I, R ^a is aliphatic; in some embodiments, cycloaliphatic.

In some embodiments of Formula I, R ^a is a polycylic cyloaliphatic group. In some embodiments of Formula I, R ^a is aromatic; in some embodiments, polycylic aromatic.

In some embodiments of Formula I, R ^a has both aromatic groups and cycloaliphatic groups.

In some embodiments of Formula I, R ^a represents the residue of a tetracarboxylic acid dianhydride.

In some embodiments of Formula I, R ^a represents the residue of a tetracarboxylic acid dianhydride selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'- hexafluoroiso-propylidenebisphthalic dianhydride (6FDA), 3, 3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA), 3, 3', 4,4'- diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic anhydride (FIQDEA), ethylene glycol bis (trimellitic anhydride) (TMEG-100), 4-(2,5- dioxotetrahydrofuran-3-yl)-1 ,2,3,4-tetrahydronapthalene-1 ,2-dicarboyxlic anhydride (DTDA); 4,4’-bisphenol A dianhydride (BPADA); cyclobutane-1 , 2, 3, 4-tetracarboxylic dianhydride (CBDA); xanthene tetracarboxylic dianhydrides; and the like. These aromatic dianhydrides may optionally be substituted with groups that are known in the art including alkyl, aryl, nitro, cyano, -N(R’)(R ^” ), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, fluoroalkyl, perfluoroalkyl, fluoroalkoxy, perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -S(0) ₂ -, -C(=0)-N(R’)(R”), (R’)(R”)N-alkyl, (R’)(R”)N- alkoxyalkyl, (R’)(R”)N-alkylaryloxyalkyl, -S(0) _s -aryl (where s=0-2) or - S(0) _s -heteroaryl (where s=0-2). Each R’ and R” is independently an optionally substituted alkyl, cycloalkyl, or aryl group. R’ and R”, together with the nitrogen atom to which they are bound, can form a ring system in certain embodiments. Substituents may also be crosslinking groups.

In some embodiments of Formula I, R ^a represents a residue from a tetracarboxylic acid dianhydride selected from the group consisting of PMDA, BPDA, 6FDA, BTDA, and CBDA. In some embodiments of Formula I, R ^a represents the residue of an aliphatic tetracarboxylic acid dianhydride or a polycyclic tetracarboxylic acid dianhydride.

In some embodiments of Formula I, R ^a is selected from the group consisting of Formulas A1 through A36

(A25) (A26)

(A35) (A36)

wherein:

R ¹ is the same or different at each occurrence and is selected from the group consisting of alkyl, fluoroalkyl, and silyl, where adjacent R ¹ groups can be joined together to form a double bond;

R ² , R ³ , and R ⁴ are the same or different at each occurrence and are selected from the group consisting of F, alkyl, fluoroalkyl, and silyl;

R ⁵ is selected from the group consisting of H, halogen, cyano, hydroxyl, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, hydrocarbon aryl, substituted hydrocarbon aryl, heteroaryl, substituted heteroaryl, vinyl, and allyl;

R ⁶ is selected from the group consisting of halogen, cyano,

hydroxyl, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, hydrocarbon aryl, substituted hydrocarbon aryl, heteroaryl, substituted heteroaryl, vinyl, and allyl;

R ⁸ and R ⁹ are the same or different at each occurrence and are selected from the group consisting of H, F, alkyl, fluoroalkyl, and silyl;

Q is selected from the group consisting of CR ⁸ R ⁹ , SiR ⁸ R ⁹ , S,

SR ⁸ R ⁹ , S=0, S0 ₂ , and C=0;

a is an integer from 0-6;

b is an integer from 0-3;

c, d, and e are the same or different and are an integer from 0-2; f is an integer from 0-4; z is an integer from 1 -6;

z1 is an integer from 0-6; and

* indicates a point of attachment.

In some embodiments of Formula I, R ^b is aliphatic; in some embodiments, cycloaliphatic.

In some embodiments of Formula I, R ^b is a polycyclic aliphatic group.

In some embodiments of Formula I, R ^b is aromatic; in some embodiments, polycyclic aromatic.

In some embodiments of Formula I, R ^b has both cycloaliphatic and aromatic groups.

In some embodiments of Formula I, R ^b represents the residue of a diamine having Formula D1

wherein:

R ¹⁰ is the same or different at each occurrence and is selected from the group consisting of fluoroalkyl and fluoroalkoxy;

R ¹¹ is the same or different at each occurrence and is selected from the group consisting of F, alkyl, fluoroalkyl, and silyl; b is the same or different at each occurrence and is an integer from 0-3;

c is the same or different at each occurrence and is an integer from 0-2; and

y is an integer from 0-2.

In some embodiments of Formula D1 , R ¹⁰ is a C1-5 perfluoroalkyl.

In some embodiments of Formula D1 , y = 0.

In some embodiments of Formula D1 , y = 1 .

In some embodiments of Formula D1 , b = c = 0. In some embodiments of Formula I, R ^b represents the residue of an aromatic diamine selected from the group consisting of p-phenylene diamine (PPD), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 3,3'- dimethyl-4,4'-diaminobiphenyl (o-tolidine), 3,3'-dihydroxy-4,4'- diaminobiphenyl (HAB), 9,9'-bis(4-aminophenyl)fluorene (FDA), o-tolidine sulfone (TSN), 2,3,5,6-tetramethyM ,4-phenylenediamine (TMPD), 2,4- diamino-1 ,3,5-trimethyl benzene (DAM), 3,3',5,5'-tetramethylbenzidine (3355TMB), 2,2'-bis(trifluoromethyl) benzidine (22TFMB or TFMB), 2,2- bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-methylene dianiline (MDA), 4,4'-[1 ,3-phenylenebis(1 -methyl-ethylidene)]bisaniline (Bis-M), 4,4'- [1 ,4-phenylenebis(1 -methyl-ethylidene)]bisaniline (Bis-P), 4,4'-oxydianiline (4,4’-ODA), m-phenylene diamine (MPD), 3,4'-oxydianiline (3,4’-ODA), 3,3'-diaminodiphenyl sulfone (3,3’-DDS), 4,4'-diaminodiphenyl sulfone (4,4’-DDS), 4,4'-diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-amino- phenoxy)phenyl]sulfone (BAPS), 2,2-bis[4-(3-aminophenoxy)- phenyl]sulfone (m-BAPS), 1 ,4'-bis(4-aminophenoxy)benzene (TPE-Q),

1 ,3'-bis(4-aminophenoxy)benzene (TPE-R), 1 ,3'-bis(3-amino- phenoxy)benzene (APB-133), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 4,4'-diaminobenzanilide (DABA), methylene bis(anthranilic acid) (MBAA), 1 ,3'-bis(4-aminophenoxy)-2,2-dimethylpropane (DANPG), 1 ,5-bis(4- aminophenoxy)pentane (DA5MG), 2,2'-bis[4-(4-aminophenoxy

pehnyl)]hexafluoropropane (FIFBAPP), 2,2-bis(4-aminophenyl)

hexafluoropropane (Bis-A-AF), 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (Bis-AP-AF), 2,2-bis(3-amino-4-methylphenyl) hexafluoropropane (Bis-AT-AF), 4,4'-bis(4-amino-2-trifluoromethyl phenoxy)biphenyl (6BFBAPB), 3,3'5,5'-tetramethyl-4,4'-diamino

diphenylmethane (TMMDA), and the like.

In some embodiments of Formula I, R ^b represents the residue of an aromatic diamine selected from the group consisting of PPD, MPD, m- tolidine, o-tolidine, benzidine, and TFMB.

Any of the above embodiments for Formula I can be combined with one or more of the other embodiments, so long as they are not mutually exclusive. In some embodiments of Formula I, the diamine is selected from the group consisting of Compound 1 through Compound 24

Compound 1

Compound 4

Compound 5

Compound 7

Compound 9

Compound 1 1

Compound 14

Compound 17

Compound 19

Compound 22

Compound 23

4. Dianhvdride Having Formula IV

The dianhydride described herein has Formula IV

where:

R ^d represents a tetracarboxylic acid component residue; R ^e represents a diamine residue; and

m is an integer from 1 -20.

In some embodiments of Formula IV, m = 1 .

In some embodiments of Formula IV, m = 2-20.

In some embodiments of Formula IV, m = 2-5.

In some embodiments of Formula IV, m = 6-10.

In some embodiments of Formula IV, m = 1 1 -20. Any of the above-listed tetracarboxylic acid dianhydrides suitable to form residue R ^a in Formula I are also suitable to form residue R ^d in Formula IV.

In some embodiments of Formula IV, R ^d represents a residue from a tetracarboxylic acid dianhydride selected from the group consisting of PMDA, BP DA, 6FDA, BTDA, and CBDA.

Any of the above-listed diamines suitable to form residue R ^b in Formula I are also suitable to form residue R ^e in Formula IV.

In some embodiments of Formula IV, R ^e represents the residue of a fluorinated aromatic diamine.

In some embodiments of Formula IV, R ^e is selected from the group consisting of Formulas E1 through E16

(E16)

where:

R ⁷ is the same or different at each occurrence and is selected from the group consisting of F, alkyl, aryl, Rf, and ORf;

R ⁸ and R ⁹ are the same or different at each occurrence and are selected from the group consisting of H, F, alkyl, fluoroalkyl, and silyl;

R ¹⁰ is the same or different at each occurrence and is selected from the group consisting of fluoroalkyl and fluoroalkoxy; R ¹¹ is the same or different at each occurrence and is selected from the group consisting of F, alkyl, fluoroalkyl, and silyl;

Rf is a Ci-3 perfluoroalkyl;

Q is selected from the group consisting of CR ⁸ R ⁹ , SiR ⁸ R ⁹ , S,

SR ⁸ R ⁹ , S=0, S0 ₂ , and C=0;

b is the same or different at each occurrence and is an integer from

0-3;

c is the same or different at each occurrence and is an integer from 0-2;

g is an integer from 0-4;

h is an integer from 0-6;

p is an integer from 1 -10;

q is an integer from 0-5;

y is an integer from 0-2; and

* indicates a point of attachment.

In some embodiments of E1 to E16, R ⁷ is selected from the group consisting of F, Rf, and ORf.

In some embodiments of E1 to E16, g is an integer from 1-4. Any of the above embodiments for Formula IV can be combined with one or more of the other embodiments, so long as they are not mutually exclusive.

In some embodiments of Formula IV, the dianhydride is selected from the group consisting of Compound 25 through Compound 38

Compound 25

Compound 28

Compound 29

Compound 32

Compound 35

Compound 36

5. The Polvamic Acid

The polyamic acid described herein is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein (a) the diamines comprise 1 -100 mol% of a diamine having Formula I, and/or (b) the tetracarboxylic acid components comprise 1 -100 mol% of a tetracarboxylic acid dianhydride having Formula IV. In some embodiments, the polyamic acid is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein either

(a) the diamines comprise 1 -100 mol% of a diamine having Formula I, or

(b) the tetracarboxylic acid components comprise 1 -100 mol% of a tetracarboxylic acid dianhydride having Formula IV.

A first polyamic acid is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the diamines comprise 1 -100 mol% of a diamine having Formula I. In some embodiments of the first polyamic acid, the diamine having Formula I is 1 -5 mol% of the total diamine; in some embodiments, 6-10 mol%; in some embodiments, 10-25 mol%; in some embodiments 25-50 mol%; in some embodiments, 50-75 mol%; in some embodiments, 75-100 mol%; in some embodiments, 100 mol%.

In some embodiments of the first polyamic acid, there is a single tetracarboxylic acid component.

In some embodiments of the first polyamic acid, there are two tetracarboxylic acid components.

In some embodiments of the first polyamic acid, there are three tetracarboxylic acid components.

In some embodiments, the first polyamic acid is the reaction product of a single diamine having Formula I and a single tetracarboxylic acid component.

The first polyamic acid has repeat units of Formula II

where:

R ^a and R ^c are the same or different and represent a tetracarboxylic acid component residue;

R ^b represents a diamine residue; and

m is an integer from 1 -20.

All of the above-described embodiments for R ^a , R ^b , and m in Formula I, apply equally to R ^a , R ^b , and m in Formula II.

Any of the above-listed tetracarboxylic acid dianhydrides suitable to form residue R ^a in Formula I are also suitable to form residue R ^c in Formula II. In some embodiments of Formula II, R ^c represents a residue from a tetracarboxylic acid dianhydride selected from the group consisting of PMDA, BP DA, 6FDA, BTDA, and CBDA.

A second polyamic acid is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the tetracarboxylic acid components comprise 1-100 mol% of a tetracarboxylic acid dianhydride having Formula IV.

In some embodiments of the second polyamic acid, the dianhydride having Formula IV is 1 -5 mol% of the total dianhydride; in some

embodiments, 6-10 mol%; in some embodiments, 10-25 mol%; in some embodiments 25-50 mol%; in some embodiments, 50-75 mol%; in some embodiments, 75-100 mol%; in some embodiments, 100 mol%.

In some embodiments of the second polyamic acid, there is a single diamine component.

In some embodiments of the second polyamic acid, there are two diamine components.

In some embodiments of the second polyamic acid, there are three diamine components.

In some embodiments, the second polyamic acid is the reaction product of a single dianhydride having Formula IV and a single diamine component.

The second polyamic acid has repeat units of Formula V

where:

R ^d represents a tetracarboxylic acid component residue;

R ^e and R ^f are the same or different and represent a diamine

residue; and

m is an integer from 1 -20. All of the above-described embodiments for R ^d , R ^e , and m in Formula IV, apply equally to R ^d , R ^e , and m in Formula V.

Any of the above-listed diamines suitable to form residue R ^e in Formula IV are also suitable to form residue R ^f in Formula V.

In some embodiments of Formula V, R ^f represents the residue of an aromatic diamine selected from the group consisting of PPD, MPD, m- tolidine, o-tolidine, benzidine, and TFMB.

In some embodiments of the above polyamic acids, moieties resulting from monoanhydride monomers are present as end-capping groups.

In some embodiments, the monoanhydride monomers are selected from the group consisting of phthalic anhydrides and the like and derivatives thereof.

In some embodiments, the monoanhydrides are present at an amount up to 5 mol% of the total tetracarboxylic acid composition.

In some embodiments of the above polyamic acids, moieties resulting from monoamine monomers are present as end-capping groups.

In some embodiments, the monoamine monomers are selected from the group consisting of aniline and the like and derivatives thereof.

In some embodiments, the monoamines are present at an amount up to 5 mol% of the total amine composition.

In some embodiments, the polyamic acid has a weight average molecular weight (Mw) greater than 100,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight (Mw) greater than 150,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a molecular weight (Mw) greater than 200,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight (Mw) greater than 250,000 based on gel permeation chromatography with polystyrene standards. In some embodiments, the polyamic acid has a weight average molecular weight (Mw) greater than 300,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight (Mw) between 100,000 and 400,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight (Mw) between 150,000 and 350,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight (Mw) between 200,000 and 300,000 based on gel permeation chromatography with polystyrene standards.

Overall polyamic acid compositions can be designated via the notation commonly used in the art. For example, a polyamic acid having a tetracarboxylic acid component that is 100% ODPA, and a diamine component that is 90 mol% Bis-P and 10 mol% TFMB, would be represented as:

ODPA//Bis-P/22TFMB 100//90/10.

There is also provided a first liquid composition comprising (a) the polyamic acid having a repeat unit of Formula II, and (b) at least one high- boiling aprotic solvent. The first liquid composition is also referred to herein as the“first polyamic acid solution”.

There is also provided a second liquid composition comprising (a) the polyamic acid having a repeat unit of Formula V, and (b) at least one high-boiling aprotic solvent. The second liquid composition is also referred to herein as the“second polyamic acid solution”.

In some embodiments, the high-boiling aprotic solvent has a boiling point of 150°C or higher.

In some embodiments, the high-boiling aprotic solvent has a boiling point of 175°C or higher.

In some embodiments, the high-boiling aprotic solvent has a boiling point of 200°C or higher. In some embodiments, the high-boiling aprotic solvent is a polar solvent. In some embodiments, the solvent has a dielectric constant greater than 20.

Some examples of high-boiling aprotic solvents include, but are not limited to, N-methyl-2-pyrrolidone (NMP), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), N- butylpyrrolidinone (NBP), N,N-diethylacetamide (DEAc), tetramethylurea,

1 ,3-dimethyl-2-imidazolidinone, g-butyrolactone, dibutyl carbitol, butyl carbitol acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like, and combinations thereof.

In some embodiments of the liquid composition, the solvent is selected from the group consisting of NMP, DMAc, and DMF.

In some embodiments of the liquid composition, the solvent is NMP.

In some embodiments of the liquid composition, the solvent is

DMAc.

In some embodiments of the liquid composition, the solvent is DMF.

In some embodiments of the liquid composition, the solvent is NBP.

In some embodiments of the liquid composition, the solvent is

DEAc.

In some embodiments of the liquid composition, the solvent is tetramethylurea.

In some embodiments of the liquid composition, the solvent is 1 ,3- dimethyl-2-imidazolidinone.

In some embodiments of the liquid composition, the solvent is y-butyrolactone.

In some embodiments of the liquid composition, the solvent is dibutyl carbitol.

In some embodiments of the liquid composition, the solvent is butyl carbitol acetate.

In some embodiments of the liquid composition, the solvent is diethylene glycol monoethyl ether acetate.

In some embodiments of the liquid composition, the solvent is propylene glycol monoethyl ether acetate. In some embodiments, more than one of the high-boiling aprotic solvents identified above is used in the liquid composition.

In some embodiments, additional cosolvents are used in the liquid composition.

In some embodiments, the liquid composition is < 1 weight % polyamic acid in > 99 weight % high-boiling aprotic solvent(s). As used herein, the term“solvent(s)” refers to one or more solvents.

In some embodiments, the liquid composition is 1 - 5 weight % polyamic acid in 95 - 99 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 5 - 10 weight % polyamic acid in 90 - 95 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 10 - 15 weight % polyamic acid in 85 - 90 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 15 - 20 weight % polyamic acid in 80 - 85 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 20 - 25 weight % polyamic acid in 75 - 80 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 25 - 30 weight % polyamic acid in 70 - 75 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 30 - 35 weight % polyamic acid in 65 - 70 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 35 - 40 weight % polyamic acid in 60 - 65 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 40 - 45 weight % polyamic acid in 55 - 60 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 45 - 50 weight % polyamic acid in 50 - 55 weight % high-boiling aprotic solvent(s).

In some embodiments, the liquid composition is 50 weight % polyamic acid in 50 weight % high-boiling aprotic solvent(s).

The polyamic acid solutions can optionally further contain any one of a number of additives. Such additives can be: antioxidants, heat stabilizers, adhesion promoters, coupling agents (e.g. silanes), inorganic fillers or various reinforcing agents so long as they don’t adversely impact the desired polyimide properties. The polyamic acid solutions can be prepared using a variety of available methods with respect to the introduction of the components (i.e. , the monomers and solvents). Some methods of producing a polyamic acid solution include:

(a) a method wherein the diamine components and dianhydride components are preliminarily mixed together and then the mixture is added in portions to a solvent while stirring.

(b) a method wherein a solvent is added to a stirring mixture of diamine and dianhydride components (contrary to (a) above)

(c) a method wherein diamines are exclusively dissolved in a

solvent and then dianhydrides are added thereto at such a ratio as allowing to control the reaction rate.

(d) a method wherein the dianhydride components are exclusively dissolved in a solvent and then amine components are added thereto at such a ratio to allow control of the reaction rate.

(e) a method wherein the diamine components and the dianhydride components are separately dissolved in solvents and then these solutions are mixed in a reactor.

(f) a method wherein the polyamic acid with excessive amine

component and another polyamic acid with excessive dianhydride component are preliminarily formed and then reacted with each other in a reactor, particularly in such a way as to create a non-random or block copolymer.

(g) a method wherein a specific portion of the amine components and the dianhydride components are first reacted and then the residual diamine components are reacted, or vice versa.

(h) a method wherein the components are added in part or in whole in any order to either part or whole of the solvent, also where part or all of any component can be added as a solution in part or all of the solvent.

(i) a method of first reacting one of the dianhydride components with one of the diamine components giving a first polyamic acid. Then reacting the other dianhydride component with the other amine component to give a second polyamic acid. Then combining the polyamic acids in any one of a number of ways prior to film formation.

Generally speaking, a polyamic acid solution can be obtained from any one of the polyamic acid solution preparation methods disclosed above.

The polyamic acid solution can then be filtered one or more times in order to reduce the particle content. The polyimide film generated from such a filtered solution can show a reduced number of defects and thereby lead to superior performance in the electronics applications disclosed herein. An assessment of the filtration efficiency can be made by the laser particle counter test wherein a representative sample of the polyamic acid solution is cast onto a 5” silicon wafer. After soft baking / drying, the film is evaluated for particle content by any number of laser particle counting techniques on instruments that are commercially available and known in the art.

In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of less than 40 particles as measured by the laser particle counter test.

In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of less than 30 particles as measured by the laser particle counter test.

In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of less than 20 particles as measured by the laser particle counter test.

In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of less than 10 particles as measured by the laser particle counter test.

In some embodiments, the polyamic acid solution is prepared and filtered to yield particle content of between 2 particles and 8 particles as measured by the laser particle counter test.

In some embodiments, the polyamic acid solution is prepared and filtered to yield particle content of between 4 particles and 6 particles as measured by the laser particle counter test. Exemplary preparations of polyamic acid solutions are given in the examples.

6. The Polvimide

There is provided a first polyimide having a repeat unit structure of

Formula III

where:

R ^a and R ^c are the same or different and represent a tetracarboxylic acid component residue;

R ^b represents a diamine residue; and

m is an integer from 1 -20.

All of the above-described embodiments for R ^a , R ^b , R ^c , and m in Formula II, apply equally to R ^a , R ^b , R ^c , and m in Formula III.

There is provided a second polyimide having a repeat unit structure of Formula VI

where:

R ^d represents a tetracarboxylic acid component residue;

R ^e and R ^f are the same or different and represent a diamine

residue; and

m is an integer from 1 -20. All of the above-described embodiments for R ^d , R ^e , R ^f , and m in Formula IV, apply equally to R ^d , R ^e , R ^f , and m in Formula V.

There is also provided a polyimide film, wherein the polyimide has a repeat unit structure of Formula III or Formula VI, as described above.

Polyimide films can be made by coating a polyimide precursor onto a substrate and subsequently imidizing. This can be accomplished by a thermal conversion process or a chemical conversion process.

Further, if the polyimide is soluble in suitable coating solvents, it can be provided as an already-imidized polymer dissolved in the suitable coating solvent and coated as the polyimide.

In some embodiments of the polyimide film, the in-plane coefficient of thermal expansion (CTE) is less than 45 ppm/°C between 50 °C and 200 °C; in some embodiments, less than 30 ppm/°C; in some embodiments, less than 20 ppm/°C; in some embodiments, less than 15 ppm/°C; in some embodiments, between 0 ppm/°C and 15 ppm/°C.

In some embodiments of the polyimide film, the glass transition temperature (T _g ) is greater than 250 °C for a polyimide film cured at a temperature above 300 °C; in some embodiments, greater than 300 °C; in some embodiments, greater than 350 °C.

In some embodiments of the polyimide film, the 1 % TGA weight loss temperature is greater than 350 °C; in some embodiments, greater than 400 °C; in some embodiments, greater than 450 °C.

In some embodiments of the polyimide film, the tensile modulus is between 1.5 GPa and 8.0 GPa; in some embodiments, between 1.5 GPa and 5.0 GPa.

In some embodiments of the polyimide film, the elongation to break is greater than 10%.

In some embodiments of the polyimide film, the optical retardation is less than 2000 nm; in some embodiments, less than 1500 nm; in some embodiments, less than 1000 nm; in some embodiments, less than 500 nm.

In some embodiments of the polyimide film, the birefringence at 550 or 633 nm is less than 0.15; in some embodiments, less than 0.10; in some embodiments, less than 0.05; in some embodiments, less than 0.010; in some embodiments, less than 0.005.

In some embodiments of the polyimide film, the haze is less than 1.0%; in some embodiments less than 0.5%; in some embodiments, less than 0.1 %.

In some embodiments of the polyimide film, the b* is less than 10; in some embodiments, less than 7.5; in some embodiments, less than 5.0; in some embodiments, less than 3.0.

In some embodiments of the polyimide film, the Yl is less than 12; in some embodiments, less than 10; in some embodiments, less than 5.

In some embodiments of the polyimide film, the transmittance at 400 nm is greater than 40%; in some embodiments, greater than 50%; in some embodiments, greater than 60%.

In some embodiments of the polyimide film, the transmittance at 430 nm is greater than 60%; in some embodiments, greater than 70%.

In some embodiments of the polyimide film, the transmittance at 450 nm is greater than 70%; in some embodiments, greater than 80%.

In some embodiments of the polyimide film, the transmittance at 550 nm is greater than 70%; in some embodiments, greater than 80%.

In some embodiments of the polyimide film, the transmittance at 750 nm is greater than 70%; in some embodiments, greater than 80%; in some embodiments, greater than 90%.

Any of the above embodiments for the polyimide film can be combined with one or more of the other embodiments, so long as they are not mutually exclusive.

4. Methods for Preparing the Polyimide Films

Generally, polyimide films can be prepared from polyimide precursors by chemical or thermal conversion. In some embodiments, the films are prepared from the corresponding polyamic acid solutions by chemical or thermal conversion processes. The polyimide films disclosed herein, particularly when used as flexible replacements for glass in electronic devices, are prepared by thermal conversion processes. Generally, polyimide films can be prepared from the corresponding polyamic acid solutions by chemical or thermal conversion processes. The polyimide films disclosed herein, particularly when used as flexible replacements for glass in electronic devices, are prepared by thermal conversion or modified-thermal conversion processes, versus chemical conversion processes.

Chemical conversion processes are described in U.S. Pat. Nos. 5,166,308 and 5,298,331 which are incorporated by reference in their entirety. In such processes, conversion chemicals are added to the polyamic acid solutions. The conversion chemicals found to be useful in the present invention include, but are not limited to, (i) one or more dehydrating agents, such as, aliphatic acid anhydrides (acetic anhydride, etc.) and acid anhydrides; and (ii) one or more catalysts, such as, aliphatic tertiary amines (triethylamine, etc.), tertiary amines (dimethylaniline, etc.) and heterocyclic tertiary amines (pyridine, picoline, isoquinoilne, etc.). The anhydride dehydrating material is typically used in a slight molar excess of the amount of amide acid groups present in the polyamic acid solution.

The amount of acetic anhydride used is typically about 2.0-3.0 moles per equivalent of the polyamic acid. Generally, a comparable amount of tertiary amine catalyst is used.

Thermal conversion processes may or may not employ conversion chemicals (i.e. , catalysts) to convert a polyamic acid casting solution to a polyimide. If conversion chemicals are used, the process may be considered a modified-thermal conversion process. In both types of thermal conversion processes, only heat energy is used to heat the film to both dry the film of solvent and to perform the imidization reaction.

Thermal conversion processes with or without conversion catalysts are generally used to prepare the polyimide films disclosed herein.

Specific method parameters are pre-selected considering that it is not just the film composition that yields the properties of interest. Rather, the cure temperature and temperature-ramp profile also play important roles in the achievement of the most desirable properties for the intended uses disclosed herein. The polyamic acids should be imidized at a temperature at, or higher than, the highest temperature of any subsequent processing steps (e.g. deposition of inorganic or other layer(s) necessary to produce a functioning display), but at a temperature which is lower than the temperature at which significant thermal degradation / discoloration of the polyimide occurs. It should also be noted that an inert atmosphere is generally preferred, particularly when higher processing temperatures are employed for imidization.

For the polyamic acids/polyimides disclosed herein, temperatures of 300 °C to 400 °C are typically employed when subsequent processing temperatures in excess of 300 °C are required. Choosing the proper curing temperature allows a fully cured polyimide which achieves the best balance of thermal and mechanical properties. Because of this very high temperature, an inert atmosphere is required. Typically, oxygen levels in the oven of < 100 ppm should be employed. Very low oxygen levels enable the highest curing temperatures to be used without significant degradation / discoloration of the polymer. Catalysts that accelerate the imidization process are effective at achieving higher levels of imidization at cure temperatures between about 200 °C and 300 °C. This approach may be optionally employed if the flexible device is prepared with upper cure temperatures that are below the T _g of the polyimide.

The amount of time in each potential cure step is also an important process consideration. Generally, the time used for the highest- temperature curing should be kept to a minimum. For 320 °C cure, for example, cure time can be up to an hour or so under an inert atmosphere; but at higher cure temperatures, this time should be shortened to avoid thermal degradation. Generally speaking, higher temperature dictates shorter time. Those skilled in the art will recognize the balance between temperature and time in order to optimize the properties of the polyimide for a particular end use.

In some embodiments, the polyamic acid solution is converted into a polyimide film via a thermal conversion process.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 50 pm. In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 40 pm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 30 pm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 20 pm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is between 10pm and 20 pm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is between 15pm and 20 pm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is 18 pm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 10 pm.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft baked on a hot plate in proximity mode wherein nitrogen gas is used to hold the spin-coated matrix just above the hot plate.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft baked on a hot plate in full-contact mode wherein the spin-coated matrix is in direct contact with the hot plate surface.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft baked on a hot plate using a combination of proximity and full-contact modes.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked using a hot plate set at 80 °C. In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked using a hot plate set at 90 °C.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked using a hot plate set at 100 °C.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked using a hot plate set at 110 °C.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked using a hot plate set at 120 °C.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked using a hot plate set at 130 °C.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked using a hot plate set at 140 °C.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked for a total time of more than 10 minutes.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked for a total time of less than 10 minutes.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked for a total time of less than 8 minutes.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked for a total time of less than 6 minutes.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked for a total time of 4 minutes.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked for a total time of less than 4 minutes.

In some embodiments of the thermal conversion process, the spin- coated matrix is soft-baked for a total time of less than 2 minutes.

In some embodiments of the thermal conversion process, the soft- baked spin-coated matrix is subsequently cured at 2 pre-selected temperatures for 2 pre-selected time intervals, the latter of which may be the same or different.

In some embodiments of the thermal conversion process, the soft- baked spin-coated matrix is subsequently cured at 3 pre-selected temperatures for 3 pre-selected time intervals, each of which of the latter of which may be the same or different. In some embodiments of the thermal conversion process, the soft- baked spin-coated matrix is subsequently cured at 4 pre-selected temperatures for 4 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the thermal conversion process, the soft- baked spin-coated matrix is subsequently cured at 5 pre-selected temperatures for 5 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the thermal conversion process, the soft- baked spin-coated matrix is subsequently cured at 6 pre-selected temperatures for 6 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the thermal conversion process, the soft- baked spin-coated matrix is subsequently cured at 7 pre-selected temperatures for 7 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the thermal conversion process the soft- baked spin-coated matrix is subsequently cured at 8 pre-selected temperatures for 8 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the thermal conversion process, the soft- baked spin-coated matrix is subsequently cured at 9 pre-selected temperatures for 9 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the thermal conversion process, the soft- baked spin-coated matrix is subsequently cured at 10 pre-selected temperatures for 10 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 80 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is equal to 100 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 100 °C. In some embodiments of the thermal conversion process, the pre- selected temperature is equal to 150 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 150 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is equal to 200 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 200 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is equal to 250 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 250 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is equal to 300 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 300 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is equal to 350 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 350 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is equal to 400 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 400 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is equal to 450 °C.

In some embodiments of the thermal conversion process, the pre- selected temperature is greater than 450 °C.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 2 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 5 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 10 minutes. In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 15 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 20 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 25 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 30 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 35 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 40 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 45 minutes.

In some of the thermal conversion process, one or more of the pre- selected time intervals is 50 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 55 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is 60 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is greater than 60 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is between 2 minutes and 60 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is between 2 minutes and 90 minutes.

In some embodiments of the thermal conversion process, one or more of the pre-selected time intervals is between 2 minutes and 120 minutes.

In some embodiments of the thermal conversion process, the method for preparing a polyimide film comprises the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components in a high-boiling, aprotic solvent onto a matrix; soft-baking the spin-coated matrix; treating the soft-baked spin-coated matrix at a plurality of pre- selected temperatures for a plurality of pre-selected time intervals whereby the polyimide film exhibits properties that are satisfactory for use in electronics applications like those disclosed herein.

In some embodiments of the thermal conversion process, the method for preparing a polyimide film consists of the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components in a high-boiling, aprotic solvent onto a matrix; soft-baking the spin-coated matrix; treating the soft-baked spin-coated matrix at a plurality of pre- selected temperatures for a plurality of pre-selected time intervals whereby the polyimide film exhibits properties that are satisfactory for use in electronics applications like those disclosed herein.

In some embodiments of the thermal conversion process, the method for preparing a polyimide film consists essentially of the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine

components in a high-boiling, aprotic solvent onto a matrix; soft-baking the spin-coated matrix; treating the soft-baked spin-coated matrix at a plurality of pre-selected temperatures for a plurality of pre-selected time intervals whereby the polyimide film exhibits properties that are satisfactory for use in electronics applications like those disclosed herein.

Typically, the polyamic acid solutions / polyimides disclosed herein are coated / cured onto a supporting glass substrate to facilitate the processing through the rest of the display making process. At some point in the process as determined by the display maker, the polyimide coating is removed from the supporting glass substrate by a mechanical or laser lift off process. These processes separate the polyimide as a film with the deposited display layers from the glass and enable a flexible format.

Often, this polyimide film with deposition layers is then bonded to a thicker, but still flexible, plastic film to provide support for subsequent fabrication of the display. There are also provided modified-thermal conversion processes wherein conversion catalysts generally cause imidization reactions to run at lower temperatures than would be possible in the absence of such conversion catalysts.

In some embodiments, the polyamic acid solution is converted into a polyimide film via a modified-thermal conversion process.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains conversion catalysts.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains conversion catalysts selected from the group consisting of tertiary amines.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains conversion catalysts selected from the group consisting of tributylamine, dimethylethanolamine, isoquinoline, 1 ,2-dimethylimidazole, N-methylimidazole, 2- methylimidazole, 2-ethyl-4-imidazole, 3,5-dimethylpyridine, 3,4- dimethylpyridine, 2,5-dimethylpyridine, 5-methylbenzimidazole, and the like.

In some embodiments of the modified-thermal conversion process, the conversion catalyst is present at 5 weight percent or less of the polyamic acid solution.

In some embodiments of the modified-thermal conversion process, the conversion catalyst is present at 3 weight percent or less of the polyamic acid solution.

In some embodiments of the modified-thermal conversion process, the conversion catalyst is present at 1 weight percent or less of the polyamic acid solution.

In some embodiments of the modified-thermal conversion process, the conversion catalyst is present at 1 weight percent of the polyamic acid solution.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains tributylamine as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains dimethylethanolamine as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains isoquinoline as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains 1 ,2-dimethylimidazole as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains 3,5-dimethylpyridine as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains 5-methylbenzimidazole as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains N-methylimidazole as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains 2-methylimidazole as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains 2-ethyl-4-imidazole as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains 3,4-dimethylpyridine as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution further contains 2,5-dimethylpyridine as a conversion catalyst.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 50 pm. In some embodiments of the modified-thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 40 pm.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 30 pm.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 20 pm.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is between 10pm and 20 pm.

In some embodiments of the modified- thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is between 15pm and 20 pm.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is 18 pm.

In some embodiments of the modified-thermal conversion process, the polyamic acid solution is spin-coated onto the matrix such that the soft- baked thickness of the resulting film is less than 10 pm.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft baked on a hot plate in proximity mode wherein nitrogen gas is used to hold the spin-coated matrix just above the hot plate.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft baked on a hot plate in full-contact mode wherein the spin-coated matrix is in direct contact with the hot plate surface.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft baked on a hot plate using a combination of proximity and full-contact modes.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked using a hot plate set at 80 °C. In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked using a hot plate set at 90 °C.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked using a hot plate set at 100 °C.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked using a hot plate set at 110 °C.

In some embodiments of the modified- thermal conversion process, the spin-coated matrix is soft-baked using a hot plate set at 120 °C.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked using a hot plate set at 130 °C.

In some embodiments of the modified- thermal conversion process, the spin-coated matrix is soft-baked using a hot plate set at 140 °C.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked for a total time of more than 10 minutes.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked for a total time of less than 10 minutes.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked for a total time of less than 8 minutes.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked for a total time of less than 6 minutes.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked for a total time of 4 minutes.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked for a total time of less than 4 minutes.

In some embodiments of the modified-thermal conversion process, the spin-coated matrix is soft-baked for a total time of less than 2 minutes.

In some embodiments of the modified-thermal conversion process, the soft-baked spin-coated matrix is subsequently cured at 2 pre-selected temperatures for 2 pre-selected time intervals, the latter of which may be the same or different.

In some embodiments of the modified-thermal conversion process, the soft-baked spin-coated matrix is subsequently cured at 3 pre-selected temperatures for 3 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the modified-thermal conversion process, the soft-baked spin-coated matrix is subsequently cured at 4 pre-selected temperatures for 4 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the modified- thermal conversion process, the soft-baked spin-coated matrix is subsequently cured at 5 pre-selected temperatures for 5 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the modified-thermal conversion process, the soft-baked spin-coated matrix is subsequently cured at 6 pre-selected temperatures for 6 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the modified-thermal conversion process, the soft-baked spin-coated matrix is subsequently cured at 7 pre-selected temperatures for 7 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the modified-thermal conversion process the soft-baked spin-coated matrix is subsequently cured at 8 pre-selected temperatures for 8 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the modified-thermal conversion process, the soft-baked spin-coated matrix is subsequently cured at 9 pre-selected temperatures for 9 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the modified-thermal conversion process, the soft-baked spin-coated matrix is subsequently cured at 10 pre-selected temperatures for 10 pre-selected time intervals, each of which of the latter of which may be the same or different.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 80 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 100 °C. In some embodiments of the modified- thermal conversion process, the pre-selected temperature is greater than 100 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 150 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 150 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 200 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 200 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 220 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 220 °C.

In some embodiments of the modified- thermal conversion process, the pre-selected temperature is equal to 230 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 230 °C.

In some embodiments of the modified- thermal conversion process, the pre-selected temperature is equal to 240 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 240 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 250 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 250 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 260 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 260 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 270 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 270 °C. In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 280 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 280 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 290 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is greater than 290 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is equal to 300 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is less than 300 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is less than 290 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is less than 280 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is less than 270 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is less than 260 °C.

In some embodiments of the modified-thermal conversion process, the pre-selected temperature is less than 250 °C.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 2 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 5 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 10 minutes.

In some embodiments of the modified-conversion process, one or more of the pre-selected time intervals is 15 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 20 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 25 minutes. In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 30 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 35 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 40 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 45 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 50 minutes.

In some embodiments of the modified- thermal conversion process, one or more of the pre-selected time intervals is 55 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is 60 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is greater than 60 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is between 2 minutes and 60 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is between 2 minutes and 90 minutes.

In some embodiments of the modified-thermal conversion process, one or more of the pre-selected time intervals is between 2 minutes and 120 minutes.

In some embodiments of the modified-thermal conversion process, the method for preparing a polyimide film comprises the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components and a conversion chemical in a high-boiling, aprotic solvent onto a matrix; soft-baking the spin-coated matrix; treating the soft-baked spin-coated matrix at a plurality of pre-selected temperatures for a plurality of pre- selected time intervals whereby the polyimide film exhibits properties that are satisfactory for use in electronics applications like those disclosed herein.

In some embodiments of the modified-thermal conversion process, the method for preparing a polyimide film consists of the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components and a conversion chemical in a high-boiling, aprotic solvent onto a matrix; soft-baking the spin-coated matrix; treating the soft-baked spin-coated matrix at a plurality of pre-selected temperatures for a plurality of pre- selected time intervals whereby the polyimide film exhibits properties that are satisfactory for use in electronics applications like those disclosed herein.

In some embodiments of the modified-thermal conversion process, the method for preparing a polyimide film consists essentially of the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components and a conversion chemical in a high-boiling, aprotic solvent onto a matrix; soft-baking the spin-coated matrix; treating the soft-baked spin-coated matrix at a plurality of pre-selected temperatures for a plurality of pre-selected time intervals whereby the polyimide film exhibits properties that are satisfactory for use in electronics applications like those disclosed herein.

5. The Electronic Device

The polyimide films disclosed herein can be suitable for use in a number of layers in electronic display devices such as OLED and LCD Displays. Nonlimiting examples of such layers include device substrates, touch panels, substrates for color filter sheets, cover films, and others. The particular materials’ properties requirements for each application are unique and may be addressed by appropriate composition(s) and processing condition(s) for the polyimide films disclosed herein.

In some embodiments, the flexible replacement for glass in an electronic device is a polyimide film having the repeat unit of Formula III, as described in detail above. Organic electronic devices that may benefit from having one or more layers including at least one compound as described herein include, but are not limited to, (1 ) devices that convert electrical energy into radiation (e.g., a light-emitting diode, light emitting diode display, lighting device, luminaire, or diode laser), (2) devices that detect signals through electronics processes (e.g., photodetectors, photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, IR detectors, biosensors), (3) devices that convert radiation into electrical energy, (e.g., a photovoltaic device or solar cell), (4) devices that convert light of one wavelength to light of a longer wavelength, (e.g., a down-converting phosphor device); and (5) devices that include one or more electronic components that include one or more organic semi-conductor layers (e.g., a transistor or diode). Other uses for the compositions according to the present invention include coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as a rechargeable battery, and electromagnetic shielding applications.

One illustration of a polyimide film that can act as a flexible replacement for glass as described herein is shown in FIG. 1. The flexible film 100 can have the properties as described in the embodiments of this disclosure. In some embodiments, the polyimide film that can act as a flexible replacement for glass is included in an electronic device. FIG. 2 illustrates the case when the electronic device 200 is an organic electronic device. The device 200 has a substrate 100, an anode layer 110 and a second electrical contact layer, a cathode layer 130, and a photoactive layer 120 between them. Additional layers may optionally be present. Adjacent to the anode may be a hole injection layer (not shown), sometimes referred to as a buffer layer. Adjacent to the hole injection layer may be a hole transport layer (not shown), including hole transport material. Adjacent to the cathode may be an electron transport layer (not shown), including an electron transport material. As an option, devices may use one or more additional hole injection or hole transport layers (not shown) next to the anode 110 and/or one or more additional electron injection or electron transport layers (not shown) next to the cathode 130. Layers between 110 and 130 are individually and collectively referred to as the organic active layers. Additional layers that may or may not be present include color filters, touch panels, and / or cover sheets. One or more of these layers, in addition to the substrate 100, may also be made from the polyimide films disclosed herein.

The different layers will be discussed further herein with reference to FIG. 2. However, the discussion applies to other configurations as well.

In some embodiments, the different layers have the following range of thicknesses: substrate 100, 5-100 microns, anode 110, 500-5000 A, in some embodiments, 1000-2000 A; hole injection layer (not shown), 50- 2000 A, in some embodiments, 200-1000 A; hole transport layer (not shown), 50-3000 A, in some embodiments, 200-2000 A; photoactive layer 120, 10-2000 A, in some embodiments, 100-1000 A; electron transport layer (not shown), 50-2000 A, in some embodiments, 100-1000 A; cathode 130, 200-10000 A, in some embodiments, 300-5000 A. The desired ratio of layer thicknesses will depend on the exact nature of the materials used.

In some embodiments, the organic electronic device (OLED) contains a flexible replacement for glass as disclosed herein.

In some embodiments, an organic electronic device includes a substrate, an anode, a cathode, and a photoactive layer therebetween, and further includes one or more additional organic active layers. In some embodiments, the additional organic active layer is a hole transport layer.

In some embodiments, the additional organic active layer is an electron transport layer. In some embodiments, the additional organic layers are both hole transport and electron transport layers.

The anode 110 is an electrode that is particularly efficient for injecting positive charge carriers. It can be made of, for example materials containing a metal, mixed metal, alloy, metal oxide or mixed-metal oxide, or it can be a conducting polymer, and mixtures thereof. Suitable metals include the Group 11 metals, the metals in Groups 4, 5, and 6, and the Group 8-10 transition metals. If the anode is to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin- oxide, are generally used. The anode may also include an organic material such as polyaniline as described in“Flexible light-emitting diodes made from soluble conducting polymer,” Nature vol. 357, pp 477 479 (11 June 1992). At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.

Optional hole injection layers can include hole injection materials. The term“hole injection layer” or“hole injection material” is intended to mean electrically conductive or semiconductive materials and may have one or more functions in an organic electronic device, including but not limited to, planarization of the underlying layer, charge transport and/or charge injection properties, scavenging of impurities such as oxygen or metal ions, and other aspects to facilitate or to improve the performance of the organic electronic device. Hole injection materials may be polymers, oligomers, or small molecules, and may be in the form of solutions, dispersions, suspensions, emulsions, colloidal mixtures, or other compositions.

The hole injection layer can be formed with polymeric materials, such as polyaniline (PANI) or polyethylenedioxythiophene (PEDOT), which are often doped with protonic acids. The protonic acids can be, for example, poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1 - propanesulfonic acid), and the like. The hole injection layer 120 can include charge transfer compounds, and the like, such as copper phthalocyanine and the tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In some embodiments, the hole injection layer 120 is made from a dispersion of a conducting polymer and a colloid-forming polymeric acid. Such materials have been described in, for example, published U.S. patent applications 2004-0102577, 2004-0127637, and 2005-0205860.

Other layers can include hole transport materials. Examples of hole transport materials for the hole transport layer have been summarized for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transporting small molecules and polymers can be used. Commonly used hole transporting molecules include, but are not limited to: 4,4’,4”-tris(N,N- diphenyl-amino)-triphenylamine (TDATA); 4,4’,4”-tris(N-3-methylphenyl-N- phenyl-amino)-triphenylamine (MTDATA); N,N'-diphenyl-N,N'-bis(3- methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine (TPD); 4, 4’-bis(carbazol-9- yl)biphenyl (CBP); 1 ,3-bis(carbazol-9-yl)benzene (mCP); 1 ,1 -bis[(di-4- tolylamino) phenyl]cyclohexane (TAPC); N,N'-bis(4-methylphenyl)-N,N'- bis(4-ethylphenyl)-[1 ,1 '-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD); tetrakis-(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA); a- phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis[4-(N,N- diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP);

1 -phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl ] pyrazoline (PPR or DEASP); 1 ,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N'-tetrakis(4-methylphenyl)-(1 ,T-biphenyl)-4,4'-diamine (TTB); N,N’-bis(naphthalen-1 -yl)-N,N’-bis-(phenyl)benzidine (a-NPB); and porphyrinic compounds, such as copper phthalocyanine. Commonly used hole transporting polymers include, but are not limited to,

polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophenes), polyanilines, and polypyrroles. It is also possible to obtain hole

transporting polymers by doping hole transporting molecules such as those mentioned above into polymers such as polystyrene and

polycarbonate. In some cases, triarylamine polymers are used, especially triarylamine-fluorene copolymers. In some cases, the polymers and copolymers are crosslinkable. Examples of crosslinkable hole transport polymers can be found in, for example, published US patent application 2005-0184287 and published PCT application WO 2005/052027. In some embodiments, the hole transport layer is doped with a p-dopant, such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10- tetracarboxylic-3,4,9, 10-dianhydride.

Depending upon the application of the device, the photoactive layer 120 can be a light-emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), a layer of material that absorbs light and emits light having a longer wavelength (such as in a down-converting phosphor device), or a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector or photovoltaic device). In some embodiments, the photoactive layer includes a compound comprising an emissive compound having as a photoactive material. In some embodiments, the photoactive layer further comprises a host material. Examples of host materials include, but are not limited to, chrysenes, phenanthrenes, triphenylenes, phenanthrolines, naphthalenes, anthracenes, quinolines, isoquinolines, quinoxalines, phenylpyridines, carbazoles, indolocarbazoles, furans, benzofurans, dibenzofurans, benzodifurans, and metal quinolinate complexes. In some embodiments, the host materials are deuterated.

In some embodiments, the photoactive layer comprises (a) a dopant capable of electroluminescence having an emission maximum between 380 and 750 nm, (b) a first host compound, and (c) a second host compound. Suitable second host compounds are described above.

In some embodiments, the photoactive layer includes only (a) a dopant capable of electroluminescence having an emission maximum between 380 and 750 nm, (b) a first host compound, and (c) a second host compound, where additional materials that would materially alter the principle of operation or the distinguishing characteristics of the layer are not present.

In some embodiments, the first host is present in higher

concentration than the second host, based on weight in the photoactive layer.

In some embodiments, the weight ratio of first host to second host in the photoactive layer is in the range of 10:1 to 1 :10. In some

embodiments, the weight ratio is in the range of 6:1 to 1 :6; in some embodiments, 5:1 to 1 :2; in some embodiments, 3:1 to 1 :1.

In some embodiments, the weight ratio of dopant to the total host is in the range of 1 :99 to 20:80; in some embodiments, 5:95 to 15:85.

In some embodiments, the photoactive layer comprises (a) a red light-emitting dopant, (b) a first host compound, and (c) a second host compound.

In some embodiments, the photoactive layer comprises (a) a green light-emitting dopant, (b) a first host compound, and (c) a second host compound. In some embodiments, the photoactive layer comprises (a) a yellow light-emitting dopant, (b) a first host compound, and (c) a second host compound.

Optional layers can function both to facilitate electron transport, and also serve as a confinement layer to prevent quenching of the exciton at layer interfaces. Preferably, this layer promotes electron mobility and reduces exciton quenching.

In some embodiments, such layers include other electron transport materials. Examples of electron transport materials which can be used in the optional electron transport layer, include metal chelated oxinoid compounds, including metal quinolate derivatives such as tris(8- hydroxyquinolato)aluminum (AIQ), bis(2-methyl-8-quinolinolato)(p- phenylphenolato) aluminum (BAIq), tetrakis-(8-hydroxyquinolato)hafnium (HfQ) and tetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds such as 2- (4-biphenylyl)-5-(4-t-butylphenyl)-1 ,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1 ,2,4-triazole (TAZ), and 1 ,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthrolines such as 4,7-diphenyl-1 ,10-phenanthroline (DPA) and 2,9-dimethyl-4,7- diphenyl-1 ,10-phenanthroline (DDPA); triazines; fullerenes; and mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinolates and phenanthroline derivatives. In some embodiments, the electron transport layer further includes an n-dopant. N-dopant materials are well known. The n-dopants include, but are not limited to, Group 1 and 2 metals; Group 1 and 2 metal salts, such as LiF, CsF, and CS2CO3; Group 1 and 2 metal organic compounds, such as Li quinolate; and molecular n-dopants, such as leuco dyes, metal complexes, such as W2(hpp) ₄ where hpp=1 ,3,4,6,7,8- hexahydro-2FI-pyrimido-[1 ,2-a]-pyrimidine and cobaltocene,

tetrathianaphthacene, bis(ethylenedithio)tetrathiafulvalene, heterocyclic radicals or diradicals, and the dimers, oligomers, polymers, dispiro compounds and polycycles of heterocyclic radical or diradicals.

An optional electron injection layer may be deposited over the electron transport layer. Examples of electron injection materials include, but are not limited to, Li-containing organometallic compounds, LiF, U2O,

Li quinolate, Cs-containing organometallic compounds, CsF, CS2O, and CS2CO3. This layer may react with the underlying electron transport layer, the overlying cathode, or both. When an electron injection layer is present, the amount of material deposited is generally in the range of 1 - 100 A, in some embodiments 1 -10 A.

The cathode 130 is an electrode that is particularly efficient for injecting electrons or negative charge carriers. The cathode can be any metal or nonmetal having a lower work function than the anode. Materials for the cathode can be selected from alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, including the rare earth elements and lanthanides, and the actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations, can be used.

It is known to have other layers in organic electronic devices. For example, there can be layers (not shown) between the anode 110 and hole injection layer (not shown) to control the amount of positive charge injected and/or to provide band-gap matching of the layers, or to function as a protective layer. Layers that are known in the art can be used, such as copper phthalocyanine, silicon oxy-nitride, fluorocarbons, silanes, or an ultra-thin layer of a metal, such as Pt. Alternatively, some or all of anode layer 110, active layer 120, or cathode layer 130, can be surface-treated to increase charge carrier transport efficiency. The choice of materials for each of the component layers is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescence efficiency.

It is understood that each functional layer can be made up of more than one layer.

The device layers can generally be formed by any deposition technique, or combinations of techniques, including vapor deposition, liquid deposition, and thermal transfer. Substrates such as glass, plastics, and metals can be used. Conventional vapor deposition techniques can be used, such as thermal evaporation, chemical vapor deposition, and the like. The organic layers can be applied from solutions or dispersions in suitable solvents, using conventional coating or printing techniques, including but not limited to spin-coating, dip-coating, roll-to-roll techniques, ink-jet printing, continuous nozzle printing, screen-printing, gravure printing and the like.

For liquid deposition methods, a suitable solvent for a particular compound or related class of compounds can be readily determined by one skilled in the art. For some applications, it is desirable that the compounds be dissolved in non-aqueous solvents. Such non-aqueous solvents can be relatively polar, such as Ci to C20 alcohols, ethers, and acid esters, or can be relatively non-polar such as C1 to C12 alkanes or aromatics such as toluene, xylenes, trifluorotoluene and the like. Other suitable liquids for use in making the liquid composition, either as a solution or dispersion as described herein, including the new compounds, includes, but not limited to, chlorinated hydrocarbons (such as methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (such as substituted and non-substituted toluenes and xylenes), including triflurotoluene), polar solvents (such as tetrahydrofuran (THP), N-methyl pyrrolidone) esters (such as ethylacetate) alcohols (isopropanol), ketones (cyclopentatone) and mixtures thereof. Suitable solvents for

electroluminescent materials have been described in, for example, published PCT application WO 2007/145979.

In some embodiments, the device is fabricated by liquid deposition of the hole injection layer, the hole transport layer, and the photoactive layer, and by vapor deposition of the anode, the electron transport layer, an electron injection layer and the cathode onto the flexible substrate.

It is understood that the efficiency of devices can be improved by optimizing the other layers in the device. For example, more efficient cathodes such as Ca, Ba or LiF can be used. Shaped substrates and novel hole transport materials that result in a reduction in operating voltage or increase quantum efficiency are also applicable. Additional layers can also be added to tailor the energy levels of the various layers and facilitate electroluminescence.

In some embodiments, the device has the following structure, in order: substrate, anode, hole injection layer, hole transport layer, photoactive layer, electron transport layer, electron injection layer, cathode.

Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.

EXAMPLES

The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.

In the examples, Mw is the weight-average molecular weight; Mn is the number-average molecular weight; Mz is the Z-average molecular weight; and Mp is the peak molecular weight.

Abbreviations

APB-133 - 1 ,3'-bis(3-amino-phenoxy)benzene

BPDA = 3,3',4,4'-biphenyl tetracarboxylic dianhydride

4,4’-DDS = 4,4'-diaminodiphenyl sulfone

6FDA = 4,4'-hexafluoroiso-propylidenebisphthalic dianhydride

ODRA = 4,4'-oxydiphthalic anhydride

PMDA = pyromellitic dianhydride

TFMB = 2,2'-bis(trifluoromethyl) benzidine

XFDA = 1 H-Difuro[3,4-b:3',4'-i]xanthene-1 ,3, 7, 9(1 1 H)-tetrone, 1 1 -methyl- 1 1 -(trifluoromethyl)- Synthesis Examples

These examples illustrate the preparation of compounds having Formula I.

Synthesis Example 1

2,6-bis(2,2'-Bis(trifluoromethyl)-4'-amino-1 , 1 '-biphenyl-4-yl)-hexahvdro- benzoM .2-c:4.5-c'ldipyrrole-1.3.5.7(2H.6H)-tetrone (2).

A mixture of 2,2'-bis(trifluoromethyl)benzidine (171.4 g, 535.3 mmole, 4 equivalents), 1 ,2,4, 5-cyclohexanetetracarboxylic dianhydride (5 g), pyridine (50 ml) and N-methylpyrrolidinone (200 ml) was heated at 130°C under nitrogen atmosphere for 1 hour. After that remaining amount of 1 ,2, 4, 5-cyclohexanetetracarboxylic dianhydride was added in 5g portions (30 g totally, 133.8 mmole totally) over 5 hours period at 130°C. After that the mixture was heated at 150°C for 2 days and at 180°C for 1 day. The mixture was cooled down to ambient temperature, solvents distilled off using rotary evaporator, the residue extracted several times with hot mixture of 10% ethyl acetate and heptane to recover excess of 2,2'-bis(trifluoromethyl)benzidine. The residue was absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of ethyl acetate and hexanes. Fractions containing diimide- diamine combined, eluent evaporated, the residue dissolved in mixture of ethyl acetate and hexanes 1 :1 , crystallized product combined by filtration, dried in vacuum to give 40.2 g of compound 2. Compound 2 can also be obtained by direct crystallization from crude reaction mixture. In this manner, a mixture of 2,2'-bis(trifluoromethyl)benzidine (171.4 g, 535.3 mmole, 4 equivalents), 1 ,2, 4, 5-cyclohexanetetracarboxylic dianhydride (5 g), pyridine (50 ml) and N-methylpyrrolidinone (200 ml) was heated at 130°C under nitrogen atmosphere for 1 hour. After that additional amount of 1 ,2, 4, 5-cyclohexanetetracarboxylic dianhydride was added in 5g portions over 5 hours period at 130°C (30 g totally). After that the mixture was heated at 150°C for 16 hours. The mixture was cooled down to ambient temperature, solvents distilled off using rotary evaporator, the residue dissolved in 1 L of 1 : 1 ethyl acetate and hexanes and allowed to stand at ambient temperature collecting precipitated product periodically to give 33.36 g of the product. The product can be additionally recrystallized from propyl acetate. ¹ H-NMR (DMSO-de, 500 MHz): 2.02-2.09 (m, 2H), 2.29-2.34 (m, 2H), 3.25-3.30 (m, 4H), 5.71 (s, 4H), 6.77 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.94-6.96 (m, 4H), 7.39-7.41 (m, 2H), 7.52 (2, 2H, J = 9 Hz), 7.68-7.70 (m, 2H). ¹³ C-NMR (DMSO-de, 125 MHz): 178.4, 149.5, 138.4, 133.6, 132.6, 132.1 , 130.1 , 128.3, 122.8, 122.2, 1 16.1 , 1 10.7, 38.4, 22.3. ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.4, 57.1 . Matrix Assisted Laser Desorption/Ionization time-of-flight mass spectrometry (“MALDI TOF MS”): 829.1671 (MH+).

Synthesis Example 2

2, 6-bis(2,2'-Bis(trifluoromethyl)-4' -amino-1 , 1 '-biphenyl-4-yl)-hexahvdro-4,8- ethanobenzoM ,2-c:4,5-c'1dipyrrole-1 ,3,5,7(2H,6H)-tetrone (4).

Method A:

To a stirred solution of 2,2'-bis(trifluoromethyl)benzidine (76.86 g, 240 mmole, 4 equivalents) in pyridine (30 ml) and N-methylpyrrolidinone (150 ml) was added portionwise a suspension of bicyclo[2.2.2]octane- 2,3:5,6-tetracarboxylic dianhydride (“bicyclooctanetetracarboxylic dianhydride”) (15 g , 60 mmole) in 50 ml under nitrogen atmosphere.

Resulting mixture heated at 180°C for 2 days. The mixture was cooled down to ambient temperature, solvents distilled off using rotary

evaporator, the residue extracted several times with hot mixture of 10% ethyl acetate and heptane to recover excess of 2,2'- bis(trifluoromethyl)benzidine. The residue was absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of ethyl acetate and hexanes. Fractions containing diimide- diamine combined, eluent evaporated, dried in vacuum to give 21 .23 g of compound 4.

Method B:

A mixture of 2,2'-bis(trifluoromethyl)benzidine (51 .2 g, 4

equivalents) and bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride (10 g , 39.97 mmole) was heated at 220C under intert atmosphere for 2 hours. The mixture was cooled down to ambient temperature, dissolved in ethyl acetate, absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of propyl acetate and hexanes. Fractions containing diimide-diamine combined, eluent evaporated, dried in vacuum to give 21 .82 g of compound 4.

¹ H-NMR (DMSO-de, 500 MHz): 1 .53 (s, 4H), 2.61 (s, 2H), 3.40 (s, 4H), 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 2 Hz, J2 = 8 Hz), 6.97 (s, 2H), 6.98 (d, 2H, J = 7 Hz), 7.46 (d, 2H, J = 8 Hz), 7.67 (dd, 2H, J1 = 2 Hz, J2 = 8 Hz), 7.80 (d, 2H, J = 2 Hz). ¹³ C-NMR (DMSO-de, 125 MHz): 177.9, 149.6, 138.6, 133.8, 132.6, 132.2, 130.3, 129.0, 128.8, 128.2, 128.0, 125.7, 125.0, 124.7, 123.5, 122.9, 122.2, 1 16.2, 1 10.7, 43.1 , 28.8, 17.6. ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.3, 57.0. MALDI TOF MS: 855.1810 (MH+).

Synthesis Example 3

2, 6-bis(2,2'-Bis(trifluoromethyl)-4' -amino-1 , 1 '-biphenyl-4-yl)-hexahvdro-4,8- ethenobenzoM ,2-c:4,5-c'1dipyrrole-1 ,3,5,7(2H,6H)-tetrone (5).

To a stirred solution of 2,2'-bis(trifluoromethyl)benzidine (77.43 g, 241.8 mmole, 4 equivalents) in pyridine (30 ml) and N-methylpyrrolidinone (150 ml) was added portionwise a suspension of bicyclooctenetetracarboxylic dianhydride (15 g, 60.45 mmole) in 50 ml N- methylpyrrolidinone under nitrogen atmosphere. Resulting mixture heated at 180°C for 7 days. The mixture was cooled down to ambient

temperature, solvents distilled off using rotary evaporator, the residue extracted several times with hot mixture of 10% ethyl acetate and heptane to recover excess of 2,2'-bis(trifluoromethyl)benzidine. The residue was absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of ethyl acetate and hexanes. Fractions containing diimide-diamine combined, eluent evaporated, dried in vacuum to give 21.23 g of compound 5. ¹ H-NMR (DMSO-de, 500 MHz): 3.49 (s, 4H), 3.57 (br. S, 2H), 5.72 (s, 4H), 6.37 (t, 2H, J = 4 Hz), 6.78 (dd, 2H, J1 = 8Hz, J2 = 2 Hz), 6.95-6.97 (m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.47 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.61 (d, 2H, J = 2 Hz). ¹³ C-NMR (DMSO-de, 125 MHz): 176.9, 149.6, 138.5, 133.5, 133.9, 132.6, 132.0, 131.6, 129.9, 129.0, 128.7, 128.2, 128.0, 125.7, 125.0, 124.2, 123.5, 122.8, 122.1 ,

116.2, 110.6, 43.0, 34.5. ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.4, 57.1.

MALDI TOF MS: 853.1654 (MH+).

Synthesis Example 4

2.2'-(6-Bis(2.2'-bis(trifluoromethyl)-4'-amino-1.T-biohenyl- 4.4’-diyl)bis[6- bis(2,2'-bis(trifluoromethyl)-4'-amino-1 , 1 '-biphenyl-4-yl)-hexahvdro-4,8- ethenobenzoM ,2-c:4,5-c'1dipyrrole-1 ,3,5,7(2H,6H)-tetrone1 (7).

A mixture of 2,2'-bis(trifluoromethyl)benzidine (77.43 g, 241.8 mmole, 2 equivalents), pyridine (20 ml), N-methylpyrrolidinone (100 ml) and bicyclooctenetetracarboxylic dianhydride (15 g, 60.45 mmole) was stirred with heating at 180°C under nitrogen atmosphere for 6 days. The mixture was cooled down to ambient temperature, solvents distilled off using rotary evaporator, the residue absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of ethyl acetate and hexanes. Fractions containing diimide-diamine combined, eluent evaporated, dried in vacuum to give 14.8 g of compound 5.

Fractions containing tetraimide-diamine combined, eluent evaporated, dried in vacuum to give 8.75 g of compound 7. Compound 7: ¹ H-NMR (DMSO-de, 500 MHz): 3.50 (s, 4H), 3.51 (s, 4H), 3.58 (br. S, 4H), 5.72 (s, 4H), 6.38 (t, 4H, J = 4 Hz), 6.78 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.95-6.97

(m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.47 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.56- 7.61 (m, 6H), 7.72 (s, 2H). ¹³ C-NMR (DMSO-de, 125 MHz): 176.92, 176.86, 149.6, 138.6, 136.1 , 133.9, 133.0, 132.9, 132.6, 132.0, 131 .7, 130.2, 129.9, 128.2, 128.0, 125.7, 1245.0, 124.8, 124.5, 124.4, 124.2, 123.5, 122.8, 122.6, 122.1 , 1 16.2, 1 10.67, 1 10.62, 48.9, 43.00, 42.96,

34.5. ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.4, 57.2, 57.1 . MALDI TOF MS: 1385.2532 (MH+).

Synthesis Example 5

3a,3b,4,4a,7a,8,8a,8b-Octahvdro-9-(1 ,1 -dimethylethyl)-4,8- ethenofuro[3',4':3,41cvclobut[1 ,2-f1isobenzofuran-1 ,3,5,7-tetrone.

Maleic anhydride (37.4 g, 0.38 mole) and acetophenone (22.9 g, 0.191 mole) dissolved in tert-butylbenzene (approx. 0.8 L), placed into 1 L photochemical reactor, irradiated with 200W medium pressure Hanovia mercury lamp using borosilicate glass immersion well. Precipitate collected by filtration. Yield of crude product after irradiation for 42 hours - 33.3 g. The product can be recrystallized from hot acetone. ¹ H-NMR (acetone-de, 500 MHz): 1 .14 (s, 9H), 2.99-3.09 (m, 4H), 3.31 (dd, 1 H, J1 = 9 Hz, J2 = 3 Hz), 3.41 (dd, 1 H, J1 = 9 Hz, J2 = 3 Hz), 3.45-3.48 (m, 1 H), 3.71 -3.72 (m, 1 H), 6.29 (dd, 1 H, J1 = 7 Hz, J2 = 2 Hz).

In control experiments tert-butyltricyclotetradecenetetracarboxylic dianhydride was found to be unreactive with BPDA even at elevated temperature.

2,6-bis(2,2'-Bis(trifluoromethyl)-4'-amino-1 , 1 '-biphenyl-4-yl)-9-( 1 , 1 - dimethylethyl)-3a,3b,4,4a,7a,8,8a,8b-octahvdro-4,8-ethenopyr rolo[3',4':3, 41cvclobut[1 ,2-f1isoindole-1 ,3,5,7(2H,6H)-tetrone (6).

To a stirred solution of 2,2'-bis(trifluoromethyl)benzidine (19.4 g, 60.55 mmole, 4 equivalents) in pyridine (10 ml) and N-methylpyrrolidinone (80 ml) was added dropwise a solution of tert- butyltricyclotetradecenetetracarboxylic dianhydride (5 g, 15.14 mmole) in N-methylpyrrolidinone (50 ml) over 6 hours at 100°C under nitrogen atmosphere. After that the mixture was heated at 180°C for 8 days. The mixture was cooled down to ambient temperature, solvents distilled off using rotary evaporator, the residue absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of hexanes - dichloromethane and hexanes - ethyl acetate. Fractions containing diimide-diamine combined, eluent evaporated, the residue dried in vacuum to give 8.7 g of compound 6. ¹ H-NMR (DMSO-d6, 500 MHz):

1 .06 (s, 9H), 2.77 (dd, 1 H, J1 = 7 Hz, J2 = 3 Hz), 2.83 - 2.85 (m, 1 H), 2.93-2.96 (m, 2H), 3.02 (dd, 1 H, J1 = 9 Hz, J2 = 2 Hz), 3.07-3.09 (m, 1 H), 3.33-3.35 (m, 1 H), 3.52 (br.s, 1 H), 5.73 (s, 4H), 6.22 (dd, 1 H, J1 = 7 Hz, J2 = 1 .5 Hz), 6.80 (t, 2H, J = 8 Hz), 6.97-7.00 (m, 4H), 7.45-7.47 (m, 3H), 7.59-7.61 (m, 2H), 7.80 (s, 1 H). ¹³ C-NMR (DMSO-de, 125 MHz): 177.9, 177.85, 177.5, 177.1 , 152.1 , 149.57, 149.54, 138.44, 138.37, 134.0,

133.7, 132.8, 132.6, 132.2, 130.2, 129.8, 129.7, 129.9, 128.96, 128.3, 128.0, 125.7, 125.68, 125.1 1 , 1245.0, 124.9, 124.8, 123.53, 123.5, 122.9,

122.8, 122.3, 122.2, 122.1 , 1 16.2, 1 10.7, 1 10.66, 43.3, 43.2, 41 .8, 41 .2, 36.4, 34.5, 34.0, 29.8. ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.6, 57.3, 57.1 , 57.0. MALDI TOF MS: 935.2439 (MH+).

Synthesis Example 6

3a,3b,4,4a,7a,8,8a,8b-Octahydro-9-methyl-4,8- ethenofuro[3',4':3,41cvclobut[1 ,2-f1isobenzofuran-1 ,3,5,7-tetrone.

Maleic anhydride (37.4 g, 0.38 mole) and acetophenone (22.9 g, 0.191 mole) dissolved in toluene (approx. 0.8 L), placed into 1 L

photochemical reactor, irradiated with 200W medium pressure Hanovia mercury lamp. Precipitate collected by filtration. Yield of crude product after irradiation for 28.5 hours - 24 g as a mixture of 9-methyl and 3- methyl regioisomers. The product can be recrystallized from hot acetone. Data for 9-methyl regioisomer: ¹ H-NMR (acetone-d6, 500 MHz): 1.97 (s, 3H), 2.96-3.00 (m, 2H), 3.02-3.05 (m, 1 H), 3.10-3.12 (m, 1 H), 3.31 -3.34 (m, 2H), 3.40-3.44 (m, 2H), 6.18 (d, 1 H, J = 6 Hz). ¹³ C-NMR (acetone-de, 125 MHz): 173.1 , 173.0, 172.5, 172.3, 142.2, 123.6, 43.1 , 42.8, 41 ,7, 41.5, 39.9, 38.8, 38.4, 35.0, 22.0.

In control experiments methyltricyclotetradecenetetracarboxylic dianhydride was found to be unreactive with BPDA even at elevated temperature.

2,6-bis(2,2'-Bis(trifluoromethyl)-4'-amino-1 , 1 '-biphenyl-4-yl)-9-( 1 , 1 - dimethylethyl)-3a,3b,4,4a,7a,8,8a,8b-octahvdro-4,8-ethenopyr rolo[3',4':3,

4lcvclobut[1 .2-flisoindole-1.3.5.7(2H.6H)-tetrone (6a).

A mixture of 2,2'-bis(trifluoromethyl)benzidine (66.66 g, 208.15 mmole, 4 equivalents), methyltricyclotetradecenetetracarboxylic

dianhydride (2.5 g, mixture of 9-methyl and 3-methyl regioisometrs in ratio 1 :0.2), pyridine (20 ml) and N-methylpyrrolidinone (100 ml) was heated at 150°C under nitrogen atmosphere for 1 hour. After that additional amount of methyltricyclotetradecenetetracarboxylic dianhydride was added in 2.5g portions (15 g totally) over 5 hours period at 130°C. After that the mixture was heated at 180°C for 6 days. The mixture was cooled down to ambient temperature, solvents distilled off using rotary evaporator, the residue extracted several times with hot mixture of 10% propyl acetate and heptane to recover excess of 2,2'-bis(trifluoromethyl)benzidine. The residue was absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of propyl acetate and hexanes. Fractions containing diimide-diamine combined, eluent evaporated, dried in vacuum to give 20.1 g of compound 6a. Data for 9- methyl regioisomer: ¹ H-NMR (DMSO-de, 500 MHz): 1 .92 (s, 3H), 2.72- 2.74 (m, 1 H), 2.84-2.86 (m, 1 H), 2.89-2.92 (m, 1 H), 2.94-2.98 (m, 1 H),

3.03 (dd, 1 H, J1 = 8 Hz, J2 = 3 Hz), 3.1 1 (dd, 1 H, J1 = 8 Hz, J2 = 3 Hz), 3.16 (br. s, 1 H), 3.25 (p, 1 H, J = 3 Hz), 7.73 (s, 4H), 6.1 1 (br. s, 1 H), 6.78- 6.81 (m, 2H), 6.97-6.99 (m, 4H), 7.41 -7.47 (m, 3H), 7.56-7.62 (m, 2H),

7.80 (d, 1 H, J = 1 .5 Hz). ¹³ C-NMR (DMSO-de, 125 MHz): 177.9, 177.8,

177.5, 177.3, 149.58, 149.55, 141 .2, 138.5, 138.4, 134.0, 133.7, 132.7,

132.6, 132.2, 130.3, 129.9, 128.9, 128.7, 128.3, 128.0, 127.3, 125.7,

125.1 , 125.0, 124.9, 124.8, 124.2, 123.5, 122.9, 122.8, 122.3, 122.1 ,

1 16.2, 1 10.7, 43.1 1 , 42.35, 41 .6, 41.3, 39.2, 35.7, 22.8. ¹⁹ F-NMR (DMSO- de, 470 MHz): 57.5, 57.3, 57.04, 57.02. MALDI TOF: 893.1969 (MH+).

Synthesis Example 7

2.5-bis(2.2'-Bis(trifluoromethyl)-4'-amino-1.1 '-biohenyl-4-yl)-hexahvdro- benzoM ,2-c:4,5-c'1dipyrrole-1 ,3,5,7(2H,6H)-tetrone (8). A mixture of 2,2'- bis(trifluoromethyl)benzidine (153 g, 477.8 mmole), 1 , 2,4,5- cyclohexanetetracarboxylic dianhydride (5 g), pyridine (20 ml) and N- methylpyrrolidinone (150 ml) was heated at 150°C under nitrogen atmosphere for 1 hour. After that remaining amount of 1 ,2,3,4- cyclohexanetetracarboxylic dianhydride was added in 5g portions (25 g totally, 118.97 mmole totally) over 4 hours period at 150°C. After that the mixture was heated at 180°C for 2.5 weeks. The mixture was cooled down to ambient temperature, solvents distilled off using rotary evaporator, the residue extracted several times with hot mixture of 20% ethyl acetate and heptane to recover excess of 2,2'-bis(trifluoromethyl)benzidine. The residue was absorbed onto celite and subjected to chromatography (2 times) on silica gel using gradient eluation with mixtures of ethyl acetate and hexanes. Fractions containing diimide-diamine combined, eluent evaporated, dried in vacuum to give 3 g of compound 8. ¹ FI-NMR (DMSO- de, 500 MHz): 2.56 (t, 2H, J = 9 Hz), 3.73 (q, 2H, J = 8 Hz), 3.80 (d, 2H, J = 8 Hz), 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.97-6.99 (m, 4H), 7.46 (d, 2H, J = 9 Hz), 7.65 (d, 2H, J = 9 Hz), 7.85 (s, 2H). ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.0, 57.2.

Synthesis Example 8

Compound 9. A mixture of 2,2'-bis(trifluoromethyl)benzidine (132.6 g,

414.08 mmole), 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)- naphtho[1 ,2-c]furan-1 ,3-dione (5 g), pyridine (20 ml) and N- methylpyrrolidinone (150 ml) was heated at 150°C under nitrogen atmosphere for 1 hour. After that remaining amount of dianhydride was added in 5g portions (30 g totally, 118.97 mmole totally) over 2.5 hours period at 150°C. After that the mixture was heated at 180°C for 3 days. The mixture was cooled down to ambient temperature, solvents distilled off using rotary evaporator, the residue extracted several times with hot mixture of 10% propyl acetate and heptane to recover excess of 2,2'- bis(trifluoromethyl)benzidine. The residue was absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of propyl acetate and hexanes. Fractions containing diimide- diamine combined, eluent evaporated, dried in vacuum to give totally 34.1 g of Compound 9. Synthesis Example 9.

5.5'-oxybisr2.2'-bis(trifluoromethyl)-4'-amino-1.1 '-biphenyl-4-nP-I H- isoindole-1 ,3(2H)-dione (10) and Compound 11. A mixture of 2,2'- bis(trifluoromethyl)benzidine (61 .94 g, 6 equivalents) and oxydiphthalic dianhydride (10 g , 32.24 mmole) was heated at 220C under intert atmosphere for 1 hour. After that excess of diamine was sublimed at 260- 265C in vacuum. The residue dissolved in 150 ml of ethyl acetate, absorbed onto celite and subjected to chromatography on silica gel using gradient eluation with mixtures of hexanes and ethyl acetate. Fractions containing pure trimer combined, eluent evaporated using rotary evaporator, the residue dried in vacuum inside glovebox at 150C for 1 hour to give 16.13 g of the product 10. Fraction containing somewhat impure trimer combined, eluent evaporated, the residue dried using rotary evaporator to give 3.53 g of compound 10. Fractions containing pure compound 11 combined, eluent evaporated, the residue dried in vacuum at 150C to give 2.24 g of compound 11.

Compound 10: ¹ H-NMR (DMSO-de, 500 MHz): 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.98 (d, 2H, J = 3 Hz), 7.00 (d, 2H, J = 9 Hz), 7.48 (d, 2H, J = 8 Hz), 7.65-7.68 (m, 4H), 7.75 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.94 (d, 2H, J = 2 Hz), 8.1 1 -8.13 (m, 2H). ¹³ C-NMR (DMSO-de, 125 MHz): 166.4, 166.3, 161.4, 149.5, 138.0, 135.0, 133.7, 132.7, 132.0, 130.0, 129.0, 128.7, 128.3, 128.0, 127.7, 126.7, 125.7, 125.6, 125.1 , 124.8, 123.6, 122.6, 122.9, 122.33, 122.31 , 1 16.2, 1 14.3, 1 10.69, 1 10.65,

1 10.61 . ¹⁹ F-NMR (DMSO-de, 470 MHz): 56.97, 56.98, 57.3.

Compound 11 : ¹ H-NMR (DMSO-de, 500 MHz): 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.98 (d, 2H, J = 2 Hz), 7.00 (d, 2H, J = 8 Hz), 7.48 (d, 2H, J = 9 Hz), 7.67-7.69 (m, 10 H), 7.75 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.86 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.94 (d, 2H, J = 2 Hz), 8.05 (d, 2H, J = 2 Hz), 8.1 1 -8.15 (m, 4H).

Synthesis Example 10.

5.5'-oxybis[1 .3-phenylenebis(oxy-3.1 -phenylene)yll-1 H-isoindole-1.3(2H)- dione (12). A mixture of 1 ,3-bis(3-aminophenoxy)benzene (56.55 g, 193.44 mmole, 6 equivalents) and oxydiphthalic dianhydride (10 g , 32.24 mmole) was heated at 220C under intert atmosphere for 1 hour and then at 265C in vacuum. The residue dissolved in 150 ml of ethyl acetate, absorbed onto celite and subjected to partial chromatography purification on silica gel using gradient eluation with mixtures of hexanes and ethyl acetate. Fractions containing pure trimer combined, eluent evaporated using rotary evaporator, the residue dried in vacuum inside glovebox at 150C for 1 hour. Compound 12: ¹ H-NMR (DMSO-de, 500 MHz): 5.21 (s,

4H), 6.16 (dd, 2H, J1 = 8 Hz, J2 = 3 Hz), 6.22 (t, 2H, J = 2 Hz), 6.33 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.66 (t, 2H, J = 2 Hz), 6.74-6.78 (m, 4H), 6.98 (t, 2H, J= 8 Hz), 7.1 1 (dd, 2H, J1 = 8Hz, J2 = 2 Hz), 7.16 (t, 2H, J = 2Hz), 7.23 (br d, 2H, J = 8 Hz), 7.36 (t, 2H, J = 8 Hz), 7.53 (t, 2H, J = 8 Hz), 7.59-7.52 (m, 4H), 8.04 (d, 2H, J = ). ¹³ C-NMR (DMSO-de, 125 MHz):

166.5, 166.3, 161 .3, 159.0, 157.7, 157.3, 156.9, 156.0, 134.9, 133.7,

131.5, 130.7, 130.6, 127.6, 126.56, 125.4, 122.9, 1 18.6, 1 17.9, 1 14.2, 1 14.0, 1 13.4, 1 10.4, 109.4, 106.6, 104.6.

Synthesis Example 1 1 .

2,2"-bis(2,2'-bis(trifluoromethyl)-4'-amino-1 , T-biphenyl-4-yl)(dodecahvdro- 1 , 1 ",2',3,3"-pentaoxodispiro[4,7-methano-5H-isoindole-5, 1 '-cyclopentane- 3',5"-[4,71methano[5H1isoindole (13). A mixture of 2,2'- bis(trifluoromethyl)benzidine (41.66 g, 130.08 mmole, 10 equivalents) and the corresponding spirocyclic dianhydride (5 g , 13.01 mmole) was heated at 220C under intert atmosphere for 1.5 hours. The residue dissolved in ethyl acetate, absorbed onto celite and subjected to chromatography 5 purification on silica gel using gradient eluation with mixtures of hexanes and ethyl acetate and hexanes - ptopyl acetate. Fractions containing pure product combined, eluent evaporated using rotary evaporator, the residue dried in vacuum inside glovebox at 150C for 1 hour to give 8.59 g of compound 13. ¹ H-NMR (DMSO-de, 500 MHz): 1.30-1.47 (m, 4H), 1.75- ID 2.13 (m, 8H), 2.65 (br. s, 4H), 2.97-3.26 (m, 4H), 5.72 (s, 4H), 6.79 (d, 2H, J = 9 Hz), 6.96-6.97 (m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.58 (d, 2H, J = 8 Hz), 7.74 (s ,2H). ¹³ C-NMR (DMSO-de, 125 MHz): 223.8, 223.3, 117.97, 117.93, 117.75, 117.81 , 149.5, 138.5, 133.8, 132.6, 132.3, 130.2, 130.1 , 129.2, 129.0, 128.75, 128.5, 128.0, 127.9, 127.8, 127.2, 125.7, 125.0,

15 124.7, 124.6, 123.5, 122.9, 122.2, 121.3, 120.7, 120.0, 116.2, 110.7,

110.6, 66.7, 53.6, 48.0, 47.9, 47.4, 46.7, 45.6, 45.1 , 42.0, 33.2, 21.2, 31.9, 30.8, 21.9, 21.1 , 10.7. ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.3, 57.0.

Synthesis Example 12.

2, 2'-bis(2,2'-bis(trifluoromethyl)-4' -amino-1 , 1 '-biphenyl-4-ylH5,5'-bi-1 H- isoindolel-1.T.3.3'(2H.2'H)-tetrone (14). A mixture of 2,2'- bis(trifluoromethyl)benzidine (113.7 g, 355.1 mmole, 6.3 equivalents) and 25 biphenyltetracarboxylic dianhydride (16.58 g , 56.35 mmole) with small amount of N-methylpyrrolidinone was heated at 220C under intert atmosphere for 1 hour and then in vacuum at the same temeperature for 3 hours. The mixture cooled down, dissolved in ethyl acetate, absorbed onto celite and subjected to chromatography purification on silica gel using 30 gradient eluation with mixtures of hexanes and ethyl acetate. Fractions containing pure product combined, eluent evaporated using rotary evaporator to volume 200 ml, and cystallized product collected by filtration to give 17.57 g of compound 14. Fractions containing lesser purity product combined, euent evaporated, the resiude duissolved in ethyl acetate followed by addition of one volume of hexanes and allowed to stand at ambient temperature for slow crystallization. Precipitated product containing impurities of oligomers collected by filtration to give 12.95 g of lesser purity material. Product containing small amount of oligomers can also be obtained by direct crystallization by dissolving initial crude mixture in ethyl acetate, addition of one volume of hexanes, collecting formed precipitate. ¹ H-NMR (DMSO-de, 500 MHz): 5.73 (s, 4H), 6.81 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.99 (d, 2H, J = 2 Hz), 7.02 (d, 2H, J = 9 Hz), 7.50 (d,

2H, J = 8 Hz), 7.79 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.98 (d, 2H, J = 2 Hz), 8.14 (d, 2H, J = 8 Hz), 8.43 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 8.50 (s, 2H). ¹³ C-NMR (DMSO-de, 125 MHz): 166.8, 149.6, 144.9, 138.0, 134.4, 133.7, 133.2, 132.7, 132.1 , 131.9, 130.3, 128.9, 128.3, 125.1 , 124.8, 124.8, 123.0, 122.9, 116.2, 110.7, 110.66. ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.3,

57.0.

Synthesis Example 13.

Dodecahvdro-2.2'-bis(2.2'-bis(trifluoromethyl)-4'-amino-1.1 '-biphenyl-4-yl)- [5 5'-bi-1 H-isoindolel-1 1 '.3 3'(2H.2'H)-tetrone (15). A mixture of 2,2'- bis(trifluoromethyl)benzidine (52.27 g, 163.24 mmole, 10 equivalents), dicyclohexyl-3, 4, 3’, 4’-tetracarboxylic dianhydride (5 g , 16.32 mmole) and N-methylpyrrolidinone (5 ml) was heated at 220C under intert atmosphere for 1 hour and then in vacuum at the same temeperature for 1 hour. The mixture cooled down, dissolved in ethyl acetate, absorbed onto celite and subjected to chromatography purification on silica gel using gradient eluation with mixtures of hexanes and ethyl acetate. Fractions containing pure product combined, eluent evaporated using rotary evaporator the residue dried in vacuum at 150C to give 8.92 g of compound 15. ¹ H-NMR (DMSO-de, 500 MHz): 0.99 (br s, 2H), 1.32 (br. s, 4H), 1.61 -1.63 (m, 4H), 1 .97-2.04 (m, 2H), 2.14-2.17 (m, 2H), 2.99-3.05 (m, 2H), 3.22-3.26 (m,

2H), 5.71 (s, 4H), 6.79 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.96-6.97 (m, 4H), 7.42 (d, 2H, J = 8 Hz), 7.61 (d, 2H, J = 8 Hz), 7.78 (s, 2H). ¹³ C-NMR (DMSO-de, 125 MHz): 179.0, 178.4, 149.5, 138.1 , 133.6, 132.64, 132.57, 132.55, 130.1 , 128.3, 125.7, 123.5, 122.3, 120.0, 1 16.2, 1 10.67, 1 10.63,

1 10.59, 29.34, 29.25, 25.52, 21 .69, 21 .66. ¹⁹ F-NMR (DMSO-de, 470 MHz): 57.25, 57.22, 57.06, 57.04.

Synthesis Example 14.

1 1 -methyl-2,8-bis(2,2'-bis(trifluoromethyl)-4'-amino-1 , 1 '-biphenyl-4-yl)-1 1 - (trifluoromethvD-1 H-pyranor2 3-f:5.6-f'ldiisoindole-1 3 7.9(2H.8H.1 1 H)- tetrone (16). A mixture of 2,2'-bis(trifluoromethyl)benzidine (51 g, 159.26 mmole, 10 equivalents), the corresponding xanthene tetracarboxylic dianhydride (10.2 g , 25.23 mmole) and N-methylpyrrolidinone (25 ml) was heated at 220C under intert atmosphere for 1 hour and then in vacuum at the same temeperature for 1 hour. The mixture diluted with ethyl acetate, absorbed onto celite and subjected to chromatography purification on silica gel using gradient eluation with mixtures of hexanes and ethyl acetate. Fractions containing pure product combined, eluent evaporated using rotary evaporator the residue dried in vacuum to give 16.62 g of compound 16. ¹ H-NMR (DMSO-de, 500 MHz): 2.39 (s, 3H), 5.74 (s, 4H), 6.82 (d, 2H, J = 8 Hz), 7.00-7.03 (m, 4H), 7.51 (d, 2H, J = 8 Hz), 7.78 (d, 2H, J = 8 Hz), 7.91 (s, 2H), 7.97 (d, 2H, J = 2 Hz), 8.51 (s, 2H). ¹³ C-NMR (DMSO-de, 125 MHz): 170.8, 166.1 , 165.7, 155.5, 149.6, 138.2, 134.8,

133.8, 132.7, 132.0, 130.3, 128.8, 128.1 , 127.9, 125.8, 125.6, 125.1 ,

124.9, 124.6, 123.6, 122.6, 122.3, 121 .4, 120.8, 1 16.2, 1 12.9, 1 10.73,

1 10.69, 1 10.64, 45.0, 19.8. ¹⁹ F-NMR (DMSO-de, 470 MHz): 75.5, 57,4, 57.0.

Synthesis Example 15. ,3

5,7(2FI,6FI)-tetrone (17). 4,4'-sulfonylbis[benzeneamine] (56.92 g, 229.2 mmole, 5 equivalents), pyromeelitic dianhydride (10 g, 45.84 mmole) and N-methylpyrrolidinone (100 ml) heated at 177C with stirring under nitrogen atmosphere for 1.5 hours. Reaction mixture cooled down, diluted with ethyl acetate (200 ml), filtered, washed with ethyl acetate, dried in vacuum to give 26 g of crude product containing approx. 10% of higher oligomeric products that was used for polymerization without further purification. ¹ H- NMR (DMSO-de, 500 MHz): 6.22 (s 4H), 6.64 (d, 4H, J = 9 Hz), 7.59 (d, 4H, J = 9 Hz), 7.72 (d, 4H, J = 9 Hz), 8.02 (d, 4H, J = 9 Hz), 8.40 (s, 2H).

Synthesis Example 16

Into a 500 mL round bottom flask equipped with Dean-Stark trap under nitrogen sweep, and stir bar were charged 22.41 g of TFMB (0.07 moles) and 250.71 g of 1-Methyl-2-Pyrrolidinone (NMP). The mixture was stirred under nitrogen at room temperature for about 30

minutes. Afterwards, 26.74 g (0.06 moles) of 6FDA was added slowly in portions to the stirring solution of the diamine. After completion of the dianhydride addition, and additional 27.86 g of NMP were used to wash in any remaining dianhydride powder from containers and the walls of the flask and the resulting mixture was stirred overnight at room

temperature. Afterwards, 80 mL of m-xylene was added to the mixture and refluxed for 8 hours to remove water with Dean-Stark trap. Mixture was cooled to room temperature, follow by precipitation into 1 ,500 mL of methanol with agitation, resulting suspension was filtered and the collected solid was dried under vacuum.

The resulting diamine monomer had a molecular weight of ~5,000 Da. Thus it had about 7 repeating dimiides in the core (m~7 in Formula I). The solid was used without further separation or purification in reactions with dianhydride(s) to form polyamic acid polymers.

Synthesis Example 17

6,6'-(sulfonyldi-4,1 -phenylene)bis-1 H-Furo[3,4-f1isoindole-1 ,3,5,7(6H)- tetrone (33). Synthesis of pyromellitic acid monoanhydride. To a stirred solution of pyromellitic dianhydride (43.6 g, 0.2 mole) in 400 ml of THF was added a mixture of 30 ml of tetrahydrofuran and 5 ml of water at ambient temperature over period of 48 hours. After that 250 ml of tetrahydrofuran was evaporated using rotary evaporator, resulting solution treated with hexanes (100 ml) until precipitation occurred. Precipitate removed by filtration. Filtrate kept at -24C for 3 hours. Precipitate filtered, dried in vacuum to give 14.9 g of the product. Additional amount of the product formed overnight at -24C was filtered, dried in vacuum to give 6.85 g of the product. ¹ H-NMR (acetone-de, 500 MHz): 6.39 (s 2H), 12.46 (br. s, 2H).

The above pyromellitic acid monoanhydride (28.16 g, 119.26 mmole,

2.3 equivalents) was stirred with 4,4'-sulfonylbis[benzeneamine] (12.97 g, 52.2 mmole) in 200 ml of dry tetrahydrofuran at ambient temeperature for 1 hour. The mixture was diluted with acetone (100 ml), passed through a column filled with silica gel washing with acetone. Fractions containing product combined, solvents evaporated using rotary evaporator, the residue treated with approximately 500 ml of water, fine precipitate filtered, washed with water, dried in vacuum to give amic hexaacid (31.1 g): ¹ H- NMR (DMSO-de, 500 MHz): 7.78 (s, 2H), 7.86 (d, 4H, J = 9 Hz), 7.91 (d, 4H, J = 9 Hz), 8.16 (s, 2H), 10.89 (s, 2H), 13.56 (br. s, 6H).

The above amic hexaacid (31.1 g) was stirred with heating at reflux in acetic anhydride (300 ml) under nitrogen atmosphere for 2 hours. Hot reaction mixture was filtered, washed with 50 ml of acetic anhydride, dichloromethane (50 ml), suspended in 150 ml of chloroform, filtered, dried in vacuum to give 20.9 g of compound 33: ¹ H-NMR (DMSO-d6, 500 MHz): 7.81 (d, 4H, J = 9 Hz), 8.23 (d, 4H, J = 9 Hz), 8.57 (s, 4H).

Polymer examples

These examples illustrate the preparation of polyamic acids having Formula II.

Polymer Example 1

Polymer 1 . Polymerization of compound 6 with BPDA:

Diimide-diamine monomer 6 (5.23 g, 5.60 mmole), BPDA (1 .616 g, 5.488 mmole) and N-methylpyrrolidinone (38 ml) were added to 250 ml glass reactor, the mixture was stirred under nitrogen atmosphere at ambient temperature until final viscosity of the polyamic acid of 7283 cP. GPC: Mn = 73713, Mw = 139448, Mp = 121967, Mz = 222437, PDI = 1 .89. ¹ H-NMR: (DMSO-de, 500 MHz): 1 .08 (s, 9H), 2.78-3.10 (m, 6H), 3.36 (br. s, 1 H), 3.54 (br. s, 1 H), 6.24 (br. d, 1 H, J = 6 Hz), 7.44-8.36 (m, 18H), 10.90 (br. s, 2H), 13.30 (br. s, 2H).

Polymer Example 2

Polymer 2. Polymerization of compound 2 with BPDA:

Diimide-diamine monomer 2 (2 g, 2.41 mmole) obtained by direct crystallization from crude reaction mixture and recrystallized from propyl acetate, BPDA (0.689 g, 2.34 mmole) and N-methylpyrrolidinone (15.2 g) were mixed using roller and allowed to react at ambient temperature until final viscosity of the polyamic acid of 1 1620 cP. GPC: Mn=127781 , Mw=300128, Mp=258512, Mz=496954, PDI=2.35. ¹ H-NMR: (DMSO-de, 500 MHz): 2.05 (br. s, 2H), 2.35 (br. s,24H), 3.30 (br. s, 4H), 7.41 -8.34 (m, 18H), 10.89 (br. s, 2H), 13.30 (br. s, 2H).

Polymer Example 3

Polymer 3. Polymerization of compound 4 with BPDA:

Diimide-diamine monomer 4 (6.70 g, 7.84 mmole), BPDA (2.237 g, 7.60 mmole) and N-methylpyrrolidinone (50 ml) were added to 250 ml glass reactor, the mixture was stirred under nitrogen atmosphere at ambient temperature followed by addition of final PMDA (39 mg) until final viscosity of the polyamic acid of 7890 cP. GPC: Mn = 88795, Mw = 175396, Mp = 168430, Mz = 282955, PDI = 1 .98. ¹ H-NMR: (DMSO-de, 500 MHz): 1.56 (br. s, 4H), 2.63 (br. s, 2H), 3.43 (br. s, 4H), 7.44-8.36 (m, 18H), 10.90 (br. s, 2H), 13.30 (br. s, 2H).

Polymer Example 41

Polymer 4. Polymerization of compound 5 with BPDA:

Diimide-diamine monomer 5 (6.71 g, 7.87 mmole), BPDA (2.246 g, 7.63 mmole) and N-methylpyrrolidinone (50 ml) were added to 250 ml glass reactor, the mixture was stirred under nitrogen atmosphere at ambient temperature followed by addition of final PMDA (39 mg) until final viscosity of the polyamic acid of 6033 cP. GPC: Mn = 93567, Mw = 184524, Mp = 178922, Mz = 297891 , PDI = 1 .97. ¹ H-NMR: (DMSO-de, 500 MHz): 3.49 (br. s, 4H), 3.59 (br. s, 2H), 6.40 (s, 2H), 7.41 -8.34 (m,

18H), 10.89 (br. s, 2H), 13.26 (br. s, 2H).

Polymer Example 5 monomers

Polymer 5. Polymerization of compound 9 with BPDA

Diimide-diamine monomer 9 (3 g, 3.316 mmole), BPDA (0.956 g, 3.25 mmole) and N-methylpyrrolidinone (22.6 g) were mixed using roller under inert atmosphere and allowed to react at ambient temperature followed by addition of PMDA (7 mg) until final viscosity of the polyamic acid of 3135 cP. GPC: Mn= 106690, Mw= 240045, Mp= 210783, Mz= 420038, PDI=2.25. Polymer Example 6

monomers

Polymer 6. Polymerization of compound 8 with BPDA

Diimide-diamine monomer 8 (2.572 g, 3.157 mmole), BPDA (0.91 g, 3.093 mmole) and N-methylpyrrolidinone (19.8 g) were mixed using roller under inert atmosphere and allowed to react at ambient temperature followed by addition of PMDA (10 mg) until final viscosity of the polyamic acid of 7779 cP. GPC: Mn= 92903, Mw= 175925, Mp= 165061 , Mz= 278182, PDI=1.89. Polymer Example 7 monomers

Polymer 7. Polymerization of compounds 11 and 12 with oxydiphthalic anhydride

Diimide-diamine monomer 11 (1.799 g, 1.192 mmole), diimide monomer 12 (0.171 g, 0.199 mmole), oxydiphthalic anhydride (0.42 g, 1.354 mmole) and N-methylpyrrolidinone (13.6 g) were mixed using roller under inert atmosphere and allowed to react at ambient temperature followed by addition of oxydiphthalic anhydride (10 mg). GPC: Mn= 52301 , Mw= 124710, Mp= 109452, Mz= 205698, PDI=2.38.

Polymer Example 8

Polymer 8. Polymerization of compound 15 with BPDA

Diimide-diamine monomer 15 (8.5 g, 9.33 mmole), BPDA (2.73 g, 9.29 mmole) and N-methylpyrrolidinone (63.6 g) were added to 250 ml glass reactor, the mixture was stirred under nitrogen atmosphere at ambient temperature until final viscosity of the polyamic acid of 4339 cP. GPC: Mn = 104310, Mw = 234898, Mp = 222275, Mz = 378468, PDI = 2.25.

Polymer Example 9 Polymer 9:

Into a 250 ml_ reaction flask equipped with a nitrogen inlet and outlet, and mechanical stirrer were charged 3.46 g of TFMB (0.0108 moles), 6.51 g of Compound 9 (0.0072 moles), and 88.58 g of 1 -Methyl-2 - Pyrrolidinone (NMP). The mixture was agitated under nitrogen at room temperature for about 30 minutes. Afterwards, 3.64 g (0.009 moles) of XFDA was added slowly in portions to the stirring solution of the diamine followed by 3.76 g (0.00846 moles) of 6FDA. After completion of the dianhydride addition, and additional 9.84 g of NMP were used to wash in any remaining dianhydride powder from containers and the walls of the reaction flask and the resulting mixture was stirred for 6

days. Separately, a 5% solution of 6FDA in NMP was prepared and added in small amounts (ca. ~0.8 g) over time to increase the molecular weight of the polymer and viscosity of the polymer solution. Brookfield cone and plate viscometry was used to monitor the solution viscosity by removing small samples from the reaction flask for testing. A total of 3.2 g of this finishing solution was added (0.16 g, 0.00036 moles 6FDA). The reaction proceeded overnight at room temperature under gentle agitation to allow for polymer equilibration. Final viscosity of the polymer solution was 1 , 100 cps at 25C.

Polymer Examples 10-14

Polymers 10-14 were prepared using a procedure similar to

Polymer Example 9. The polymer compositions are given below in Table 1 .

Table 1 . Polymer compositions

Polymer Example 15

Polymer 15. Polymerization of in situ preimidized

bicyclooctanetetracarboxylic dianhydride with 6FDA, BPDA.

A mixture of 2,2'-bis(trifluoromethyl)benzidine (11.902 g, 37.17 mmole), bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride (6.51 g, 26.02 mmole) and 20 ml of N-methylpyrrolidinone was heated at 180C with Dean-Stark apparatus under intert atmosphere for 2.5 hours. After that N- methylpyrrolidinone was distilled in vacvuum. NMR spectral data of the resulting glassy residue showed complete imidization. Solids were redissolved in N-methylpyrrolidinone at 150C, transferred to glass reactor and stirred with 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (1.094 g, 3.717 mmole), 4,4'-hexafluoroisopropylidenebisphthalic dianhydride 6FDA (2.808 g, 6.32 mmole) at ambient temeperature under nitrogen atmosphere with total amount of N-methylpyrrolidinone of 129 g. After that additional amount of 6FDA (480 mg totally, 1.08 mmole) added until final viscosity 10430 cP. GPC: Mn = 88006, Mw = 205641 , Mp = 201618, Mz = 335818, PDI = 2.34.

Polymer Example 16

Polymer 16. Polymerization of in situ preimidized norbornane-2-spiro-a- cyclopentanone-a'-spiro-2"-norbornane-5,5",6,6"-tetracarboxy lic

dianhydride (CpODA) with BPDA.

A mixture of 2,2'-bis(trifluoromethyl)benzidine (5.95 g, 18.58 mmole), norbornane-2-spiro-a-cyclopentanone-a'-spiro-2"-norbornane- 5,5",6,6"-tetracarboxylic dianhydride CpODA (5.0 g, 13.08 mmole) and 6 ml of N-methylpyrrolidinone was heated at 180C with Dean-Stark apparatus under intert atmosphere for 3 hours followed by addition of 6 ml of N-methylpyrrolidinone and heating the mixture for additional 3 hours. After that N-methylpyrrolidinone was distilled in vacvuum. Solids were redissolved in N-methylpyrrolidinone (71 g), transferred to glass reactor and stirred at ambient temeperature under nitrogen atmosphere with 3,3',4,4'-biphenyltetracarbocylic dianhydride BPDA (1.53 g, 5.20 mmole) followed by addition of pyromellitic dianhydride PMDA (62 mg) until final viscosity 22860 cP. GPC: Mn = 80956, Mw = 188020, Mp = 169907, Mz = 313930, PDI = 2.32.

Polymer Example 17

Polymer 17. Polymerization of in situ preimidized

bicyclooctanetetracarboxylic dianhydride with PMDA, BPDA.

Polymer 17 was prepared as described above for Polymer 15, except that PMDA was used instead of 6FDA.

Polymer Example 18

Polymer 18: monomers

Diimide-dianhydride monomer 33 (2.485 g), 2,2'- bis(trifluoromethyl)benzidine (1.179 g) and N-methylpyrrolidinone (20 g) were dissolved, mixed using roller under inert atmosphere, allowed to react at ambient temperature followed by addition of pyromellitic

dianhydride (25 mg) until final viscosity 7112 cP. GPC: Mn = 92432, Mw = 197099, Mp = 173514. Mz = 347413, PDI = 2.13

Film Examples

These examples illustrate the preparation of polyimide films having

Formula IV.

A Flunter Lab spectrophotometer was used to measure b* and yellow index along with % transmittance (%T) over the wavelength range 350nm-780nm. Thermal measurements on films were made using a combination of thermogravimetric analysis and thermomechanical analysis as appropriate for the specific parameters reported herein. Mechanical properties were measured using equipment from Instron.

Film Examples 1 -7

The above polyamic acids were used to prepare polyimide films having Formula IV.

The polyamic acid solution was filtered through microfilter, spun coated onto clean silicon wafers, soft-baked at 90°C on hotplate, placed into a furnace. The furnace was purged with nitrogen and heated to a maximum cure temperature in stages. Wafers were removed from furnace, soaked in water and manually delaminated to yield samples of polyimide films. The film compositions are given below in Table 2. The film properties are given below in Table 3. Table 2. Polyimide films

Table 3. Film Properties

Haze is in %; Tg in °C; CTE is the second scan measurement in ppm/°C;

Dh is the birefringence at 633 nm; Td is the temperature in °C at which a 1 % weight loss occurs; T.M. is the tensile modulus in GPa; T.S. is the tensile strength in MPa; Elong is the elongation to break in %.

As can be seen from the above examples, the use of preimidized monomers can lead to high molecular weight polymers using conventional polymerization techniques.

As can be seen from Table 3, polymide films obtained from preimidized imide-containing monomers possess beneficial properties, such as reduced coloration b*/Yellow Index Yl, increased thermal stability Td(1 %), improved mechanical properties and other properties.

Film Examples 8-13

The above polyamic acids were used to prepare polyimide films having Formula IV, as described in Film Examples 1 -7, except for Film Example 9. In Film Example 9, the film was cured in air at a maximum temperature of 260°C.

The film compositions are given below in Table 4. The film properties are given below in Table 5. Table 4. Polyimide films

Table 5. Film Properties

Td is the temperature in °C at which a 1 % weight loss occurs; T.M. is the tensile modulus in GPa; T.S. is the tensile strength in MPa; Elong is the elongation to break in %.

Film Examples 15-17

These examples illustrate the formation of polyimide films from in situ preimidized monomers.

Polyimide films were made as described in Film Examples 1 -7. The film compositions are given below in Table 6. The film properties are given below in Table 7.

Table 6. Polyimide films

Table 7. Film Properties

Haze is in %; Tg in °C; CTE is the second scan measurement in ppm/°C; Dh is the birefringence at 633 nm; Td is the temperature in °C at which a 1 % weight loss occurs;

Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. The use of numerical values in the various ranges specified herein is stated as approximations as though the minimum and maximum values within the stated ranges were both being preceded by the word "about." In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Also, the disclosure of these ranges is intended as a continuous range including every value between the minimum and maximum average values including fractional values that can result when some of components of one value are mixed with those of different value. Moreover, when broader and narrower ranges are disclosed, it is within the contemplation of this invention to match a minimum value from one range with a maximum value from another range and vice versa.