RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application Serial No.

60/684,666 filed May 25, 2005.

Field of the Invention

This invention relates generally to the methods and compositions of olefin containing

polyhedral oligomeric silsesquioxanes (POSS). More specifically, it relates to methods for

the continuous bulk production of polyvinyl POSS and derivative chemical products.

BACKGROUND OF THE INVENTION

Recent developments in nanoscience have enabled cost effective manufacture of

commercial quantities of polyhedral oligomeric silsesquioxanes that are best described as

nanostructured chemicals due to their precise chemical formula, hybrid (inorganic-organic)

chemical composition, large physical size relative to the size of traditional chemical

molecules (0.3-0.5 nm), and small physical size relative to larger-sized traditional fillers (>50

nm).

The commodity nature of organosilane coupling agents makes them highly desirable

for use as starting materials for nanoscopic POSS molecules. Prior art has taught the use of

silane coupling agents in the formation of POSS cages (U.S. Patent No. 6,972,312) and in the

functionalization of POSS cages with reactive groups (U.S. Patent No. 6,927,270).

This invention teaches continuous production methods for olefin bearing POSS and in

particular vinyl POSS cages. This advancement was needed as vinyl silanes are the lowest

cost reactive silane coupling agent and because vinyl POSS cages are highly desirable for

chemical derivatization into other chemical groups. Applications for olefin POSS and its

derivatives include improved composite resins, paints, coatings, adhesives, and surface

properties, which lead to fire resistance, printability, biocompatibility, and permeability

controlled, high Tg and heat distortion materials, glassification agents, printing aids, and

nanofiltration materials.

SUMMARY OF THE INVENTION

The present invention describes methods of continuous synthesis of polyolefin

containing polyhedral oligomeric silsesquioxanes. It also describes compositions of

chemicals derived from them.

The preferred compositions herein contain olefin functionalities on nanostructured chemicals and nanostructured oligomers (Figure 1). The nanostructured chemical classes

include polyhedral oligomeric silsesquioxanes, polysilsesquioxanes, polyhedral oligomeric

silicates, polysilicates, polyoxometallates, carboranes, boranes, and polymorphs of carbon.

Chemical derivatives from olefin containing POSS have been prepared by hydrosilation,

phosphorylation and thiolation (U.S. Patent No. 5,939,576), epoxidation and oxidation

methods (U.S. Patent Nos. 5,942,638 and 6,100,417), crossmetathesis, Heck additions, Diels-

Alder reactions, hydroformylation and Wacker oxidation. This invention describes

polyisocyanate derivatives, dhydroamination and subsequent carboxylation. Polyalcohol

derivatives are also described through ethylene and propylene oxide additions to olefinic

POSS.

Polyfunctional POSS systems are of utility in the formation of cross-links in materials

such as polycarbonate, polyesters, urethanes, epoxides, polyethers, polyamides, polyolefines,

bismaleimides, chitin, cellulose, polyacids, and silicones.

Vinyl containing nanostructured chemicals are particularly effective in polymers as

they control the motions of polymer chains, and segments, at the molecular level. Vinyl

containing nanostructured chemicals as also highly desirable in cosmetics, adhesives, paints,

coatings and dyes as the impart unique surface and physical properties. The incorporation of a

nanostructured chemical into a polymer favorably impacts a multitude of polymer physical

properties. Properties most favorably improved are heat distortion and flammability

characteristics. Other properties improved include time dependent mechanical and thermal

properties such as creep, compression set, shrinkage, modulus, and hardness. In addition to

mechanical properties, other physical properties are favorably improved, including lower

thermal conductivity, gas oxygen barrier and permeability, surface gloss and color. In

addition, vinyl containing nanostructured chemicals are highly useful for surface glassification and for chemical derivitization. These improved properties may be useful in a

number of applications, including composite materials and durable coatings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows examples of polyvinyl containing POSS nanostructured chemicals;

FIG. 2 illustrates the effect of water on yield of octavinyl POSS;

FIG. 3 illustrates the effect of acid on yield of octavinyl POSS;

FIG. 4 shows ²⁹ Si NMR spectra of batch vs continuously produced octavinyl POSS;

FIG. 5 illustrates the process of vinyl hydroamination;

FIG. 6 illustrates the process of isocyanate formation; and

FIG. 7 illustrates the process of alcohol formation.

DEFINITION OF FORMULA REPRESENTATIONS FOR NANOSTRUCTURES

For the purposes of understanding this invention's chemical compositions the

following definition for formula representations of Polyhedral Oligomeric Silsesquioxane

(POSS) and Polyhedral Oligomeric Silicate (POS) nanostructures is made.

Polysilsesquioxanes are materials represented by the formula [RSiOi^] _x where x

represents molar degree of polymerization and R = represents organic substituent (H, siloxy,

cyclic or aliphatic or olefininc, or aromatic groups that may additionally contain reactive

functionalities such as alcohols, isocyanates, esters, amines, ketones, olefins, ethers or halides

or which may contain fluorinated groups). Polysilsesquioxanes may be either homoleptic or heteroleptic. Homoleptic systems contain only one type of R group while heteroleptic

systems contain more than one type of R group.

POSS and POS nanostructure compositions are represented by the formula:

[(RSiOj .5) _n ]∑# for homoleptic compositions

[(RSiOj _5) _n (R'Si0i 5) _m ]∑# for heteroleptic compositions (where R ≠ R')

[(RSiOj 5) _n (RXSi0j o)m]∑# for functionalized heteroleptic compositions (where R groups

can be equivalent or inequivalent)

In all of the above R is the same as defined above and X includes but is not limited to

OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR2) isocyanate

(NCO), and R. The symbols m and n refer to the stoichiometry of the composition. The

symbol ∑ indicates that the composition forms a nanostructure and the symbol # refers to the

number of silicon atoms contained within the nanostructure. The value for # is usually the

sum of m+n, where n ranges typically from 1 to 24 and m ranges typically from 1 to 12. It

should be noted that ∑# is not to be confused as a multiplier for determining stoichiometry, as

it merely describes the overall nanostructural characteristics of the system (aka cage size).

DETAILED DESCRIPTION OF THE INVENTION

The present invention teaches a continuous process for the manufacture of olefinic

containing nanostructured chemicals and chemical derivatives from them that are useful as

building blocks for the reinforcement of polymer coils, domains, chains, and segments at the

molecular level in thermoset and thermoplastic resins, oil or aqueous emulsions, latexes, and

suspensions.

Nanostructured chemicals, such as the olefin POSS structures illustrated in Figure 1,

can exist as solids, waxes, and oils. A variety of olefiinc R groups such as cyclohexene,

norbornene, allyl, and styrenyl can be considered for inclusion on nanostructured chemicals.

However, the lowest cost systems that are also commercially available commercially are the

vinylsilanes. Vinyltrialkoxysilanes and vinyltrichorosilane are commercially available in

industrial quantities. Historically the synthesis process for vinyl POSS systems has been

plaqued by low yields, long reaction times, and irreproducible product yields. The chemical

equation for synthesis of vinyl POSS involving trichloro or alkoxy silanes can be generically

represented as follows:

ViSiCl ₃ + H ₂ O → vinylPOSS + HCl (1)

ViSi(OR) ₃ + H ₂ O + HCl → vinylPOSS + ROH (2)

ViSiCl ₃ + MeOH → vinylPOSS + HCl (3)

The chemical reactions illustrated in Equations 1, 2, and 3 are shown in

nonstoichiometric form as the effects of water, HCl, ROH (alcohol), and concentration of

silane have dramatic influences on product yield and the purity of isolated product. A wide

variety of olefin POSS structures can be obtained as illustrated in Figure 1.

To illustrate this point, Figures 2 and 3 describe the complex relationship of water and

acid relative to yield of the vinyl POSS cage. Furthermore, the concentration of the acid in

equations 2 and 3 can be varied from 1% to 39% with a preferred concentration of 37.9%.

In the design of a continuous process it is also desirable to recognize the chemical

stability and the ability to isolate the olefin POSS products from the reaction medium. In

Equations 1-3, the vinyl POSS is both chemically stable to the reaction medium and

insoluble. The insolubility of the POSS product, in the reaction medium, facilitates its

collection via filtration of the reaction mixture. The collection of product is further facilitated by running the reaction at room temperature which avoids the loss of product due to reactions

or solubilzation that can occur at elevated temperatures.

The concentration of silane added to the reaction medium can be varied from 0.01 M -

5.0 M. A preferred concentration range is 0.3 M to 2.0 M, and a more preferred concentration

for continuous reaction purposes is 1.3 M - 1.5 M.

While a continuous process has been established for each reaction illustrated in

Equations 1-3, equations 1 and 3 are less desirable, as they require equipment investments to

handle corrosive HCl byproducts. Equation 2 is more easily managed though use of readily

available plastic or glass lined reaction vessels and filtration equipment.

It should be further noted that equations 1 and 3 produce three equivalents of HCl for

each equivalent of vinyltrichlorosilane while equation 2 produces three equivalents of alcohol

per equivalent of vinytrialkoxy silane. The liberation of alcohol in equation 2 is highly

desirable as it aids in solubilization of the starting materials and in the solubilization of vinyl

POSS intermediates and resinous by-products. In the case of equations 1 and 3, alcohol is

required to rinse the final POSS products to remove such intermediates, oligomers and

polymers.

Finally, the formation of vinyl POSS in equations 1-3 is driven by the precipitation of

the product from the acid methanol solution. A resinous by-product is also produced in the

reaction but it does not precipitate from the reaction as it remains soluble in methanol.

EXAMPLES

General Process Variables Applicable To All Processes

As is typical with chemical processes, there are a number of variables that can be used

to control the purity, selectivity, rate and mechanism of any process. Variables influencing

the process for the formation of nanostructured chemicals (ej^ POSS/POS, etc.) include the

size, polydispersity, and composition of the nanostructured chemical desired, the kinetics,

thermodynamics, and aids used during the reaction process such as catalysts, cocatalyst,

supports, and surfactants, and other factors such as temperature, pressure, templates, solvent,

gases and mixtures thereof.

Vinyl POSS can be produced from vinyltrimethoxy, vinyltriethoxy silane or

vinyltrichloro silane (or related derivatives), either via the filtration of product every 24 hours

or by filtration of the product after the addition of silane over a period of successive 24 hour

additions, hi general it is preferred to filter and collect the reaction product once every 24

hours.

Example 1 - Vinyltrichorosilane Method

In the case of synthesis from vinyltrichloro silane, the vinyltrichloro silane is

premixed for 10 minutes with 3.5 equivalents of methanol. The prereacted solution (0.85%)

is then added to a stirred solution of methanol (65.7% v/v), HCl (32.7% v/v), and water

(0.65% v/v). The periodic addition of a solubilizing amount of methanol is required to

minimize the formation of a sticky white resinous by-product that can contaminate the

octavinyl POSS. The amount of MeOH required is variable and is determined by visual

solubilization of any sticky precipitated resin on the walls of the reaction vessel.

Example Ia

In a 1000 mL round bottom flask containing methanol (500 mL), HCl (250 ml), and water (5 mL) the mixture was allowed to come to room temperature. Vinyl trimethoxy silane

(6.5 mL) was added slowly to the reaction mixture and reaction was continued for 24 hours

with stirring (magnetic stirrer). In one case it was filtered and the reactor charged with

additional silane (6.5 mL), and the process is repeated 5 to 20 times. 20 time addition and

filtration produced 35.3% Vi8T8. (Yield was based on the final product, which was washed

with methanol and dried.) 10 times addition and no filtration produces 32.8% Vi8T8. (Yield

was based on the final product, which was washed with methanol and acetone and dried in

vacuum).

Example Ib

hi a 1000 mL round bottom flask containing methanol (500 mL), HCl (250 ml), and

water (5 mL) added slowly, the mixture was allowed to come to room temperature. Vinyl

trimethoxy silane (6.5 mL) was added slowly to the reaction mixture and reaction was

continued for 24 hours with stirring (magnetic stirrer). Total yield of 5 times

addition/filtration was 40.8%. Total yield of 5 times addition/no filtration was 40.8%. (Yield

was based on the final product which was washed with methanol and dried)

Example 2 - Vinyltrialkoxysilane Method

The process for producing octavinyl POSS from vinyltrimethoxy silane involves the

room temperature addition of the silane (0.85% v/v) every 24 hours to a stirred solution of

methanol (65.7% v/v), HCl (32.7% v/v), water (0.65% v/v). The reaction mixture is capable

of continuously producing octavinyl POSS either via the successive filtration of product or by

the continuous addition of silane.

Alternately, in a 1000 mL round bottom flask containing methanol (500 mL), HCl

(250 ml), and water (5 mL) added slowly, the mixture was allowed to come to room

temperature. Vinyl trimethoxy silane (6.5 mL) was added slowly to the reaction mixture and

reaction was continued for 24 h with stirring (magnetic stirrer). In one case it was filtered and

the reactor charged with additional silane (6.5 mL), and the process repeated 5 to 20 times.

In another case the reactor was charged with additional silane (6.5 mL) and the process was

repeated 5 to 20 times.

Example 3 - Hydroamination of Vinyl POSS

The hydroamination of olefins is a well known reaction. Figure 5 illustrates

hydroamination of vinyl POSS. A 50 g sample of vinyl POSS is suspended in a liquid

ammonia solution and to this PtBr ₂ and nBuψPBr is added. The mixture was allowed to react

over 8 hours to product the desired octaminoethyl POSS. The product was isolated as a white

solid.

Example 4 - Polyisocvanate Formation

A 50g sample of octaminoethyl POSS was reacted with phosgene for 4 hours at 50°C to

produce the octaethylisocyante POSS. The product was isolated as a white solid. Figure 6

illustrates polyisocyanate formation with POSS.

Example 5 - Hvdrolvtic Oxidation of Vinyl POSS

Transition metal oxides such as OsO ₄ and MnO ₄ ^" have long been known to be

powerful oxidizing agents. Amine catalyzed osmylation followed by hydrolysis is a known

method to produce dialcohol products from vinyl groups. A 50 g sample of vinyl POSS was

stirred into osmium tetroxide. The mixture was allowed to react for 2 hours and then washed

with aqueous acid to produce a white solid of octaethylglycol POSS that was collected

through filtration. Figure 7 schematically shows the process of alcohol formation.

While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and apparatus disclosed herein may be made without departing from the scope of the invention which is defined in the appended claims.

What is claimed is: