UV ACTIVE DERIVATIVES OF Pd(AcAc)2 CATALYZED POLYCYCLOOLEFIN COMPOSITIONS AS OPTICAL MATERIALS

CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U. S. Provisional Application No. 62/954,911, filed December 30, 2019, which is incorporated herein by reference in its mtirety.

BACKGROUND OF THE INVENTION

Field of the Invention

Embodiments in accordance with the present invention relate generally to a single component mass polymerizable polycycloolefin monomer compositions having high optical transparency and exhibiting suitable refractive index that match the refractive index of layers in optical devices, such as optical sensors, light emitting diodes (LEDs), organic light emitting diode (OLED), among other devices. More specifically, this invention relates to single component compositions encompassing norbomene (NB) based olefinic monomers, which undergo mass vinyl addition polymerization to form optical layers having utility in a variety of opto-electronic applications including as encapsulates, coatings, and fillers.

Description of the Art

Organic light emitting diodes (OLEDs) are gaining importance in a variety of applications, including flat panel televisions and other flexible displays, among other applications. However, conventional OLEDs, particularly, bottom emitting OLEDs suffer from a drawback in that only about half of the generated photons are emitted into the glass substrate out of which 25% are extracted into air. The other half of the photons are wave- guided and dissipated in the OLED stack. This loss of photons is primarily attributed to the refractive index (n) mismatch between the organic layers (n = 1.7-1.9) and the glass substrate (n = 1.5). By matching the refractive index of the substrate (n = 1.8) and organic layers and augmenting the distance of the emission zone to the cathode to suppress plasmonic losses light extraction into the substrate can be increased to 80-90%. See, for example, G. Gaertner et al., Proc. of SPIE, Vol. 6999, 69992T pp 1-12 (2008).

In addition, OLEDs also pose other challenges; in that OLEDs being organic materials, they are generally sensitive to moisture, oxygen, temperature, and other harsh conditions. Thus, it is imperative that OLEDs are protected from such harsh atmospheric conditions. See for example, U. S. Patent Application Publication No. US2012/0009393 Al. In order to address some of the issues faced by the art, U. S. Patent No. 8,263,235 discloses use of a light emitting layer formed from at least one organic light emitting material and an aliphatic compound not having an aromatic ring, and a refractive index of the light emitting from 1.4 to 1.6. The aliphatic compounds described therein are generally a variety of polyalkyl ethers, and the like, which are known to be unstable at high temperatures, see for example, Rodriguez et al., I & EC Product Research and Development, Vol. 1, No. 3, 206- 210 (1962).

U. S. Patent No. 9,944,818 and U. S. Patent No. 10,266,720, disclose atwo component mass polymerizable composition which is capable of tailoring to the desirable refractive index and is suitable as a filler and a protective coating material, thus potentially useful in the fabrication of a variety of OLED devices.

The co-pending U. S. Patent Application No. 15/861,801, filed January 4, 2018, discloses a single component mass vinyl addition polymerizable composition which is thermally activated and capable of tailoring to the desirable refractive index and is suitable as a filler and a protective coating material, thus potentially useful in the fabrication of a variety of OLED devices.

However, there is still a need for organic filler materials that complement the refractive index of OLEDs and yet exhibit high transparency and good thermal properties, among other desirable properties. In addition, it is desirable that such organic filler materials readily form a permanent protective coatings and are available as a single component composition for dispensing with such OLED layers simply by exposing to suitable actinic radiation at ambient temperature.

Thus, it is an object of this invention to provide organic materials that overcome the gaps faced by the art. More specifically, it is an object of this invention to provide a single component composition that will mass polymerize when exposed to suitable actinic radiation under the conditions of the fabrications of an OLED device. It is further an object of this invention to provide stable single component mass polymerizable composition with no change in viscosity at or below normal storage conditions but which undergoes mass polymerization only when exposed to suitable actinic radiation. It is further an object of this invention to provide single component composition that can be used in a variety of other applications including for example 3D printing, ink-jettable coatings, sealants, and the like.

Other objects and further scope of the applicability of the present invention will become apparent from the detailed description that follows.

SUMMARY OF THE INVENTION

Surprisingly, it has now beat found that by employing a single component composition, it is now possible to fabricate a variety of devices including for example an OLED device having a transparent optical layer which feathures hitherto unachievable properties, i.e., refractive index in the range of 1.4 to 1.6 or higher, high colorless optical transparency, desirable film thickness of the filler layer typically in the range of 10 to 20 μm but can be tailored to lower or higher film thickness depending upon the intended application, compatible with the OLED stack, particularly the cathode layer (a very thin layer on the top of the OLED stack), compatible with polymerization of the formulation on the OLED stack, including fast polymerization time and can be photolytically treated at ambient fabrication conditions, adhesion to both OLED stack and glass cover, and the like. It is also important to note that the compositions of this invention arc expected to exhibit good uniform leveling across the OLED layer which typically requires a low viscosity. Further, compositions of this invention are also expected to exhibit low shrinkage due to their rigid polycycloolefinic structure. In addition, as the of this invention undergo fast mass polymerization upon application they do not leave behind any fugitive small molecules which can damage the OLED stack. Generally, no other small molecule additives need to be employed thus offering additional advantages. Most importantly, the compositions of this invention are stable (i. e., no change in viscosity) at ambient atmospheric conditions including up to 40 °C for several days and undergo mass polymerization only when exposed to suitable actinic radiation. The compositions undergo mass vinyl addition polymerization very quickly when subjected to such actinic radiation ami generally the compositions become solid objects in few minutes, i.e., within 1-10 minutes and more generally in less than one hour.

Advantageously, the compositions of this invention are also compatible with a “one drop fill” (commonly known as “ODF”). In a typical ODF process, which is commonly used to fabricate a top emission OLED device, a special optical fluid is applied to enhance the transmission of light from the device to the top cover glass, and the fluid is dispensed by an ODF method. Although the method is known as ODF which can be misleading because several drops or lines of material arc generally dispensed inside die seal lines. After applying die fluid, the fluid spreads out as the top glass is laminated, analogous to die-attach epoxy. This process is generally carried out under vacuum to prevent air entrapment The present invention allows for a material of low viscosity which readily and uniformly coats the substrate with rapid flow in a short period of time. Even more advantageously, the present invention overcomes the deficiencies faced by the prior art in that a single component composition is much more convenient than employing a two component system especially in an ODF method.

Accordingly, there is provided a single component composition encompassing a) one or more olefinic monomers; b) an organopalladium compound of formula (I) as described herein; c) a photoacid generator as described herein; and d) a photosensitizer.

In another aspect of this invention there is also provided a kit encompassing the composition of tiiis invention for forming a three dimensional object, such as for example, a transparent film.

BRIEF DESCRIPTION OF THE DRAWINGS Embodiments in accordance with the present invention are described below with reference to the following accompanying figures and/or images. Where drawings are provided, it will be drawings which are simplified portions of various embodiments of this invention and are provided for illustrative purposes only.

FIG. 1 shows a graphical illustration of the viscosity change of an embodiment of the composition of tiiis invention.

FIG. 2 shows a graphical illustration of the viscosity change of an embodiment of the composition of this invention.

FIG.3 shows a film embodiment of this invention having optical transmittance of 90 percent FIG. 4 shows a 3D printed object from the composition embodiment of this invention.

FIGs. 5A and 5B show optical micrographs of different resolutions of typical patterned surface of a conventional digital video disk (DVD): FIG. 5A - 10 μm and FIG. 5B - 20 μm.

FIGs. 6A and 6B show optical micrographs of different resolutions of patterned surface obtained from a composition embodiment of tiiis invention: FIG.6A - 10 μm and FIG. 6B - 20 μm magnification, which are identical replica of the patterned surface of a DVD having periods of channel surface of about 760 ran ± 20 nm.

DETAILED DESCRIPTION The tenns as used herein have the following meanings: As used herein, the articles “a,” “an,” and “the" include plural referents unless otherwise expressly and unequivocally limited to one referent.

Since all numbers, values and/or expressions referring to quantities of ingredients, reaction conditions, etc., used herein and in the claims appended hereto, are subject to the various uncertainties of measurement encountered in obtaining such values, unless otherwise indicated, all are to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous, inclusive of both the minimum and maximum values of the range as well as every value between such minimum and maximum values. Still further, where a range refers to integers, every integer between the minimum and maximum values of such range is included, In addition, where multiple ranges are provided to describe a feature or characteristic, such ranges can be combined. That is to say that, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. For example, a stated range of from “1 to 10” should be considered to include any and all sub-ranges between the minimum value of 1 and the maximum value of 10. Exemplary sub-ranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, etc.

As used herein, the symbol denotes a position at which the bonding takes place with another repeat unit or another atom or molecule or group or moiety as appropriate with the structure of the group as shown.

As used herein, “hydrocarbyl” refers to a group that contains carbon and hydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term “halohydrocarbyl” refers to a hydrocarbyl group where at least one hydrogen has been replaced by a halogen. The term perhalocarbyl refers to a hydrocarbyl group where all hydrogens have been replaced by a halogen.

As used herein, the expression “(C ₁ -C ₆ )alkyl" includes methyl and ethyl groups, and straight-chained or branched propyl, butyl, pentyl and hexyl groups. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyl and tert-butyl. Derived expressions such as “(C ₁ -C ₄ )alkoxy", “(C ₁ -C ₄ )thioalkyl” “(C ₁ -C ₄ )alkoxy(C ₁ -C ₄ )alkyr, “hydroxy(C ₁ -C ₄ )alkyr, “(C ₁ -C ₄ )alkylcarbonyl", “(C ₁ -C ₄ )alkoxycarbonyl(C ₁ -C ₄ )alkyr, “(C ₁ -C ₄ )alkoxycaibonyl", “diphenyl(C ₁ -C ₄ )alkyr, “phenyl(C ₁ -C ₄ )alkyr, “phenylcarboxy(C ₁ -C ₄ )alkyl" and “phenoxy(C ₁ -C ₄ )alkyr are to be construed accordingly. As used herein, the expression “cycloalkyl” includes all of the known cyclic groups. Representative examples of “cycloalkyl” includes without any limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derived expressions such as “cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl" are to be construed accordingly.

As used herein, the expression “(C ₁ -C6)perfluoroaIkyr means that all of the hydrogen atoms in said alkyl group are replaced with fluorine atoms. Illustrative examples include trifluoromethyl and pcntafluoroethyl, and straight-chained or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl groups. Derived expression, “(C ₁ -C ₆ )perfluoroalkoxy”, is to be construed accordingly. It should further be noted that certain of the alkyl groups as described herein, such as for example, “(C ₁ -C ₆ )alkyP may partially be fluorinated, tint is, only portions of the hydrogen atoms in said alkyl group are replaced with fluorine atoms and shall be construed accordingly.

As used heron, the expression “(C ₆ -C ₁₀ )aryr means substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. “Substituted phenyl” or “substituted naphthyl” also include any of the possible substituents as further defined herein or one known in the art

As used herein, the expression “(C ₆ -C ₁₀ )aryl(C ₁ -C ₄ )alkyr means that the (C ₆ -C ₁₀ )aiyl as defined herein is further attached to (C ₁ -C ₄ )alkyl as defined herein. Representative examples include benzyl, phenylethyl, 2-phenyIpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.

“Halogen" or “halo” means chkno, fluoro, bromo, and rodo. hr a broad sense, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a few of the specific embodiments as disclosed herein, the term “substituted” means substituted with one or more substituents independently selected from tire group consisting of (C ₁ -C ₆ )alkyl, (C ₂ -C ₆ )alkenyl, (C ₁ -C ₆ )perfluoroalkyl, phenyl, hydroxy, -CO ₂ H, an ester, an amide, (C ₁ -C ₆ )alkoxy, (C ₁ -C ₆ )tfaioalkyl and (C ₁ -C ₆ )perfliioroalkoxy. However, any of the other suitable substituents known to one skilled in the art can also be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text, schemes, examples and tables herein is assumed to have the appropriate number of hydrogen atom(s) to satisfy such valences.

By the term "derived" is meant that the polymeric repeating units are polymerized (formed) from, for example, polycyclic norbomene-type monomers in accordance with formulae (I) to (IV) wherein the resulting polymers are formed by 2,3 enchainment of norbomene-type monomers as shown below:

Accordingly, in accordance with die practice of this invention there is provided a single component composition encompassing: a) one or more olefinic monomers; b) an organopalladium compound of formula (I): herein: each A independently is a bidentatc monoanionic ligand of formula (Π): herein: n is an integer 0, 1 or 2;

X and Y are independently of each other selected from 0, N and S;

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R7 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C ₃ -C ₁₆ )alkyl, (C ₁ -C ₁₆ )perfluoroalkyl, partially (C ₁ -C ₁₆ )fhioroaIkyl, (C ₃ -C ₁₀ )cycloalkyl,

(C ₆ -C ₁₀ )aryl(C ₁ -C ₁₆ )alkyl and substituted or unsubstituted (C ₆ -C ₁₀ )aryl; provided when either X or Y is 0 or S, R ₁ and R ₅ , respectively, do not exist; c) a photoacid generator selected from the group consisting of: a compound of the formula (II): wherein: a is an integer from 0 to 5;

An® is selected from the group consisting of Cl®, Br®,I®, Ns®, BF4®, tetrakis(p fluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyI)phenyl)borBte, tetralris(2- fluorophenyl)borate, tetrakis(3-fluorophenyl)borale, tetrakis(4-fluorophenyl)borate, tetraltis(3,5- difluorophenyl)borale, tetrakis(2,3,4,5-tetrafluorophenyl)bQrate, tetraltis(3, 4,5,6- tetrafluoropheiiyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyhris(perfluorophenyl)borale, ethyhris(perfluorophenyl)borate, phenyltra(perfhiorophenyl)borate, tetrakis(1^2- trifluoroethylcnyl)borate, tetrakis(4-trM-propylsilyltetnrfhiorophenyl)boiate, tetralds(4-dimethyl- tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pen(tafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, telrakis[3,5-bis[l-methoxy-2A2-trifluoro-l- (trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[l-methoxy-2^,2-trifluoro-l-

(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]boraie, and tetrakis[3-[2A2-trifluoro-l-(2,2,2- trifluoroetiK)xy>l-(trifluoromcthyl> ethyl]-5-(trifliioromethyl)phenyl]borale, PFe®, SbFe® ,

1HC ₄ F9SQ3® , CF3SO3 ® andp-O¾(<¾H*)-S03®;

¾,¾, Rio, R11 and R12 are the same or different and each independently selected from the group consisting of halogen, methyl, ethyl, linear or branched (C ₃ -C2o)alkyl, (C ₃ -Ci2)cycloalkyl,

(Ci-Ci2)bicycloalkyl, (C7-Ci4)tricycloalkyl, (Ce-C ₁₀ )aiyl, (Ci-C ₁₀ )aiyl(C ₁ -C3)alkyl, (C ₁ -Ci2>alkoxy, (C ₃ -Ci2)cycloalkoxy, (Ce-C i2)bicyck)alkoxy , (C?-Ci4)tricycloalkoxy, (Ci-Ci2)aiyloxy(C ₁ -C3)alkyl, (Ce-Ci2)aryloxy, (C*-Ci2)aryloxy(C ₁ -C6)aIkyl, (C6-Ci2>thioaiyl, (C i-C6>Ikanoyl(C6-Cu)tiiioaryl, (Ci<l6)alkoxy(C6-Ci2)aroyl(C ₁ -C6)alkyl and (C6-Ci2)-diioaryI-(C6-Ci2)diaylsulf(mium salt; and d) a photosensitizer.

Accordingly, various ole&dc monomers which undergo vinyl addition polymerization can be employed in foe composition of this invention. Such olefinic monomers include without ary limitation alicyclic olefins, such as ethylene, propylene, butylene, styrene, and the like. Other olefinic monomers include cyclo-olefins and bicyclo-olefins, and so on.

In some embodiments of this invention the olefinic monomers which are suitable in foe composition of this invention are of foe formula (V): wherein: m is an integer 0, 1 or 2;

== is a single bond or a double bond;

Ri3, Ri4, RIS and Ri6 are the same or different and each independently selected from the groiq) consisting of hydrogen, halogen, a hydrocaibyl or halohydrocarbyl groiq) selected from methyl, ethyl, linear or branched (C ₃ -C2o)alkyl, perfluoro(C ₁ -Cu)aIkyl, (C ₃ -Cn)cycloalkyl,

(Ce-C i2)bicycloalkyl, (CT-CwXricycloalkyl, (CVC ₁₀ ^uyl, ((¾-C ₁₀ )aryl(C ₁ -(¾)alkyl, perfluoro(C ₆ -C ₁₀ )aryl, perfluoro(CfrC ₁₀ )aryl(C ₁ -C3)alkyl, methoxy, ethoxy, linear or branched (C ₃ -Cie)alkoxy, perfluoro(C ₁ -Ci2)alkoxy, (C ₃ -Ci2)cycloalkoxy, (C6-Ci2)bicycloalkoxy, (CT-C u)tricycloalkoxy, (C«-Ci2)aryloxy, (Ce-Ci2)aryloxy(C ₁ -C6)alkyl, (C6-Ci2)aryl(C ₁ -C6)alkoxy, perfluOTo(C6-Ci2)aiyk)xy, perfluoro(C6-Ci2)aiyl(C ₁ -C3)alkoxy, a groiq) of formula (A):

-Z-Aiyl (A); a group of formula (Al): a groiq) of formula (A2): Q a group of formula (A3): a group of formula (A4): herein:

Z is selected from the group consisting of:

0, CO, C(0)0, 0C(0), 0C(0)0, S, (CRpRjsJb, <XCRI ₇ RII>, (CRnR»)bO, CXOXCRnRuX (CRnRiiMXOX C(0)0(CRi7Ris)b, (CRnRi*)bC(0)0, 0C(0XCRi7Ris)b, (CRnRiiMXXO), (CRi ₇ Rii)b0C(0)0, (CRi ₇ R«)b0C(0)0(CRi7Rn)b, 0C(0)0(CRi7Ris)b, S(CRnRis) _b , (CRj ₇ Rii) _b S, (SiRnRu) _b , 0(SiRnRn)b, (SiRi?Rii)bO, where

Ri7 and RII are the same or different and cadi independently selected from hydrogen, methyl, ethyl, linear or branched (C ₃ -Ci2)alkyl, substituted or unsubstituted (C¾-Ci4)aiyl, methoxy, ethoxy, linear or branched (C ₃ -Ce)alkyloxy, (Cz-Cyacyl, (C2-C«)acyloxy, and substituted or unsubstituted (C6-Cu)aryloxy; and bis an integer from 0 to 12, inclusive;

Aryl is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted mthracenyl substituted or unsubstituted fluorenyl, wherein said substituents are selected from the group consisting of halogen, methyl, ethyl, linear or branched (C ₃ -Ce)alkyl, perfluoro(C ₁ -Ci2)alkyl, (C ₃ -Ci2)cycloalkyl, (Ce-C ₁₀ )aiyl, (Ce-C ₁₀ )aiyl(C ₁ -C6)allqd, perfluoro(Ce-C ₁₀ )aiyl, perfluoro(C ₆ -C ₁₀ )aryl(C ₁ -C3)alkyl, methoxy, ethoxy, linear or branched (Cs-CwXdkoxy, perfluoro(C ₁ -Ci2)alkoxy, (C ₃ -C n)cycloalkoxy , (C6-Ci2)aryloxy, (Ce-Ci2)aryloxy(C ₁ -C«)alkyl, (C6-Cu)aiyl(C ₁ -C6)aIkoxy, perfluoro(C6-C i2)ary loxy and perfluoro(C6-Ci2)aryl(C ₁ -C3)alkoxy; k is an integer from 1 to 12;

R23, ¾4 and ¾s arc the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C ₃ -Cn)alkyl, perfluoro(C ₁ -Ci2)alkyl, methoxy, ethoxy, linear or branched (C ₃ -Cu)alkoxy, (C ₃ -C u)cycloalkyl, (Ce-C i2)bicycloalkyl, (C?-Ci4)tricycloaIkyl, (Ce-C ₁₀ )aryI, (C«-C ₁₀ )aryl(Ci«C6)aIkyl, perfluoro(C«-C ₁₀ )aiyl and perfluoro(C ₆ -C ₁₀ )aiyl(C ₁ -C3)alkyl; or

R23 and R24 taken together witii the intervening carbon atoms to which they arc attached to form a substituted or unsubstituted (Cs-CiOcyclic, (Cs-Ci4)bicyclic or (Cs-Ci4)tricydic ring; and Arylene is substituted or unsubstituted bivalent (Ce-Cu)aryl;

ΟΓ

(me of Ri and R2 taken together with one of R3 and R4 and the carbon atoms to which they are attached to form a substituted at unsubstituted (C _$ -Ci4)cyclic, (Cs-Ci4)bicyclic or (C5-Ci4)tricyclic ring.

More specifically, the Aryl as defined herein is substituted or unsubstituted biphenyl of formula: substituted or unsubstituted substituted at unsubstituted terphenyl of formula: substituted or unsubstituted anthracenyl of formula: substituted or unsubstituted fluorenyl of formula: where R* in each occurrence is independently selected from methyl, ethyl, linear or handled (C ₃ -Cn)alkyl or (Ce-C ₁₀ )aiyl;

The monomers of formula (V) as described herein are themselves known in the literature or can be prepared by any of the known methods in the art to make such or similar types of monomers.

In addition, the monomers as described herein readily undergo mass vinyl addition polymerization, Le., in their neat form without use of any solvents by vinyl addition polymerization using transition metal procatalysts, such as for example, organopalladium compounds as described herein. See for example, U. S. Patent Nos. 7,442,800 B2; and 7,759,439 B2; pertinent portions of which are incorporated herein by reference. The tom “mass polymerization” as used herein shall have the generally accepted meaning in the art That is, a polymerization reaction that is generally carried out substantially in the absence of a solvent In some cases, however, a small proportion of solvent is present in the reaction medium. For example, such small amounts of solvent may be used to dissolve the organopalladium compound of formula (I), a photoacid generator or photosensitizer as described herein or convey the same to the reaction medium. Also, some solvent may be used to reduce the viscosity of the monomer. The amount ofsolvcnt that can be used in the reaction medium may be in the range of 0 to 5 weight percent based on the total weight of the monomers employed. Any of the suitable solvents that dissolves the organopalladium compound of formula (I), a photoacid generator or photosensitizer and/or monomers can be employed in this invention. Examples of such solvents include alkanes, cycloalkanes, aromatics, such as toluene, ester solvents such as ethyl acetate, THF, dichloromethane, dichloroethane, and the like.

Advantageously, it has now been found that one or more of the monomers themselves can be used to dissolve the organopalladium compound of formula (I) or a photoacid generator or photosensitizer and thus avoiding the need for the use of solvents. In addition, one monomer can itself serve as a solvent for die other monomer and dins eliminating the need for an additional solvent For example, if a first monomer of formula (V) is a solid at room temperature, then a second monomer of formula (V), which is a liquid at room temperature can be used as a solvent for the first monomer of formula (V) which is a solid or vice versa. Therefore, in such situations more than one monomer can be employed in the composition of this invention. in some embodiments, the monomers of formula (V) employed in the composition of this invention may serve as high refractive index materials imparting high refractive index to the resulting polymeric film upon mass polymerization. In general, the monomers of formula (V) which are suitable in this invention feature a refractive index of at least lJ. In some embodiments die refractive index of the monomers of formula (V) is higher than 1.5. In some other embodiments the refractive index of the monomers of formula (V) is in the range from about 1.5 to 1.6. In yet some other embodiments die refractive index of the monomers of formula (V) is higher than 1.55, higher than 1.6 or higher than 1.65. In some other embodiments it may even be higher than 1.7,

In some other embodiments, it is generally contemplated that monomer of formula (V) may also be used as a viscosity modifier. Accordingly, in general, such a monomer of formula (V) is a liquid at room temperature and can be used in conjimction with another monomer of formula (V) which is a solid or a high viscosity liquid.

In a further embodiment of this invention die composition of tins invention encompasses at least two different monomers of formula (V) and is in a clear liquid state having a viscosity below 100 centipoise. In general, the composition of this invention exhibits low viscosity, which can be below 100 centipoise. In some embodiments, the viscosity of die composition of this invention is less than 90 centipoise. In some other embodiments the viscosity of die composition of this invention is in the range from about 10 to 100 centipoise. hi yet some other embodiments the viscosity of die composition of this invention is lower than 80 cP, low» than 60 cP, lower than 40 cP, lower than 20 cP, . In some other embodiments it may even be lower than 20 cP.

When the composition of this invention contains two monomers, they can be present in any desirable amounts that would bring about the intended benefit, including either refractive index modification or viscosity modification or both or any other desirable property depending upon the intended final application. Accordingly, the molar ratio of first monomer of formula (V) to second monomer of formula (V) can be from 0:100 to 100:0. That is, only one monomer of formula (V) can be employed in certain applications. In other words, any amount of these two monomers can be employed. In sane embodiments, the molar ratio of first monomer of formula (V):second monomer of formula (V) is in the range from 1:99 to 99:1; in some other embodiments h is from 5:95 to 95:5; it is from 10:90 to 90:10; it is from 20:80 to 80:20; it is from 30:70 to 70:30; it is from 60:40 to 40:60; and it is 50:50, and so on.

In general, the compositions in accordance with the present invention encompass the above described one or more of monomer of formula (V), as it will be seen below, various composition embodiments are selected to provide properties to such embodiments that are appropriate and desirable for the use for which such embodiments are directed, thus such embodiments are tailorable to a variety of specific applications. Accordingly, in some embodiments the composition of this invention contains more than two distinct monomers of formula (V), such as for example three different monomers of formula (V) or four different monomers of formula (V).

For example, as already discussed above, proper combination of different monomers of fbnnula (V) makes it possible to tailor a composition having the desirable refractive index, viscosity and optical transmission properties, among other properties, hi addition, it may be desirable to include other polymeric or monomeric materials which are compatible to provide desirable optical properties depending upon the end use application. Accordingly, the compositions of this invention can also include other high refractive polymeric materials which will bring about such intended benefit Examples of such polymers include without any limitation, poly(<x-methylstyrene), poly(vinyl-toluene), copolymers of a-methylstyrene and vinyl-toluene, and the like.

Advantageously, it has further been found that the compositions of this invention can also contain additional monomers different from the monomer of formula (V). In some embodiments, the composition according to this invention may further contain one or more monomers selected from monomer of formula (VI) or monomer of formula (VII).

The monomer of formula (VI) is: wherein: o is an integer from 0 to 2, inclusive;

D is S1R29R30R31 or a group selected from: c isan integer from 1 to 10, inclusive, and where one or more of GHz is optionally substituted with (C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )perfluoroalkyl;

Ras, R27 and Rae are the same or different and independently of each other selected from hydrogen, halogen and hydrocaibyl, where hydrocarbyl is selected from methyl, ethyl, linear or branched (C ₃ -Ci2)alkyl, (C ₃ -Ci2)cycloalkyl, (C6-Ci2)bicycloalkyl, (C7-Cu)tricycloalkyl, (Ce-C ₁₀ )aiyl, (CVC ₁₀ )aryl(C ₁ -C3)aIkyl, (C ₁ -Cu)alkoxy, (C ₃ -Ciz)cycloalkoxy, (Ο _ό -C i2)bicycloalkoxy, (C7-Ci4)tricycloalkoxy, (C ₆ -C ₁₀ )aiyloxy(C ₁ -Cs)alkyl and (C ₆ -C ₁₀ )aryloxy; and

R», R30 and R31 arc each independently of one another methyl, ethyl, linear or branched (C ₃ -C9)alkyl, substituted or unsubstituted (C6-Ci4)aryl, metiioxy ethoxy, linear or branched (C ₃ - Cg)alkoxy or substituted or unsubsrituted (C6-Ci4)aiyloxy.

In this aspect of the invention, it has now been found that monomers of formula (VI) provides further advantages. Namely, the monomers of formula (VI) depending upon the nature of the monomer may impart high or low refractive index to the composition, thus it can be tailored to meet the need. In addition, the monomers of formula (VI) generally improve the adhesion properties and thus can be used as “adhesion modifiers.” Finally, the monomers of formula (VI) may exhibit low viscosity and good solubility for the procatalyst and/or activator, among various other advantages. The monomer of formula (VII) is: vAerein:

Zi is selected from the group consisting of substituted or unsubstituted (C ₁ -Ci ₂ )alkylene, -(ΟΗ2>Κχα½>Γ, -(CHaMSiRasRasXOSiRwRnMCHz)·- where d, e and fare independently integers from 0 to 6, inclusive, Ras, Ra& R«o and R41 are the same or different and independently of each other selected from methyl, ethyl, linear or branched (C ₃ -Cn)alkyl, and an arylene selected from the following:

R32, R33, R34, R35, R36 and R37 are the same or different and independently of each other selected from hydrogen, halogen and hydrocarbyl, where hydrocarbyl is selected from methyl, ethyl, linear or branched (C ₃ -Ci2)alkyl, (C ₃ -Ci2)cycloalkyl, (C«-Ci2)bicycloalkyl, (C7-Ci4)tiicyck)alkyl, (C«-C ₁₀ )aryl, (C ₆ -C ₁₀ >nyl(C ₁ -C3)alkyl, (C ₁ -Ci2)alkoxy,

(C ₃ -Cu)cycloalkoxy, (OCi2)bicycloalkoxy, (CrCu)tricycloalkoxy, (Ce-C ₁₀ )aiyloxy(C 1 -C3)alkyl or (C«-C ₁₀ )aryloxy.

The monomers of formula (VII) are bifunctional monomers and may exhibit high refractive index especially when Zi is an aiylene group. Accordingly, it is contemplated that incorporation of monomers of formula (VII) into composition of this invention generally increases the refractive index of the composition and also increase crosslinkability with other molecules. Thus, by incorporation of monomers of formula (VII) into the composition of this invention it may be possible to increase compatibility with other materials depending upon the intended application thereby enhancing the properties of the composition of the invention.

In another aspect of this invention it is conceivable that the composition of this invention may contain only one monomer of formula (V) or formula (VI) or formula (VII). That is, any one of die monomers of formulae (V) to (VII) may be sufficient to form a composition of this invention. In some other embodiments the composition of this invention encompasses any two monomers of formulae (V) to (VII) and in any desirable proportions. In some other emb i the composition of this invention encompasses any three monomers of formulae (V) to (VII) in any combinations thereof and in any desirable proportions. All such possible permutations and combinations of monomers of formulae (V) to (VII) are part of this invention.

Accordingly, any of the monomers within the scope of monomer of formula (V) can be employed in the composition of the invention. Representative examples of monomer of formula (V) include the following without any limitations: 2-(bicyclo[2.2.1 ]hept-5-en-2-ylmcthyl)naphthalene;

1 -<bicyclo[22.1 ]hept-5-m-2-ylmethyl)naphthalene;

2-((3-methylbicyclo[2.2, 1 ]hcpt-5^-2-yl)methyl)naphthalcne;

2-(bicyclo[2.2.1 jhcpt-5-en-2-yfaethyl)-7-methylnaphthalene;

5-([l,l '-biphcnyl]-3-ylmethyl)bicyck)[22.1 ]hept-2-ene;

5-((2'-methyl-[l ,1 '-biphenyl]-3-yl)mctiiyl)bicyclo[22.1 ]hept-2-ene;

5-([l,l '-biphery l]-4-ylmethyl)bicyclo[2.2.1 ]hept-2-ene:

5-([l,l '4>iphenyl]-2-ylmethyl)bicyclo[2.2.1 ]hept-2-ene;

5-(2-([l, 1 '-biphenyl]-4-yl)ethoxy)bicyclo[2.2. l]hept-2-ene;

5-(2-(2 ^, ,4 ^, -dimethyl-[ 1 , 1 '-biphenyl]-4-yI)ethoxy)bicyclo[22.1 ]hept-2-ene; bicyck>[2.2.1 ]hept-5-en-2-yl 2-([l , 1 '-biphenyl]-4-yl)acetate;

X bicyclo[22.1 ]hept-5-en-2-ylmethyl [l,l'-biphcnyll-4-carboxylate;

5-(2-([l ,1 '-biphenyl]-4-yloxy)cthyl)bicyclo[2.2.1 Jhept-2-ene;

X

5-(2-([l , 1 '-biphenyl]-2-yloxy)ethyl)bicyck>[2.2.1 ]hept-2-ene (NBEtOPhPh);

5-(2-([l,l ^, -biphenyl]-2-yloxy)mcibyl)bicyclo[2.2.1]hq)t-2-ene (NBMeOI¾Ph); >

[1,1 '-biphenyl]-4-yl 2-(bicyclo[2.2.1 ]hept-5-cn-2-yl)acctatc;

5-(4-([l , 1 '-biphenyl]-4-yl)butyl)bicyclo[2.2.1 ]hept-2-ene; u

(9H-fluoren-9-yl)methyl (bicyclo[22.1 ]h wept-5-en-2-y hnethy 1) carbonate;

(9R,10S,11 R, 12S)-9, 10-dihydro-9, 10-[2]bicycloanthracene;

1 -(4-bicyclo[2.2.1 ]hept-5-en-2-ylmethyl)-3, 4-dimethyl- 1 H-pyirole-2^-dione

(McDMMINB); l-(4-bicyclo[2.2.1]hq>t-5-en-2-ylethyl)-3,4-dimcthyl-lH-p ym)le-2,5-dione

(EtDMMINB); l-(4-bicyclo[2.2.l]hept-5-en-2-ylpropyl>3,4-dimetiiyl-lHi )ym)le-2^-dione

(PrDMMINB);

^Q l-(4-bicyclo[2.2.1]l^)t-5-en-2-ylbutyl>3,4-dimcthyl-lH-py rrole-2^-dione l -<4-bicyclo [2.2.1 ]hqrt-5-en-2-ylpentyl)-3,4-dimctiiyl- 1 H-pyrrolc-2^-dione

(PentylDMMINB); l -(4-bicyclo[22.1 ]hept-5-en-2-ylhexyl)-3,4-dimcthyl- 1 H-pyrrole-2,5-dione

(HxDMMINB);

1 -(4-bicyclo[2.2.1 ]hept-5-en-2-ylethyl)l,4-jdiaiylene-3,4-dimetiiyl-lH-pym)le- 2^- dione (EtPhDMMINB);

1 -(4-bicyclo[2.2.1 ]hept-5-en-2-ylmethyl)-3-methyl- 1 H-pyrrole-2^-dione

(MeMMINB);

1 -(4-bicyclo [22.1 ]hept-5-en-2-ylmethyl)- 1 H-pyrrole-2^-dione (MeMINB);

1 -(4-bicyclo [2.2.1 ]hcpt-5-cn-2-ylethyl)- 1 H-pyirole-2,5-dioBe (EtMINB);

NBDHNMI; bicyclo[2.2.1 ]hept-5-en-2-ylmethyl 4-methoxy-cinnamate (NBMcMeOCmn);

0 bicyclo[2.2.1]hept-5-en-2-ylmcthyl cinnamatc (NBMeCinn); bicyclo[22.1 ]hept-5-en-2-ylethyl 4-metboxy-cinnamate (NBEtMeOCinn);

7-(bicyclo[2.2.1 ]hejrt-5-en-2-ylmcthoxy)-2H-chromen-2-onc (NBMeCoum);

7-(2-(bicyclo[2.2. lJhept-5-en-2-yl)ethoxy)-2H-diromen-2-onc (NBEtCoum);

5-(4-phenylbutyI)bicyclo[2.2.1 ]hept-2-ene (phenylbutyINB); .0.

5-(2-phenoxyethyl)bicyclo[2.2.1 ]hcpt-2-cne; xX XX

5^3-phenylpropyl)bicyclo[2.2.1 ]hept-2-ene;

5-phenethoxybicyclo [2.2.1 ]hept-2-cne;

5-{(benzyloxy)methyl)bicyclo[2.2.1 ]hept-2-ene;

5-(pfaenoxymethyl)bicyclo[2.2.1]hept-2-cnc;

5-pheaethy lbicyclo[2.2.1 ]hept-2-me (PENB);

5-(benzyloxy)bicyclo[22.1 ]hept-2-ene;

5-cy clohcxy ^Q Ibicyc ^y lo[2.2. ^O 1 ]hept-2-ene (cyclohexylNB); 5-ph GenylbicKyclo[2.2. l]hept>-2-ene (PtiNB);

5-hexylbicyclo[2.2.1 ]hept-2-eoe (HexNB);

5-octyIbicyclo[2.2.1 ]hcpt-2-ene (OctNB);

5-decylbicyclo[22.1 ]hept-2-ene (DecNB);

5-dodecylbicyclo[22.1 ]hept-2-ene (DoDccNB);

5-tetradccylbicyclo[2.2.1]hq)t-2-cne (TetraDecNB);

5-hexadecyIbkyclo[2.2.1 ]hept-2-ene (HexaDecNB); tetracyclododecene (TD); V

2-phcnyl-tetracyclododecenc (PhTD);

2-benzyl-lA3,4,4a^,8,8a-octahydro-l,4:5,8-(Umethanon¾)ht iialene;

2-phe∞thyl-1^3,4,4a^,8,8a-octahydro-l,4:5,8-dimcthaim¾ *thalaM (PETD);

2-butyl-lA3A4a^8,8a-octahydro-M:5,8-dimethanonaphthalene (ButylTD);

2-hexyl-1^3,4,4a^,8.8a-octahydro-l ,4:5,8-dimethanonq)hthal«ie (HexylTD);

2-octyl- 1 Λ3 ,4,4a,5 ,8,8a-octahydro- 1 ,4:5,8-dimetiianoiM¾)hthalaie (OctylTD);

2-decyl-l^A4a^,8,8a-octahydro-l _> 4:5,8-dimethanonaphthalene (DecylTD); 2-cyclohexyl-tetracyclododecene (CyclohexylTD);

2-cyclohexyhnethyl-½3,4,4a,5,8,8a-octidiydro-l,4:5,8-dim ethanonq)htiialene;

( 1 _> 2 _> 3 _> 4 _t 4a,5 _t 8 _> 8a-octahydro-l _> 4:5,8-dime&anonaphflialen-2-yl)m^lyl acetate

(TDMeOAc).

Turning now to monomer of formula (VI) to form the composition of this invention it is contemplated that any monomer within the scope of monomer of formula (VI) can be employed. Exemplary monomers of such type include but not limited to those selected from the group consisting of:

(bicyclo[22.1 ]hept-5-m-2-ylmethoxyXmethyl)diphenylsilarie (NBCHaOSiMePhz); XX

%

(bicyclo[22.1 ]hept-5^-2-ylmethoxyXethyl)diphenylsilane;

(bicyclo[22. l]hq)t-5-en-2-ylmctiioxyXe%lXmctiiylXphenyl)silanc;

(bicyclo[22.1 ]hqjt-5-en-2-ylnwthoxy)dimethyl(phaiyl)silanc;

SKOCH ₃ ) ₃ bicyclo[2.2.1 ]hept-5-en-2-yltrimetiK)xy silane; bicyclo[2.2.1 ]hept-5-en-2-yltriethoxysilane (TESNB, NBSi(OC2¾)3);

Si(OCH ₃ )2(Ot-Bu) bicyclo[22. l]hept-5^-2-yl(tert-butoxy)dimethoxysilane; Si(OMe) ₃

(2-(bicyclo[2.2.1 ]hept-5-en-2-yl)e&yl)trimethoxy silane;

(2<bicyclo[2.2.1 ]hept-5-en-2-yl)ethylXmethyl)diphenylsilane; and

1 -(bicyclo[2.2. l]bept-5-en-2-yl)-l,l ,3,3^-pcntamethyldisiloxanc.

Turning now to monomer of formula (VII) to form the composition of this invention it is contemplated that any monomer within the scope of monmner of formula (VII) can be employed. Exemplary monomers of such type include but not limited to those selected from the group consisting of:

1 ,4-di(bicyclo[22.1 ]hept-5-en-2-yl)benzene;

4, 4'-di(bicyclo[2^. l]hept-5-en-2-yl)-l ,1 '-biphenyl; 4,4 ⁿ -di(bicyclo[22.1 ]hept-5-en-2-yl)- 1,1':4\ 1 "-taphcnyl;

U-di(bicyclo[22.1 ]hept-5 -ca-2-y 1)- 1 , 13^-tetrametiiyklisiloxane, when x - 1 and 1 ,5-di(bicyclo[2.2.1 ]hept-5-cn-2-yl)- 1 , l^^-hexamethyhrisiloxaiie, when x=2;

1 ,4-di(bicyck)[22.1 ]hept-5-en-2-yl)butane;

5^*-(oxybis(etiiane-2, 1 -diyl))bis(bicyclo[2.2.1 ]hept-2-ene);

5^'-((F ^t ¾> ^ane -22-diylbis(oxy))bis(mediyleac))bis(bicyclo[22.1 ]hept-2-ene); kNi

13-W∞*ommylethylH ,1 _» 3^-tetrame%ldisiloxane (BisNBEt-Disiloxane); and /N- ίι

1 ,5-bis(norbomenylethyl)- 1 , 1 ,33,5,5, -hexamethyltrisiloxane (BisNBEt-Trisiloxane).

In a further embodiment, the composition of this invention encompasses one or more monomers of formula (V) and at least one monomer of formula (VI).

In another embodiment, the composition of this invention encompasses one or more monomers of formula (VI) and at least one monomer of formula (VII) and optionally one monomer of formula (V).

In yet a further embodiment, the composition of this invention encompasses at least one monomer of formula (V) and at least one monomer of formula (VI), and optionally one monomer of formula (VII).

In yet a further embodiment, the composition of this invention encompasses one monomer of formula (VI), optionally one or more monomers of formula (V) or monomer of formula (VII).

In a further embodiment of this invention, the composition contains any of the organopalladium compounds of formula (I) that would bring about the mass polymerization as described herein. Generally, such suitable organopalladium compound of formula (I) contains a bidentate monoanionic ligand which is selected from the group consisting of: Several of die oiganopalladium compounds of formula (I) that are suitable to be employed in die compositions of this invention are known in the literature or can be readily made by any of the known procedures in the art. See for example, U. S. Patent Nos. 7,442,800 B2 and 7,759,439 B2, pertinent portions of which are incorporated herein by reference.

Exemplary oiganopalladium compounds of formula (I) that can be employed in the composition of this invention without any limitation include the following: palladium (acetylacetonate)2 (Pd(acac)2 or Pd304); palladium (hexafluoroacetylacetonatc)2 (Pd(hfac)2 or Pd520); palladium d(tmhd)2 or Pd473); palladium (trifluoroacetylacetonate)2 (Pd(tfacac)2); palladium (l,l,l,5,5,6,6,6-octafluorohexane-2,4-dionate)2; CFi 5

Pd X

Vs 1 palladium (1,1,1 ^^,6,6,6-octafluorohexane-2,4-dionale)2 (Pd620); palladium (1,1,1 ^J,3,7,7,8,8,9^>4etradecafliiorononan&4,6-dionatc)2 (Pd920); palladium (l-phenylbutane-l,3-dionate)2 Pd428;

J a

'3 palladium (2-((phmylimmo)methyl)phaioate)2 (Pd498).

As noted, the conyosition of this invention further contains a photoacid generator which when combined with the oiganopalladium compound of formula (I) and a photosensitizer will cause mass polymerization of the monomers contained therein when exposed to suitable radiation as described herein. Any of the known photoacid generators can be used in the compositions of this invention, such as for example, certain of the halonium salts.

In some embodiments the photoacid generator of the formula (TV.) are employed in the composition of this invention:

Aryli-Hal®-Aiyh An© (IV.)

Wherein Aryh and Aiyh are the same or different and are independently selected from the group consisting of substituted or unsubstituted phenyl, biphenyl and naphthyl; Hal is iodine or bromine; and An© is a weakly coordinating anion (WCA) which is weakly coordinated to the cation complex. More specifically, the WCA anion functions as a stabilizing anion to the cation complex. The WCA anion is relatively inert in that it is non-oxidative, non-reducing, and non-nucleophilic. In general, the WCA can be selected from borates, phosphates, arsenates, antimonates, aluminates, boratobenzene anions, carborane, halocaiboianc anions, sulfonamidate and sulfonates

Representative examples of the compounds of formula (IV ·) may be listed as follows: Wherein Rii and R« are as defined herein. Similarly various sulfonhim salts can be used as photoacid generators, which include broadly compounds of formula (ΠΙ) as described hoein.

Accordingly, non-limiting examples of suitable photoacid generators of formula (ΙΠ) that may be employed in the composition of this invention are listed below: (2-(4-methoxynaphthalen-l -yl)-2-oxoethyl)dimethylsulfonium tetrakis(perfluorophenyl)boiHte, commercially available as TAG 382; tris(4-((4-acetylphcnyl)titio)phenyl)sulfbmum tris((trifluoromethyl)sulfiMiyl>ndhanide;

Φ e

PF«

(4-tMophenyl)phenyl-diphenylsulfomum hexafluoiophosphate; bis-(triphenylsulfbimmi) sulfide bis- hexafluorophospha!e; tris(4-tert¾itylphenyl)sulfomum perfluoro-1 -butanesulfonate; tris(4-tert-butyl^Knyl)sulfonhmi Inflate;

Θ

Cl triphenylsulfonium chloride;

(4-phenoxyphenyl)diphenylsulibmum triflate; and tris(4-((4-acetylphenyl)ttio)phenyl)sulfbnimn tetrakis-pcrrtafluorophcnylborate (Irgacure

PAG290).

Non-limiting examples of suitable photoacid generators of formula (IV) that may be employed in the composition of this invention are listed below:

F F tolylcumyliodonium-tetrakis pentafluorophenylborate, commercially available under the tradename Rhodorsil 2074® fiom Bluestar Silicones;

[4-(octyloxy)phenyl]-phenylioclomum (hexafluoro)phosphatc (OPPI PF();

[4-(cretyloxy)pbcnyl]-phenyliodcMiium (hexafluoro)anlimonate (OPPI SbFe);

(4-ethylphcnylX4-isopropylphe^l)i<xk>nium tctralds(perfluorophcnyl)boraie; e CF ₃

0 ^sS ^ ii ^¾¾ 0 X

L di-(p4¾tylphenyI)iodomum tris(trifluoromcthanesulfbnyl^iaetiiam(k; bis(4-tCTt-butylphenyl)iodonium perfluoro- 1 -butanesulfonate; bi3(4-tert-butylphet]yl)iodonium p-toluenesulfonate;

FJC ,θ bis(44ert-butylphmyl)iodonium inflate;

E,

R42

F where R42 and R43 are the same or different and each independently selected from linear or branched (C ₁₀ -Ci3)alkyl, for example, iodonium, diphenyl-4, 4'<li-(C ₁₀ -Ci3)alkyl derivatives, tetrakis(2^4,5,6^entafluorophenyl)borates is commercially available under the tradename SHCOLEASE UV CATA 243; and ΐ cr diphenyliodonium chloride.

Other exemplary PAGs that may be suitable in the composition of this invention include the following: triphenylsulfonium 4,4,5,5,6,6-hexafhioro-l ,3,2-dithiazinan-2-ide 1,1,3,3-tetraoxide; tris(4^tcrt4>utyl)phenyl)sulfonium 4,4,5,5,6,6-hexafluoro- 1 ^^-dhhiazinan-2-ide 1, 1,3,3- tctraoxidc;

Θ

F ₂ 1 -{4-(tcrt-butyl)phmyI)hexahydrothiopyrylium 4,4,5,5,6,6-hexafluoro-l 3^-dithiazinan-2-ide

1,1,33-tctraoxide;

1 -(4-(tert-butyl)pbenyl)tetrahydro- 1 H-thiophcn-1 -ium 4,4,5,5,6,6-hexafiuoro- 1 ,3 ,2-dithiazinan-2- ide 1,1,3,3-tetraoxide; and

2,4,6-triisopropylbaizcncsulfonyl azide. However, any of die other known photoacid generators which can activate the organopalladium compounds of formula (I) as employed herein when exposed to suitable radiation can also be used in the composition of this invention. All such compounds are part of this invention.

As noted, the composition of this invention additionally contains a photosensitizer compound which further facilitates the formation ofthe active catalyst when the composition is exposed to suitable radiation in the presence ofthe photoacid generator as employed herein. For this purpose, any suitable sensitizer compound can be employed in the compositions of the present invention, which activates tiie photoacid generator and/or the organopalladium compound of formula (I). Such suitable sensitizer compounds include, anthracenes, phenantinenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes, xanthones, indanthrenes, thioxanthen-9-ones, and mixtures thereof. In some exemplary embodiments, suitable sensitizer components include a compound of formula (VIII) or a compound of formula (IX): wherein

R44, R4 _$ and R46 are tiie same or different ami independently of each other selected from the group consisting of hydrogen, halogen, hydroxy, NQ¾ NH¾ methyl, ethyl, linear or branched (C ₃ -Cu)alkyl, (C ₃ -Ci2)cycloalkyl, (Ce-Ci2)bicyGloaIkyl, (C7-Ci4)tricycloalkyl, (C ₆ -C ₁₀ )aryl, (C ₆ -C ₁₀ )aiyl(C ₁ -C3)alkyl, (C ₁ -Ci2)alkoxy, (C ₃ -Ci2)cycloalkoxy, (C6-Ci2)bicycloalkoxy, (C7-Ci4)tricycloalkoxy, (C ₆ -C ₁₀ )aiyk>xy(C ₁ -C3)alkyl, (Ci-C ₁₀ )aiyloxy, C(OXC ₁ -C6)aIkyl, COOH, C(OXXC ₁ -C6)all^l,andS02(OC ₁₀ )aiyl;

R47 and EUs are the same or different and independently of each other selected from the group consisting of methyl, ethyl, linear or branched (C ₃ -Cn)alkyl, (C ₃ -Ci2)cycloalkyl, (C6-Cu)bicycloalkyl, (C7-Ci4)tricycloalkyl, (Ce-C ₁₀ )aryl and (C ₆ -C ₁₀ )aryl(C ₁ -C3)alkyl.

Representative examples of the compounds of formula (VIII) or the compounds of formula (DC) without any limitation may be listed as follows: X

X

1 -chloro-4-methoxy-9H-thioxantiicn-9-one;

0

V

1 -chloro-4-ethoxy-9H-thioxanlhen-9-one;

1 -chloro-4-pix¾x)xy-9H-thioxanthai-9-oM (commercially sold under the name CPTX from

Lambson);

1 ^hloro-2-propoxy-9H-thioxanthen-9-one;

1 -chloro-2-ethoxy-9H-thioxanthen-9-one;

1 -chloro-2-methoxy-9H-thioxanthen-9-one;

1 -chlao-4-methyl-9H-tiiioxantiien-9-<me;

1 -chloro-4-ethyl-9H-thioxantiien-9-one;

Ph

1 -diloro-4-phenoxy-9H-tiiioxaiithen-9-onc; o

V

2-chlorothioxanthen-9-one (CTX);

2-isopropyl-9H-thioxanthen-9-one (ITX); 4-isopropyl-9H-thioxanthen-9-one;

9,10-dimethoxyanthracene (DMA);

OEt

9, 10-diethoxyanthracene (DEA) ; and

0¾u

0¾u

9, 10-di-n-butoxyanthracene (DBA).

Other suitable photosensitizer compounds include various substituted and unsubstituted phenothiazine derivatives, such as for example: fl phenothiazine.

Generally, photosensitizers absorb energy from the radiated light source and transfers that energy to the desirable substrate/reactant, which in the present invention is the photoacid generator employed in the composition of this invention. In some embodiments the compounds of formula (ΠΙ) or the compounds of formula (IV) can be activated at certain wavelength of the electromagnetic radiation which can generally range from about 240 mn to 410 nm. Accordingly, any of the compounds which are active in this electromagnetic radiation can be employed in the compositions of this invention which are stable to various fabrications methods where the compositions of this invention can be used including for example OLED or the 3D ftbrication methods. In some embodiments the wavelength of the radiation to activate the compounds of formulae (ΠΙ) or (IV) is 260 nm. In some other embodiments the wavelength of the radiation to activate the compounds of formula (V) is 310 nm. In some other embodiments the wavelength of the radiation to activate the compounds of formula (V) is 365 nm. In yet some other embodiments the wavelength of the radiation to activate the compounds of formula (V) is 395 nm.

Any amount of organopalladium compound of formula (I), the photoacid generator of formulae (ΙΠ) or (IV) and the photosensitizer of formulae (VIII) or (IX) can be employed in the composition of this invention which will bring about the intended result Generally, the molar ratio of monomer of formula (V):compound of formula (I) is in the range of 25, 000:1 to 5, 000:1 or lower.

In some other embodiments such monomer of formula (V):compound of formula (I) is 10,000:1, 15,000:1, 20,000:1 or higher than 30,000:1. It should be noted that monomer of formula (V) as mentioned herein may include one or more monomers of formula (V) distinct from each other and may additionally contain one or more monomers of formulae (VI) or (VII), and therefore, the above ratio represents combined molar amounts of all such monomers employed. Similarly, the molar ratio of organopalladium compound of formula (I)flhe photoacid generator of formulae (ΠΙ) or (IV).-the photosensitizer of formulae (VIE) or (IX) is in the range of 1:1:0.5 to 1 ΊΊ or 1:2:1 or 1:4:1, 1:2:4, 1:1:2, 1:4:2 or such ranges which will bring about the intended benefit

Advantageously, it has further been found that the composition according to this invention forms a substantially transparent film when exposed to a suitable actinic radiation (UV irradiation). That is to say that when the composition of this invention is exposed to certain actinic radiation, the monomers undergo mass polymerization to form films which are substantially transparent to visible light That is, most of the visible light is transmitted through the film. In some embodiments such film formed from the composition of this invention exhibits a transmission of equal to or higher than 90 percent of the visible light In some other embodiments such film formed from the composition of this invention exhibits a transmission of equal to or higher than 95 percent of the visible light It should be further noted that any actinic radiation that is suitable to carry out this mass polymerization can be employed, such as for example, exposure to any actinic radiation in the wavelength of 200 nm to 400 nm. However, any radiation higher titan 400 nm can also be employed. In some embodiments the wave length of the actinic radiation employed is 250 nm, 295 nm, 360 nm, 395 nm or higher than 400 nm. in acme other embodiments the composition of this invention undergoes mas» polymerization when exposed to suitable actinic radiation and heat to form a substantially transparent film. In yet other embodiments the composition of this invention undergoes mass polymerization when exposed to suitable UV irradiation at a temperature from 50 °C to 100 °C to form a substantially transparent film.

Accordingly, exemplary compositions of tins invention without any limitation may be enumerated as follows:

5-(2-chloroethyl)bicyclo[2.2.1 ]hept-2-ene (NBEtCl), 5-phenethylbicyclo[2.2.1 ]hept-2-ene (PENB), palladium (acetylacetonate)2, tolylcumyliodonium-tetralds pentafluorophenylborate (Rhodorsil 2074) and 2<hk*o-9H-thioxanthen-9-one (CTX);

5-(2-chloroethyl)bicyclo[2.2.1 ]hept-2-ene (NBEtCl), 5-phenethylbicyclo[2.2.1 ]hept-2-ene (PENB), palladium (acetylacetonate)¾ tolylcumyUodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074) and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-(2-chloroethyl)bicyclo[2.2.1 ]hept-2-ene (NBEtCl), 5-phenethyIbicyclo[2.2.1 ]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate)2, tolylcumyliodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074) and 2-chloro-9H-thioxanthen-9-one (CTX);

5-(2-([ 1 , 1 '-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1 ]hept-2-ene (NBEtOPhPh), 5- pbenethyIbicyclo[2.2. l]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate)2, tolylcumyliodonium-tetralds pentafluorophenylborate (Rhodorsil 2074) and 2-isopropyl-9H- tiiioxantiien-9-one (ITX);

5-(2-([ 1 , 1 '-biphenyl]-2-yloxy)etiiyl)bicyclo[2.2.1 ]hept-2-ene (NBEtOPhPh), 5- phenethylbicyclo[2.2. l]bept-2-ene (PENB), palladium (hexafluoroacetylacetonate):, 4- (octyloxy)phenyl)(phenyl)kxlonium hexafluorophosphate (OPPI-PFe) and 2-isopropyl-9H- thioxanthen-9-one (ITX);

5-(2-([l , 1 '-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1 ]hept-2-ene (NBEtOPhPh), 5- phenetiiylbicyclo[2.2.1 ]hept-2-aie (PENB), palladium (hcxafluoroacetylacetonate)¾ 4- (octyloxy)phenyl)(phenyl)iodonium hexafluoroantimonate (OPPI-SbFe) and 2-isopropyl-9H- thioxanthen-9-one (ITX);

5-(2-([l,r-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-e ne (NBEtOPhPh), 5- decylbicyclo[22.1]hept-2-me (DecNB), palladium (hexafluoroacetylacetonate^, tolylcmnyliodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074) and 2-isopropyl-9H- thioxanthm-9-one (FIX); 5-phenethylbicyclo[2.2. lJhqjt-2-cnc (PENB), 5-(2-([l,l ^, -biplienyl]-2- yloxy)ethyl)bicyclo[22.1 ]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1 ]hept-2-ene (DecNB), palladium (hexafluoroacetylacetonate)2, tolylcumyliodomum-tetrakis pentafluorophenylborate (Rhodorsil 2074) and 2-isopropyl-9H-thioxanthen-9-one (ΓΓΧ);

5-(2-chloroetfayl)bicyclo[2.2.1 ]hept-2-cne (NBEtCl), 5-(2-([l,V-biphenyl]-2- yloxy)ethyl)bicyclo[2.2.1 ]hept-2-ene (NBEtOPhPh), 5-phenethylbicyclo[2.2.1 ]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate)2, tolylcumyliodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074) and 2-cMoro-9H-thioxanthcn-9-one (CTX); 5-phenethylbicyclo[2.2. l]hept-2-ene (PENB), 5-(2-([l,l'-biphenyl]-2- yloxy)ctiiyl)bicyclo[2.2.1 ]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1 ]hcpt-2-ene (DecNB), palladium (acetylacetonateX, tolylcumyliodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074) and 2-isopropyl-9H-thioxanlhen-9-one (ITX);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), 5-(2-([l,r-biphcnyl]-2- yloxy)cthyl)bicyclo[2.2.1 ]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1 ]hept-2-ene (DecNB), palladium (tetramethylheptenonoateX, tolylcumyliodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074) and 2-isopn¾>yl-9H-thioxanflien-9-one (ITX);

5-phenethylbicyclo[2.2. l]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate)2, (2- (4-metlx)xynaphthalen-l-yl)-2-oxoethyl)dimethylsulfonium tetrakis-pentafluorophenylborate (TAG 382) and 9, 10-diethoxyanthracene (DBA);

5-phenethylbicyclo[2.2.1 ]hept-2-ene (PENB), palladium (hexa£luoroacetylacetonate)¾ tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tetrakis-pentafluorophenylborate (Irgacure PAG290) and 9,10-diethoxyanthracene (DEA);

5-phenethylbicyclo[22. l]hept-2-ene (PENB), palladium (hexafluoroacetylacetonateX, iodonium, diphenyl-4, 4'-di-(C ₁₀ -Ci3)alkyl derivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borates (SILCOLEASE UV CATA 243) and 2-isopropyl-9H-thioxanthen-9-one (ITX); 5-hexadecylbicyclo[22.1 ]hept-2-ene (HexaDecNB), palladium (hexafluoroacetylacetonate)2, iodonium, diphenyl-4, 4'-di-(C ₁₀ -Ci3)alkyl derivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borates (SILCOLEASE UV CATA 243) and 2-isopropyl-9H- thioxanthen-9-one (ITX);

5-phenylbicyclo[2.2.1 ]hept-2-ene (PhNB), palladium (hexafluoroacetylacetonate)2, iodonium, diphenyl-4, 4'-di-(C ₁₀ -Ci3)alkyl derivatives, tetrakis(23,4 _» 5,6-pentafluoioi*enyl)borates (SILCOLEASE UV CATA 243) and 2-isopropyl-9H-thioxanthen-9-one (ITX); and 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), 5-(2-([l,l -biphenyl]-2- yloxy)methyl)bicyclo[2.2.1 Jhept-2-ene (NBMeOFhPhX palladium (hexafluoroacetylacetonate)*, kxkmium, diphenyI-4,4'-di-(C ₁₀ -Ci3)alkyl derivatives, tdrakis(23,4^,6-pentafluorophcnyl)borates (SDLCOLEASE UV CATA 243) and 2-isopropyl-9H-thioxanthen-9-one (ΓΓΧ).

In a further aspect of this invention than is provided a kit fin forming a substantially transparent film. There is dispensed in this kit a composition of this invention. Accordingly, in some there is provided a kit in which there is dispensed one or more olefinic monomers; an organopalladium compound of formula (I) as described herein; a photoacid generator of formulae (ΠΙ) or (IV) as described herein and a photosensitizer of formulae (VIII) or (IX). In some embodiments the kit of this invention contains one or more monomers of formula (V) optionally in combination with one or more monomers of formulae (VI) or (VII) so as to obtain a desirable result and/or for intended purpose.

In some ant i, the aforementioned kit encompasses one or more monomers of formula (V) and one or more monomers of formulae (VI) or (VII). In some other embodiments die kit of this invention encompasses at least two monomers wherein first monomer serves as a solvent for the second monomer. Any of the monomers of formulae (V) to (VII) as described herein can be used in this embodiment The molar ratio of such two monomers contained in these embodiments can vary and may range from 1:99 to 99:1, or 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 60:40 to 40:60 or 50:50, and so on. In sane other embodiments the kit may encompass a composition wherein dispensed two monomers which could be one monomer of formula (V) and another mononer of formula (VI). Further, the monomer of formula (VI) is completely soluble in monomer of formula (V) to form a clear solution at room temperature. In some embodiments the monomer mixture may become a clear solution at slightly elevated temperature, such as for example, 30 °C or 40 °C or 50 °C, before they undergo mass polymerization. In another aspect of tins embodiment of this invention the kit of this invention undergoes mass polymerization when exposed to suitable actinic radiation for a sufficient length of time to form a polymeric film. That is to say that the composition of this invention is poured onto a surface or onto a substrate which needs to be encapsulated and exposed to suitable radiation in onto fa the nmomers to undergo polymerizatiai to form a solid transparent polymer which could be in the form of a transparent film. Generally, as already noted above, such polymerization can take place at various wavelengths of actinic radiation, such as for example, at 265 nm 315 nm 365 nm or 395 nm and so OL The mass polymerization may further be accelerated by heating, which can also be in stages, fa example heating to 40 ⁰ C a 50 °C or 60 °C for 5 minutes each, and if necessary further heating to 70 °C for various lengths of time such as from 5 minutes to 15 minutes and so on. By practice of tins invention it is now possible to obtain polymeric films on such substrates which are substantially transparent film. The “substantially transparent film" as used herein means that the films formed from the composition of this invention are optically clear in tire visible light Accordingly, in some embodiments of this invention such films are having at least 90 percent of visible light transmission, in some other embodiments foe films framed from the composition of this invention exhibit at least 95 percent of visible light transmission.

In some embodiments of this invention the kit as described herein encompasses a composition which further contains one or more monomers selected from monomer of formula (HI) or monomer of formula (TV) as described hereinabove. Again, any of foe monomers of fbnnula (III) or (TV) as described herein can be used in this embodiment, and in any desirable amounts depending on the nature of the intended use.

In some embodiments, the kit as described herein encompasses various exemplary compositions as described hereinabove.

In yet another aspect of this invention there is further provided a method of forming a substantially transparent film for foe fabrication of a variety of optoelectronic device comprising: forming a homogeneous clear composition comprising one or more monomers of formula

(V); an organopalladium compound of fbnnula (I); a photoacid generator of formulae (ΙΠ) or (IV); andari ¾zer of formulae (VIII) or (IX); coating a suitable substrate with the composition or pouring the composition onto a suitable substrate to form a film; and exposing the film to a suitable actinic radiation to cause polymerization of the monomers.

The coating of the desired substrate to form a film with the composition of this invention can be performed by any of the coating procedures as described herein and/or known to one skilled in the art, such as by spin coating. Other suitable coating methods include without any limitation spraying, doctor blading, meniscus coating, inkjet coating and slot coating. The mixture can also be poured onto a substrate to form a film. Suitable substrate includes any appropriate substrate as is, or may be used fra- electrical, electronic or optoelectronic devices, for example, a semiconductor substrate, a ceramic substrate, a glass substrate.

Next, foe coated substrate is baked, i.e., heated to facilitate the mass polymerization, for example to a temperature from 50°C to 100°C for about 1 to 60 minutes, although other appropriate temperatures and times can be used. In some embodiments the substrate is baked at a temperature of from about 60°C to about 90°C for 2 minutes to 10 minutes. In some other embodiments the substrate is baked at a temperature of from about 60°C to about 90°C for 5 minutes to 20 minutes.

The films thus formed are then evaluated for their optical properties using any of the methods known in tiie art For example, the refractive index of the film across the visible spectrum can be measured by ellipsometry. The optical quality of the film can be determined by visual observation. Θυανητατιοελψ the percent transparency can be measured by visible spectroscopy. Generally, the films formed according to tins invention exhibit excellent optical transparent properties and can be tailored to desirable refractive index as described herein.

Accordingly, in some of the of tiiis invention there is also provided an optically transparent film obtained by the mass polymerization of the composition as described herein. In another embodiment there is also provided an optoelectronic device comprising the transparent film of tiiis invention as described herein.

In yet some other embodiments the composition of this invention can also be used in a variety of photo induced nanoimprint lithography (NIL), such as for example, UV-NIL. For instance, the compositions of tiiis invention can be used in a variety of photocurable imprint technology. Typically in such applications, the composition of tiiis invention is suitably placed on a substrate (far example by coating or similar means), which is then covered by a suitable stamp and exposed to radiation so as to allow the composition of this invention to cure to a solid. The stamp is then released to obtain the nano-imprinted film. Such substrates can include for example a master digital video disk (DVD).

The following examples are detailed descriptions of methods of preparation and use of certain compounds/monomers, polymers and compositions of the present invention. The detailed preparations fall within the scope of, and serve to exemplify, the more generally described methods of preparation set forth above. The examples are presented for illustrative purposes only, and are not intended as a restriction on the scope of the invention. As used in the examples and throughout the specification the ratio of monomer to catalyst is based on a mole to mole basis.

Examples

The following abbreviations have been used hereinbefore and hereafter in describing some of the compounds, instruments and/or methods employed to illustrate certain of the embodiments of tiiis invention: NBEtCl - 5-(2-chloroethyl)bicyclo[2.2. l]hept-2-ene; NBEtOPhPh - 5-(2-([l,r-biphenyl]-2- yloxy)ethyl)bicyclo[2.2.1 ]hept-2-ene; NBMeOPhPh - 5-(2-([l,l'-biphenyl]-2- yloxy)mrihyl)bicyclo[2.2.1 ]hept-2-ene; PENS - 5-phcncthylbicycIo[22.1 ]hept-2-ene; PhNB - 5- phenylbicyclo[2.2. l]hept-2-ene; DecNB - 5-decylbicyclo[2.2. l]hept-2-ene; HexaDecNB - 5- hexadecylbicyclo[2.2. l]hept-2-ene; TD - tetracydododeceae ; Pd304 - palladium

(acetylacdonate)2; Pd520 - palladium (hexafluoroacetylacetonate)^ Pd428 - palladium (1- phenylbutane- 1 ,3-dionate)2; Pd473 - palladium (tetramethylheptenonoate)2; Pd498 - palladium (2-((phenylimino)mdhyl)phenoate)2; Pd620 - palladium (l,l,l,5^,6,6,6-octafluorohexane-2,4- dionate)2; Pd920 - palladium (1,1, 1 Λ2^ J ,7,7,8,8,9,9,9-tetradecafluorononane-4,6-dionate)2; Rhodorsil 2074 - tolylcumyliodonium-tetrakis pentafluorophenylbonite; OPPI-SbFe - [4- (octyloxy)phenyl]phenyliodonium hexafluoroantimonate; OPPI-PFe - [4- (octyloxy)phenyllphenyliodonium hexafluorophosphate; Irgacure PAG290 - tris(4-(4- acetylphenylthio)phenyl)sulfbmum tetrakis(penlafluorophenyl)borate; TAG 382 - (2-(4- methoxynaphthalen- 1 -y l)-2-oxoethyl)dimethylsulfonium tetrakis(pentafluorophenyl)borate; UV CATA 243 - iodonium, 4,4'-di-(C ₁₀ -Ci3)alkyl derivatives, tetrakis(2,3, 4,5,6- pentafluorophenyl)borales; ΓΓΧ - 4-isopropylthioxanthone; CTX - 2-chlorothioxanthone;

DEA - 9, 10-diethoxyanthracene; GPC - gel permeation chromatography, M _w - weight average molecular weight; PDI - polydispersity index; cP - centipoise; DSC - differential scanning calorimetry; TGA - thermogravimetric analysis; UV-NIL - ultraviolet nanoimprint lithography.

Various oganopalladium compounds of formula (I) are either commercially available or known in the literature and can be readily prepared following the procedures as described in the literature. Examples A - D illustrate preparation of a few of the organopalladhim compounds of formula (I).

Example A Synthesis of Pd428

To a brown suspension of Pd(II)chloride (0.4 g, 2.26 mmol) dissolved in methanol (11.3 ml) was added sodium chloride (0.132 g, 2.26 mmol). The mixture was stirred ovemigjht at ambient temperature, at which point it is filtered and diluted with 11.3 mL methanol. To a resulted brown solution (5.6 mL) was added 1-benzoylacetone (0.235 g, 1.41 mmol) and sodium carbonate (0.051 g, 0.479 mmol). An immediate yellow precipitate was formed. The solution was stirred overnight at ambient temperature at which point the solid was collected by filtration. To the yellow solid was added 5 mL dichloromethane. The solution was filtered and concentrated in vacuo to produce a yellow solid. Yield 0.178 g. ^l H NMR (CD2CI2, 500 MHz): δ 2.07 (s, 6H), 5.91 (s, 2H), 7.23 (d, 4H), 7.30 (m, 2H), 7.70 (d,

4H).

Example B Syntiiesis of Pd498

To a brown suspension of Pd(H)acetate (0.2 g 0.89 mmol) dissolved in ethanol (5 mL) was added a solution of jV-salicylideneanilline (0.351 g, 1.78 mmol) dissolved in ethanol (5 mL). The solution was refluxed for 3 h, at which point yellow-brown solid was formed which was collected by filtration and washed with 3x5 mL ethanol. To the obtained solid was added 10 mL toluene and stirred for 1 h. The solution was filtered, and the solvent was removed in vacuo to produce an orange solid. Yield, 0.32 g. Ή NMR (CeDe, 500 MHz): δ 6.36 (t, 2H), 6.48(d, 2H), 6.74 (d, 2H), 6.99 (t, 1H), 7.08 (m, 10H), 7.22 (s, 2H)

Example C Synthesis of Pd620

To a brown suspension of Pd(H)chloride (0.085 g, 0.48 mmol) dissolved in methanol (2.8 mL) was added sodium chloride (0.028 g, 0.48 mmol). The mixture was stirred for 2 h at 50°C, at which point the reaction mixture was filtered and diluted with 2.8 mL methanol. To this brown solution (5.6 mL) was added l,l,l,5,5,6,6,6-octafluoro-2,4-hexanedione (0.51 g, 1.2 mmol) and sodium carbonate (0.051 g, 0.479 mmol). The solution was stirred overnight at ambient temperature at which point the solvent was removed in vacuo. To the orange solid was added 5 mL n-hexane and stirred for 1 h. The solution was filtered and concentrated in vacuo to produce an orange solid. Yield 0.338g. *H NMR (CD2CI2, 500 MHz): δ 6.43 (s, 2H). ¹⁹ F NMR (CD2CI2, 470 MHz): δ -126.6, -118.0, -80.9.

Example D Synthesis of Pd920

To a brown suspension of Pd(II)chloride (0.1 g, 0.56 mmol) dissolved in methanol (2.8 mL) was added sodium chloride (0.033 g, 0.56 mmol). The mixture was stirred for 2 h at 50°C, at which point the reaction mixture was filtered and diluted with 2.8 mL methanol. To this brown solution (5.6 mL) was added l,l,l,2,2,3,3,7,7,8,8,9,9,9-tetradecafluoro-4,6- nonadione (0.364 g, 1.41 mmol) and sodium carbonate (0.06 g, 0.56 mmol). The solution was stirred overnight at ambient temperature at which point the solvent was removed in vacuo. To the orange solid was added 5 mL n-hexane and stirred for 1 h. The solution was filtered and concentrated in vacuo to produce an orange solid. Yield 0.182 g. ^l H NMR (CD2CI2, 500 MHz): δ 6.41 (s, 2H). ¹⁹ F NMR (CD2CI2, 470 MHz): δ -1203, -82.7, -73.6.

Various monomers as used herein are either commercially available or can be readily prepared following die procedures as described in the co-pending U. S. Patent No. 9,944,818.

The Mowing Examples 1-5 demonstrate that die composition of this invention is quite stable at room temperature for at least up to three days and can very readily be mass polymerized when exposed to UV radiation. Examples 2-5 further illustrate that the mass polymerization occurs when exposed to radiation only in the presence of organopalladium compound of formula (I), a photoacid generator of formula (ΠΙ) and a photosensitizer of formula (V).

Example 1

Mass polymerization of NBEtCl/PENB (5/95 molar ratio)

In a glass bottle, Pd304 (1 molar part), Rhodorsil 2074 (2 molar parts) and CTX (1 molar part) were dissolved in NBEtCl (250 molar parts). To this clear solution was then added PENB (4750 molar parts). The solution was purged with N2 overnight The solution was then UV light exposed for 4 sec (lJ/cm ² , 395nm) at room temperature. The solution turned to a solid in a minute indicating die monomers were polymerized, as further confirmed by TGA; the residue percentage of solids from isothermal TGA (lh at 100 °C); conversion >99 %. Based on dynamic TGA (20 °C/min), Tds (5% wt. loss) was 340.2 °C and the amount remaining at 300 °C was 97%. The unexposed solution was free flowing even after 3 days at room temperature.

Examples 2 - 5

Mass Polymerization ofPENB/NBEtCl (90/10 molar ratio)

The procedures of Example 1 were substantially followed in these Examples 2 - 5 except that Example 2 contained 90:10 molar ratio of PENB/NBEtCl. in Example 3 no photosensitizer was employed; in Example 4 no photoacid generator was employed and in Example 5 no organopalladium compound was employed, as summarized in Table 1. All of the compositions were prepared in a glass bottle, and UV light exposed for 4 sec (lJ/cm ² , 395nm) at room temperature. It is quite evident from the results presented in Table 1, only the composition of Example 2 turned to a hard solid in a minute indicating the monomers were polymerized. This clearly demonstrates that it is necessary to employ all three components of the composition of this invention in order to bring about the mass polymerization of the olefmic monomers of this invention.

Table 1

The Mowing Examples 6-8 illustrate that various different molar ratios of the photosensitizer can be employed to mass polymerize the olefmic monomers of this invention.

Examples 6-8 Different ratios of ΓΓΧ

The procedures of Example 1 were substantially repeated in these Examples 6-8 except that various different amounts of ΓΓΧ were employed as summarized in Table 2. In each of Examples 6-8, Pd304 (1 molar part), Rhodorsil 2074 (2 molar parts) and different amounts of ΓΓΧ (0.5, 2, 8 molar parts respectively) were dissolved in NBEtCl (250 molar parts) and then PENB (4750 molar parts) was added to form a clear solution. The solution was purged with dry Na overnight, then it was UV light exposed for 4 sec (lJ/cm ² , 395nm) at room temperature. In all of Examples 6-8 the solution turned to a solid in a minute indicating that the monomers were polymerized, as further confirmed by TQA as summarized in Table 2. It is further apparent from the UV-DSC data presented in Table 2, the composition of Example 6 with 0.5 molar parts ΓΓΧ loading exhibits almost similar reactivity as that of Example 7, which contained ΓΓΧ loading of 2 molar parts. Further, Example which contained 8 molar parts of ΓΓΧ appear to show slightly decreased polymerization rate. Thus, indicated smaller amounts of photosensitizer may be sufficient to carry out effectively the mass polymerization of the compositions of this invention. This is further manifested by the percentage residues of the solids remaining after mass polymerization as measured from the isothermal TGA (lh at 100 °C); the composition with 0.5 molar parts ΓΓΧ loading gave slightly higher solid residues than both the ΓΓΧ loadings at 2 molar parts and 8 molar parts. Table 2

Example 9

Mass Polymerization of PENB/NBEtCI with Pd520 (95/5 mole ratio)

The procedures of Example 1 were substantially repeated in this Example 9 except that Pd520 was used in place of Pd304. In a glass bottle, Pd520 (1 molar part), Rhodorsil

2074 (2 molar parts) and CTX (1 molar part) were dissolved in NBEtCl (250 molar parts), which was then mixed with PENB (4750 molar parts) to form a clear solution. The solution was purged with dry Na overnight, then it was UV light exposed for 4 sec (lJ/cm ² , 395nm) at room temperature. The solution turned to a solid in a minute indicating the monomers were polymerized, as also confirmed by TGA. The residue percentage of solids from isothermal TGA (lh at 100 °C) after UV exposure was >99 %. Based on dynamic TGA (20 °C/min), Tds (5% wL loss) was 339.4°C and the amount remaining at 300 °C was 97%. The unexposed solution was free flowing even after 3 days at room temperature.

Example 10

Mass Polymerization of PENB/NBEtOPhPh (90/10 mole ratio) hi a glass bottle, Pd520 (1 molar part), Rhodorsil 2074 (4 molar parts) and ΓΓΧ (1 molar part) were dissolved in NBEtOPhPh (500 molar parts), which was then added to PENB (4500 molar parts) to form a clear solution. The solution was purged with dry N2 overnight, then it was UV light exposed for 4 sec (lJ/cm ² , 395nm) at room temperature. The solution turned to a solid in a minute indicating the monomers were polymerized, as also confirmed by UV-DSC, TGA and GC/MS. The UV-DSC showed a sharp exothermic peak after UV exposure (lJ/cm ² , 395nm) for 4 sec and continued to release heat after the UV exposure. The residue percentage of solids from isothermal TGA (lh at 100 °C) after UV exposure was >99 %. Based on dynamic TGA (20 °C/min), T _d s (5% wt. loss) was 267 °C and the amount remaining at 300 °C was 93%. The residue percentage of unreacted monomers from GC/MS after UV exposure was <2%. The unexposed solution was free flowing even after 14 days at room temperature.

Example 11

Mass Polymerization of DecNB/NBEtOPhPh (90/10 molar ratio)

In a glass bottle, Pd520 (1 molar part), Rhodorsil 2074 (1 molar parts) and ΓΓΧ (0.5 molar part) were dissolved in NBEtOPhPh (500 molar parts), which was then added to DecNB (4500 molar parts) to form a clear solution. The solution was purged with dry Na overnight, then it was UV light exposed for 4 sec (lJ/cm ² , 395nm) at room temperature. The solution turned to a solid in minutes indicating the monomer was polymerized, as also confirmed by DSC, TGA and GC/MS. The UV-DSC showed a sharp exotherm after UV exposure (1 J/cm ² , 395nm) for 4 sec and continued to release heat after the UV exposure. The residue percentage of solids from isothermal TGA (lh at 100 °C) after UV exposure was >99 %. Based on dynamic TGA (20 °C/min), Tds (5% wt. loss) was 332 °C and the amount remaining at 300 °C was 97%. The residue percentage of unreacted monomers from GC/MS after UV exposure was <1 %. The unexposed solution was free flowing even after 14 days at room temperature.

Example 12

Mass Polymerization of PENB/DecNB/NBEtOPhPh (45/45/10 molar ratio)

In a glass bottle, Pd520 (1 molar part), Rhodorsil 2074 (2 molar parts) and ΓΓΧ (1 molar part) were dissolved in NBEtOPhPh (500 molar parts), which was then added to a mixture ofPENB (2250 molar parts) and DecNB (2250 molar parts) to form a clear solution. The solution was purged with dry Na overnight, then it was UV light exposed for 4 sec (1 J/cm ² , 395nm) at room temperature. The solution turned to a solid in a minute indicating the monomers were polymerized, as also confirmed by DSC, TGA and GC/MS. The residue percentage of solids from isothermal TGA (lh at 100 °C) after UV exposure was >99 %. Based on dynamic TGA (20 °C/min), Tu (5% wt. loss) was 347 °C and the amount remaining at 300 °C was 97%. The residue percentage of unreacted monomers from GC/MS after UV exposure was <1 %. The unexposed solution was free flowing even after 14 days at room temperature.

The following Examples 13 and 14 demonstrate the shelf life stability of the compositions of this invention at ambient atmospheric conditions and at sub-ambient condition (5°C). It is evident from these studies that the compositions of this invention are stable at ambient to sub-ambient temperatures and can be stored under these conditions for several days.

Example 13

Shelf Life Studies of PENB/DecNB/NBEtOPhPh (45/45/10 molar ratio)

In a glass bottle, Pd520 (1 molar part), Rhodorsil 2074 (2 molar parts) and ΓΓΧ (1 molar part) were dissolved in NBEtOPhPh (500 molar parts), which was then added to a mixture of PENB (2250 molar parts) and DecNB (2250 molar parts) to form a clear solution. The solution was purged with dry N2 overnight The viscosity of the solution was measured at a periodic interval as summarized in Table 3 and graphically shown in FIG. 1. It is evident from FIG. 1 that the viscosity remained relatively unchanged for 4 days (<10% change) and was free flowing even after 2 weeks at room temperature and started to gel after 15 days (FIG. 1, Table 3).

Table 3

Example 14

Shelf Life Studies of PENB/DecNB/NBEtOPhPh (40/40/20 molar ratio)

In a glass bottle, Pd520 (1 molar part), Rhodorsil 2074 (4 molar parts) and ΓΓΧ (1 molar part) were dissolved in NBEtOPhPh (1000 molar parts), which was then added to a mixture of PENB (2000 molar parts) and DecNB (2000 molar parts) to form a clear solution. The solution was purged with dry N2 overnight This solution was divided into two portions. One portion was stored at room temperature (RT), and the other portion was stored at 5 °C. The viscosities of these solutions were measured at periodic intervals as summarized in Table 4 and graphically shown in FIG. 2. It is evident from FIG. 2 that the viscosity remained unchanged even after for 4 days and was free flowing even after 2 weeks at room temperature (FIG. 2, Table 4). The reactivity of the solution was also measured by UV-DSC. The reactivity of the solution remained almost same even after one-week storage at room temperature as confirmed by UV DSC. But the reactivity decreased after 2 weeks of storage at room temperature as confirmed by enthalpy change from UV DSC. However, the solution stored at 5 °C retained its reactivity even after 1 month and exhibited almost identical reactivity as that of a fresh solution as confirmed by UV DSC. The isothermal TGA (lh at 100 °C) of the sample after UV DSC exposure confirmed the high conversion (>98%). Table 4 summarizes the viscosity and enthalpy change under different storage conditions.

Table 4

Examples 15 - 16 Mass Polymerization of DecNB/NBEtOPhPh (90/10 molar ratio) in N ₂ and Air Atmosphere In two separate glass bottles, Pd520 (1 molar part), Rhodorsil 2074 (1 molar part), ΓΓΧ (0.5 molar parts) were dissolved in a mixture of DecNB/NBEtOPhPh (5000 molar parts, 90/10 mole ratio) to form a clear solution. The solution of ExamplelS was purged with dry N ₂ overnight while Example 16 was not purged with dry N ₂ overnight. Both solutions of Examples 15 and 16 were UV light exposed for 4 sec (lJ/cm ² , 395nm). Both solutions became hard solid within minutes indicating that the compositions are equally reactive in both N ₂ and air environment The residue percentage of solids in both examples from isothermal TGA (lh at 100 °C) after UV exposure was ~99 % indicating high conversion. The data are summarized in Table 5.

Table 5

Examples 17 - 18

Mass Polymerization of PENB/DecNB/NBEtOPhPh (40/40/20 molar ratio) in N ₂ and Air

Atmosphere

The procedures of Examples 15 and 16 were also repeated in Examples 17 and 18 except that a monomer mixture of PENB/DecNB/NBEtOPhPh (5000 molar parts, 40/40/20 molar ratio) and Pd520 (1 molar part), Rhodorsil 2074 (4 molar parts), ΓΓΧ (1 molar part) were used, and the clear solutions were purged with either diy nitrogen or air, then it was applied to a glass slide by a doctor blade applicator to make a uniform thin film with thickness from 50~ 100 μm. Then the film was subjected to UV light exposure for 4 sec (lJ/cm ² , 395nm) in air at room temperature. After several minutes, a solid thin film was formed and was peeled from the glass slide. The conversion was determined by the residue of solids after heating at 100 X for 1 h by TGA. Both of Examples 17 and 18 showed high residue of solids (>98%) indicating high conversion and the formulations are not air-sensitive. The TGA data are summarized in Table 6.

Table 6

The following Examples 19 to 21 demonstrate the applications of the compositions of this invention in various non-limiting applications, which include optical transparent coating films, 3D printing, and UV nanoimprint lithography, among others.

Example 19

Optical Coating and Transparent Thin Film Applications In a glass bottle, Pd520 (1 molar part), Rhodorsil 2074 (2 molar parts), ΓΓΧ (1 molar part) were dissolved in NBEtOPhPh (500 molar parts), which was then added to PENB (4500 molar parts) to form a clear solution. The solution was purged with dry Nr overnight, then it was applied to glass slides with a spacer or by doctor blade applicator to make a uniform thin film with thickness from 20~ 100 μm under UV light exposure for 4 sec (lJ/cm ² , 395mn) at room temperature. After several minutes, a transparent thin film was formed and was peeled from the glass slides (FIG. 3). The transmittance of a 55 μm free-standing solid thin film was ~90% at visible wavelengths (400-700 nm) from UV-vis test.

Example 20

Formation of 3D objects

In a glass bottle, Pd520 (1 molar part), Rhodorsil 2074 (4 molar parts), CTX (1 molar part) were dissolved in a monomer mixture ofPENB/NBEtOPhPh/NBEtCl (5000 molar parts, 90/5/5 mole ratio) to form a clear solution. The composition was poured into the resin tank of the 3D printer, Hunter DLP Resin 3D Printer, Flash Forge. The composition was then exposed to UV light (405 nm) to solidify and the 3D objects layer-by-layer through Digital Light Processing (DLP). FIG. 4 shows the 3D printed object The composition exhibited relatively constant viscosity overnight in the resin tank during the 3D printing. The solution after overnight was still very reactive as confirmed by UV-DSC which showed an exothermic peak after UV exposure (1 J/cm ² , 395nm) for 4 sec and continued to release heat after stopping the UV exposure. The reaction was completed within a min and the conversion reached 90% within 0.5 mins. The residue percentage of solids from isothermal TGA (lh at 100 ^e C) after UV exposure was -98 %. The solution remained free flowing even after 4 days at room temperature.

Example 21

Stamp Fabrication (UV -NIL)

A digital-video-disk (DVD) was separated using a razor blade to expose the channel patterned surface. After cleaning with methanol the rigid polycarbonate channel pattern was exposed and ready to use. In a glass bottle, Pd520 (1 molar part), Rhodorsil 2074 (4 molar parts), ITX (1 molar part) were dissolved in NBEtOPhPh (500 molar parts), which was then added to PENB (4500 molar parts) to form a clear solution. Then the composition so formed was poured onto the surface of glass substrate. A DVD (Verbatim) was separated using a razor blade and cleaned with methanol to expose the channel patterned surface. FIGs. 5A and 5B show respectively 10 μm and 20 μm resolution optical micrograph of the patterned surface of the DVD. Subsequently, the exposed channeled surface of DVD was placed onto the composition placed on the glass substrate and exposed to UV light for 4 sec (1 J/cm ² , 395 nm) at room temperature. A cured solid film was formed after several minutes and then it was peeled off. The stamped film was characterized by optical microscopy. FIGs. 6A and 6B show the patterns formed from the DVD at 10 μm and 20 μm magnifications, respectively. It is evident from FIGs. 5 and 6, the channel surfaces imprinted on the film were essentially similar to the original channels on the exposed DVD. The channel periods were about 760 nm + 20 nm. This clearly demonstrates that the composition of this invention can be used for forming nanoimprints.

Examples 22 to 24 further illustrate various other organopalladium compounds of formula (I) can be used to form the compositions of this invention.

Example 22 - 24

In three separate glass bottles, Pd304, Pd520 and Pd473 (1 molar part) were each mixed with Rhodorsil 2074 (2 molar parts), ΓΤΧ (1 molar parts), and dissolved in NBEtOPhPh (500 molar parts), which were then added to a mixture of PENB/DecNB (4500 molar parts, for a total of 45/45/10 molar ratio of PENB/DecNB/NBEtOPhPh) to form a clear solution. The solutions were then UV light exposed for 4 sec (lJ/cm ² , 395 nm) at room temperature. All of die solutions turned to a solid in a few minutes indicating the monomers were polymerized, as also confirmed by DSC and TGA. From the TGA test, the residue percentage of solids from isothermal TGA (lh at 100 °C) after UV exposure for all compositions were ~99%. The UV-DSC studies showed that all of the compositions exhibited an exothermic peak after UV exposure for 4 secs., which continued to release heat after the UV exposure. In five minutes reaction time, the enthalpy change was measured to compare the reactivity of each of the composition. But it should be understood that the polymerization of the monomers will continue even after the actinic radiation and the TGA measurements are generally done at least after one hour of exposure. The measured enthalpy change revealed the reactivity of the catalyst as follows: Pd520>Pd304>Pd473. The measured enthalpic data are summarized in Table 7.

Table 7

The following examples demonstrate various other photoacid generators (PAGs) and photosensitizers can be used in the composition of this invention as described herein.

Examples 25

Mass Polymerization of PENB with OPPI-SbFe

In a glass bottle, Pd520 (1 molar part), OPPI-SbFs (2 molar parts), ΓΓΧ (1 molar part) were dissolved in NBEtOPhPh (500 molar parts), which was then added to PENB (4500 molar parts) to form a clear solution. The solution was purged with dry N2 for 2 hours, then it was UV light exposed for 4 sec (lJ/cm ² , 395nm) at room temperature. The solution solidified within 1 min and became hard solid after 5 mins.

Example 26

Mass Polymerization of PENB with TAG382 In a glass bottle, Pd520 (1 molar part), TAG382 (2 molar parts), DEA (1 molar part) were dissolved in PENB (5000 molar parts) to farm a clear solution. The solution was purged with dry N2 for overnight. The solution was UV light «rosed fix 4 sec ( 1 J/cm ² , 395nm) at room temperature, tiie solution turned to a viscous liquid in a minute and became soft solid in 5 mins indicating the monomer was polymerized. When the solution was first heated at 70 °C and thenUV light exposed for 4 sec (1 J/cm ² , 395nm), the solution turned to a hard solid in minutes indicating the monomer was My polymerized. The unexposed solution remained as free flowing liquid even after 2 weeks at room temperature, indicating a good pot life.

Example 27

Mass Polymerization ofPENB witii Irgacure PAG290 In a glass bottle, Pd520 (1 molar part), Irgacure PAG290 (2 molar parts), DEA (1 molar part) were first dissolved in ethyl acetate (EA) solvent and then added PENB (5000 molar parts) to form a clear solution. The solution was purged with diy N2 for overnight When the solution was UV light oposed for 4 sec (lJ/cm ² , 395nm) at room temperature, the solution turned to a viscous liquid in a minute and became soft solid in 5 mins indicating the monomer was polymerized. When the solution was first heated at 70 °C and then UV light exposed fix 4 sec (lJ/cm ² , 395nm), the solution turned to a hard solid in a minutes indicating the monomer was fully polymerized. The unexposed solution remained as free flowing liquid even after 2 months at room temperature, mHirating a good pot life.

Examples 28 - 31

Mass Polymerization of PENB/NBEtOPhPh (90/10 molar ratio) in Various

Organopalladium Compounds

In four separate glass bottles, Pd428, Pd498, Pd620 and Pd920 (1 molar part) were each mixed with Rhodorsil 2074 (2 molar parts), CTX (1 molar part), and dissolved in NBEtOPhPh (1000 molar parts), which were then added to a mixture ofPENB (9000 molar parts, for a total of 90/10 molar ratio of PENB/NBEtOPhPh) to form a clear solution. Each of these solutions were then UV light exposed separately for 4 sec (lJ/cm ² , 395 nm) at room temperature. All of the solutions turned to a solid in a few minutes indicating the monomers were polymerized, as also confirmed by DSC and TGA. The residue percentage of solids from isothermal TGA (lh at 100 °C) after UV exposure for all compositions were >98% for all examples except Example 30 as summarized in Table 8. The UV-DSC studies showed that all of the compositions exhibited an exothermic peak after UV exposure for 4 secs., which continued to release heat after the UV exposure. In five minutes reaction time, the enthalpy change was measured to compare the reactivity of each of the compositions. The measured enthalpic data are summarized in Table 8.

Table 8

Example 32

In a glass bottle A, Pd520 (1 molar part) was dissolved in PENB (2500 molar part) to form a clear solution. In another glass bottie B, UV CATA 243 (2 molar part), ΓΓΧ (1 molar part) were dissolved in PENB (2500 molar part) to form a dear solution. Both bottles were stored at room temperature and had no viscosity change over time. When the solutions were mixed, they remained as uniform clear solution to form a composition of this invention. The composition was then exposed to UV-irradiation (1 J/cm ² , 395 nm), it immediately gelled and became transparent hard solid within a minute. The composition was also spin-coated onto a 2 inch quartz wafer at 500 rpm for 10 secs and 1000 rpm for 30 secs, and then exposed to UV-irradiation (1 J/cm2, 395 nm), a transparent solid film was formed within a few minutes with a thickness of3.03±0.03 μm measured by profilometry. The transmittance of the film on quartz wafer was characterized as 92% at foe range 400-800 nm by UV-vis.

Example 33

Mass Polymerization of TD with UV CATA 243 and Pd520 In a glass bottle, Pd520(l molar part), UV CATA 243 (4 molar parts), ΓΓΧ (2 molar parts) wee dissolved in TD (5000 molar parts) to form a dear solution. The solution was then exposed to UV irradiation for 4 secs ^J/cm ² , 395 nm) at room temperature. The solution gelled within a min after UV exposure and became a hard solid within minutes indicating polymerization. The residue percentage of solids from isothermal TGA (lh at 100 °C) after UV exposure was -80%. The unexposed solution still remained as a free liquid without gelling after one week’s storage in room temperature.

Example 34

Mass Polymerization of PhenylbutylNB with UV CATA 243 and Pd520 h a glass bottle, Pd520 (1 molar part), UV CATA 243 (4 molar parts), ΓΓΧ (2 molar parts) were dissolved in phenylbutylNB (5000 molar parts) to form a clear solution. The solution was then exposed to UV irradiation for 4 secs (1 J/cm ² , 395 nm) at room temperature. The solution gelled within a min after UV exposure and became a hard solid whhin minutes indicating polymerization. The residue percentage ofsolids from isothermal TGA (1 hat 100 °C) after UV exposure was -99%.

The unexposed solution still remained as a free liquid without gelling after one week’s storage in room temperature.

Example 35

Mass Polymerization of CyclohexylNB with UV CATA 243 and Pd520 In a glass bottle, Pd520(l molar part), UV CATA 243 (4 molar parts), ΓΓΧ (2 molar parts) were dissolved in cyclohexylNB (5000 molar parts) to form a clear solution. The solution was then exposed to UV irradiation for 4 secs (1 J/cm ² , 395 mn) at room temperature. The solution gelled within a min after UV exposure and became a hard solid within minutes indicating polymerization. The residue percentage of solids from isothermal TGA ( 1 h at 100 °C) after UV exposure was -94%. The unexposed solution still remained as a free liquid without gelling after erne week’s storage in room re.

Example 36

Mass Polymerization of HexaDecNB with UV CATA 243 and Pd520 In a glass bottle, Pd520 (1 molar part), UV CATA 243 (2 molar parts), ITX (1 molar part) were dissolved in hexadecylNB (5000 molar parts) to form a clear solution. The solution was then exposed to UV irradiation for 4 secs (1 J/cm ² , 395 mn) at room temperature. The solution gelled within a min after UV exposure and became a solid within minutes indicating polymerization. The residue percentage of solids from isothermal TGA (1 hat 100 °C) after UV exposure was -99%.

Example 37

Mass Polymerization of PKNB with UV CATA 243 and Pd520 In a glass bottle, Pd520 (1 molar part), UV CATA 243 (2 molar parts), ITX (1 molar part) were dissolved in PhNB (5000 molar parts) to form a clear solution. The solution was then exposed to UV irradiation for 4 secs (1 J/cm ² , 395 mn) at room temperature. The solution gelled whhin a min after UV exposure and became a hard solid within minutes indicating polymerizatkm. The residue percentage of solids from isothermal TGA (1 h at 100 °C) after UV exposure was -90%.

Example 38

Mass Polymerization of DecNB/NBMeOPhPh with UV CATA 243 and Pd520 In a glass bottle, Pd520 (1 molar part), UV CATA 243 (2 molar parts), ΓΓΧ (1 molar part) were dissolved in a mixture of DecNB/NBMeOPhPh (SOOOmolar parts, 80/20 mole ratio) to form a clear solution. The solution was then exposed to UV irradiation for 4 secs (1 J/cm ² , 395 nm) at room temperature. The solution gelled within a min after UV exposure and became a solid within minutes indicating polymerization. The residue percentage of solids from isothermal TGA (1 hat 100 °C) after UV exposure was ~99%.

The following Comparative Examples 1-2 are provided to show that only organopalladium compounds of formula (I) are effective under the conditions as described herein, whereas analogous catalysts, such as nickel or platinum compounds are found to be ineffective under similar conditions.

Comparative Example 1

Mass Polymerization ofPENB/NBEtCl with Ni(acac)2 hi a glass bottle, Ni(acac>2 (1 molar part), Rhodorsil 2074 (2 molar parts) and CTX (1 molar part) were dissolved in NBEtCl (250 molar parts), which was then added to PENB (4750 molar parts) to form a solution. The solution was purged with dry Ni overnight, then it was UV light exposed for 4 sec (1 J/cm ² , 395nm) at room temperature. The solution remained as free liquid indicating the monomers were not polymerized. The exposed solution still remained as free flowing liquid even after 3 days at room temperature.

Comparative Example 2

Mass Polymerization of PENBZNBEtOPhPh with Pt(acac)2

In a glass bottle, Pt(acac)a (1 molar part), Rhodorsil 2074 (2 molar parts) and CTX (1 molar part) were dissolved in NBEtOPhPh (500 molar parts), which was then added to PENB (4500 molar parts) to form a solution. The solution was purged with dry Nz overnight, then it was UV light exposed for 4 sec (1 J/cm2, 395nm) at room temperature. The solution remained as free liquid indicating the monomers were not polymerized. The exposed solution still remained as free flowing even after 1 day at room temperature.

Although the invention has been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof