Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
  • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
  • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/12—Copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
  • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/85—Arrangements for extracting light from the devices
  • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses

Definitions

• Embodiments in accordance with the present invention relate generally to 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 compositions encompassing norbornene (NB) based olefinic monomers, which undergo mass polymerization to form optical layers having utility in a variety of opto-electronic applications including as encapsulants, coatings, and fillers.
• NB norbornene
• OLEDs Organic light emitting diodes
• OLEDs are gaining importance in a variety of applications, including flat panel televisions and other flexible displays, among other applications.
• 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 .
• 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).
• compositions of this invention are 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.
• components 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.
• compositions of this invention are also compatible with a "one drop fill” (commonly known as "ODF").
• ODF one drop fill
• 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.
• ODF the method is known as ODF which can be misleading because several drops or lines of material are generally dispensed inside the seal lines.
• 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.
• composition encompassing a Component A and a Component B, wherein each of Component A and Component B comprises one or more monomers of formula (I) or formula (II) and wherein Component A further comprises a procatalyst and Component B further comprises an activator, wherein:
• n is an integer 0, 1 or 2;
• Ri, R 2 , R 3 and » is a group of formula (A):
• X is selected from the group consisting of:
• Aryl is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl and substituted or unsubstituted fluorenyl; the remaining Ri, R 2 , R 3 and R4 are the same or different and each independently represents hydrogen, halogen, a hydrocarbyl or haiohydrocarbyl group selected from the group consisting of methyl, ethyl, linear or branched (C3-C] 2 )alkyl, perfluoro(Ci-Ci2)alkyl, (C3-Ci 2 )cycloalkyl, (C6-Ci 2 )bicycloalkyl, (C 7 -Ci4)tricycloalkyI, (C 6 -Cio)aryl,
• n is an integer 0, 1 or 2;
• R7, R 8 , R9 and Rio are the same or different and each independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl or haiohydrocarbyl group selected from methyl, ethyl, linear or branched (C 3 -Ci6)alkyl, perfluoro(Ci-Ci 2 )alkyl, (C 3 -Ci2)cycloalkyl, (C6-Ci 2 )bicycloalkyl, (C 7 -Ci 4 )tricycloalkyl, (C6-Cio)aryl, (C6-Cio)aryl(Ci-C 6 )alkyl, perfluoro(C6-Cio)aryl, perfluoro(C6-Cio)aryl(Ci-C 3 )alkyI and a group of formula (B):
• Y is selected from the group consisting of:
• Aryli is phenyl or phenyl substituted with one or more (Ci-Ce)alkyl
• said monomer of formula (I) is having a refractive index greater than or equal to 1.6 and said Component A and Component B are in a clear liquid form at room temperature.
• kits encompassing the Component A and Component B of the compositions of this invention for forming a transparent film.
• wv 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.
• hydrocarbyl refers to a group that contains carbon and hydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl.
• halohydrocarbyl refers to a hydrocarbyl group where at least one hydrogen has been replaced by a halogen.
• perhalocarbyl refers to a hydrocarbyl group where all hydrogens have been replaced by a halogen.
• (Ci-C6)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.
• phenylcarboyl(Ci-C 4 )alkyl and "phenoxy(Ci-C 4 )alkyl” are to be construed accordingly.
• 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.
• (Ci-C6)perfluoroalkyl means that all of the hydrogen atoms in said alkyl group are replaced with fluorine atoms.
• Illustrative examples include trifluoromethyl and pentafluoroethyl, and straight-chained or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl groups.
• Derived expression, "(Ci- C6)perfluoroaIkoxy” is to be construed accordingly.
• alkyl groups as described herein such as for example, "(Ci-C6)alkyl” may partially be fluorinated, that is, only portions of the hydrogen atoms in said alkyl group are replaced with fluorine atoms and shall be construed accordingly.
• (C6-Cio)aryl means substituted or unsubstituted phenyl or naphthyl.
• 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.
• (C6-Cio)aryl(Ci-C4)alkyl means that the (Ce-Cio)aryl as defined herein is further attached to (Ci-C4)alkyl as defined herein.
• Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.
• Halogen or "halo" means chloro, fluoro, bromo, and iodo.
• substituted is contemplated to include all permissible substituents of organic compounds.
• substituted means substituted with one or more substituents independently selected from the group consisting of O-ealkyl, C2-6alkenyl, Ci ⁇ perfluoroalkyl, phenyl, hydroxy, -CO2H, an ester, an amide, Ci-Cealkoxy, Ci-Cethioalkyl, Ci-C6perfluoroalkoxy, -NH 2 , CI, Br, I, F, - NH-lower alkyl, and -N(lower alkyl) 2 .
• any of the other suitable substituents known to one skilled in the art can also be used in these embodiments.
• modulus is understood to mean the ratio of stress to strain and unless otherwise indicated, refers to the Young's Modulus or Tensile Modulus measured in the linear elastic region of the stress-strain curve. Modulus values are generally measured in accordance with ASTM method DI708-95. Films having a low modulus are understood to also have low internal stress.
• polymeric repeating units are polymerized (formed) from, for example, polycyclic norbornene-type monomers in accordance with formulae (I) to (IV) wherein the resulting polymers are formed by 2,3 enchainment of norbornene-type monomers as shown below:
• composition encompassing a Component A and a Component B, wherein each of Component A and Component B comprises one or more monomers of formula (I) or formula (II) and wherein Component A further comprises a procatalyst and Component B further comprises an activator, wherein:
• n is an integer 0, 1 or 2;
• Ri, R 2 , R3 and R4 is a group of formula (A):
• X is selected from the group consisting of:
• R x in each occurrence is independently selected from methyl, ethyl, linear or branched (C3-Ci2)alkyl or (C6-Cio)aryl
• the remaining Ri, R 2 , R 3 and R4 are the same or different and each independently represents hydrogen, halogen, a hydrocarbyl or halohydrocarbyl group selected from the group consisting of methyl, ethyl, linear or branched (C3-Ci 2 )alkyl, perfluoro(Ci-Ci2)alkyl,
• n is an integer 0, 1 or 2;
• R 7 , Rs, R9 and Rio are the same or different and each independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl or halohydrocarbyl group selected from methyl, ethyl, linear or branched (C3-Ci6)alkyl, perfluoro(Ci-G 2 )alkyl, (C3-Ci 2 )cycloalkyl, (C 6 -Ci 2 )bicycloalkyl, (C 7 -Ci 4 )tricycloalkyl, (Ce-Cio)aryl, (C6-Cio)aryl(Ci-C6)aIkyl, perfluoro(C6-Cio)aryl, perfIuoro(C6-Cio)aryl(Ci-C3)alkyI and a group of formula (B):
• Y is selected from the group consisting of:
• Aryli is phenyl or phenyl substituted with one or more (Ci-C 6 )alkyl;
• said monomer of formula (I) is having a refractive index greater than or equal to 1.6 and said Component A and Component B are in a clear liquid form at room temperature.
• the monomers employed in the composition of this invention are mostly known in the literature or a few of them may be novel, but can be prepared by any of the known methods in the art to make such or similar types of monomers. Some such procedures have been provided hereafter in the specific examples that follows.
• the monomers as described herein readily undergo mass polymerization, i.e., in their neat form without use of any solvents by vinyl addition polymerization using transition metal catalysts, such as for example, nickel, palladium or platinum.
• transition metal catalysts such as for example, nickel, palladium or platinum.
• the term "mass polymerization” as used herein shall have the generally accepted meaning in the art. That is, a polymerization reaction that is generally carried out in the substantially absence of a solvent. In some cases, however, a small proportion of solvent is present in the reaction medium.
• solvent may be used to dissolve the procatalyst and/or the activator or convey the same to the reaction medium.
• some solvent may be used to reduce the viscosity of the monomer.
• the amount of solvent that can be used in the reaction medium may be in the range of 0 to 50 weight percent based on the total weight of the monomers employed.
• Any of the suitable solvents that dissolves the catalyst, activator and/or monomers can be employed in this invention.
• suitable solvents include alkanes, cycloalkane, toluene, THF, methylene chloride, dichloroethane, and the like.
• one or more of the monomers themselves can be used to dissolve the procatalyst as well as the activator and thus avoiding the need for the use of solvents.
• one monomer can itself serve as a solvent for the other monomer and thus eliminating the need for an additional solvent.
• a monomer of formula (I) is a solid at room temperature
• a monomer of formula (II) (or even a different monomer of formula (I)), which is liquid at room temperature can be used as a solvent for the monomer of formula (I) which is a solid or vice versa. Therefore, in such situations more than one monomer can be employed in the composition of this invention.
• monomers of formula (I) serve as high refractive index materials imparting high refractive index to the resulting polymeric film upon mass polymerization by mixing Component A and Component B together.
• monomers of formula (I) as used herein may be termed as "Refractive index modifiers" of the composition of this invention.
• the monomers of formula (I) which are suitable in this invention feature a refractive index of equal to 1.6 or higher.
• the refractive index of the monomers of formula (I) is higher than 1.6.
• the refractive index of the monomers of formula (I) is in the range from about 1.6 to 1.8.
• the refractive index of the monomers of formula (I) is higher than 1.65, higher than 1.7 or higher than 1.75. In some other embodiments it may even be higher than 1.8.
• monomer of formula (II) if employed, serves as a viscosity modifier.
• monomer of formula (II) is a liquid at room temperature and can be used in conjunction with monomer of formula (I) which can be a solid, high viscosity liquid and/or a low viscosity liquid.
• monomer of formula (I) is a low viscosity liquid which can be used in combination with a high viscosity liquid of monomer of formula (II). Accordingly, all such combinations are part of this invention.
• composition of this invention encompasses only one monomer of formula (I). In some other embodiments of this invention the composition of this invention encompasses only one monomer of formula (II). Such compositions results in a film having a homopolymer of the respective monomer of formula (I) or (II).
• the composition of this invention encompasses at least two monomers wherein first monomer is of formula (I) and a second monomer is of formula (II).
• the monomer of formula (II) can exhibit a refractive index less than 1.6.
• the refractive index of the monomers of formula (II) is less than 1.59.
• the refractive index of the monomers of formula (II) is in the range from about 1.4 to 1.6.
• the refractive index of the monomers of formula (II) is lower than 1.55, lower than 1.5 or lower than 1.45. In some other embodiments it may even be lower than 1.4. It should however be noted that two different monomers of formula (I) or two different monomers of formula (II) can also be employed. All such permissible combinations are to be considered part of this invention.
• the monomer of formula (II) also generally exhibit low viscosity, which can be below 100 centipoise. In some embodiments, the viscosity of the monomers of formula (II) is less than 90 centipoise. In some other embodiments the viscosity of the monomers of formula (II) is in the range from about 40 to 100 centipoise. In yet some other embodiments the viscosity of the monomers of formula (II) is lower than 80 cP, lower than 60 cP or lower than 50 cP. In some other embodiments it may even be lower than 40 cP.
• the first monomer e.g., monomer of formula (I) is completely miscible with the second monomer, e.g., monomer of formula (II) and forms a clear solution. Accordingly, the monomer of formula (II) serves as a "Viscosity modifier" of the composition of this invention.
• the composition of this invention contains two monomers, for example, the monomer of formula (I) and the monomer of formula (II), 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. Accordingly, the molar ratio of monomer (I) to monomer (II) can be from 0: 100 to 100:0. That is, only monomer of formula (I) or monomer of formula (II) can be employed in certain applications. In other words, any amount of these two monomers can be employed.
• the molar ratio of monomer of formula (I):monomer of formula (II) is in the range from 5:95 to 95:5; in some other embodiments 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.
• composition according to this invention forms a substantially transparent film when Component A and Component B are mixed together at a temperature from 50 °C to 150 °C. That is to say, that when Component A and Component B are mixed together at a temperature from 50 °C to 150 °C. That is to say, that when Component A and
• Component B are mixed together and heated to certain elevated temperature, the monomers undergo mass polymerization to form films which are substantially transparent to visible light.
• 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 temperature that is suitable to carry out this mass polymerization can be employed, such as for example, 50 °C to 150 °C as indicated above.
• any temperature below 50 °C or higher than 150 °C can also be employed.
• compositions in accordance with the present invention encompass the above described one or more of the monomer of formula (I) and if needed one or more monomer of formula (II), 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.
• compositions of this invention can also include other high refractive polymeric materials which will bring about such intended benefit.
• polymers include without any limitation, poly(ot- methylstyrene), poly(vinyl-toluene), copolymers of a-methylstyrene and vinyl-toluene, and the like.
• various known optically transparent inorganic materials can also be used to increase the refractive index of the compositions of this invention.
• Such examples include silicon based inorganic materials, including but not limited to bentonite, aluminum-magnesium silicate, aluminum silicate, magnesium silicate, calcium silicate, barium silicate, strontium silicate, montmorillonite, beidellite, nontronite, saponite, hectorite, silica, silicic anhydride, silylated silica, and the like.
• inorganic materials include but not limited to titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, cerisite, white mica, synthetic mica, bronze mica, lepidolite, black mica, lithia mica, silicic acid, silicic acid anhydride, metal tungstate, hydroxyapatite, vermiculite, higilite, hectolite, zeolite, ceramics powder, dibasic calcium phosphate, alumina, aluminum hydroxide, boron nitride, and silicon nitride.
• such inorganic materials are present in the form of a nanoparticles so as to obtain fine dispersion of the inorganic materials into the compositions of this invention and provide optical transparency in the visible region, thus providing a homogeneously dispersed composition exhibiting uniformly high refractive index property throughout the dispersed composition of this invention.
• the average particle size distribution of such inorganic nanoparticle materials is generally less than 100 nm, less than 50 nm or less than 25 nm.
• nanoparticles of titania is uniformly dispersed throughout the film formed from the composition of this invention.
• any amount of one or more of the aforementioned inorganic materials can be used in the composition of this invention so as to bring about the required change in refractive index.
• 5 to 60 weight percent of the inorganic materials can be used.
• 10 to 50 weight percent of the inorganic materials can be used.
• 20 to 40 weight percent of the inorganic materials can be used.
• compositions of this invention can also contain additional monomers.
• the composition according to this invention may further contain one or more monomers selected from monomer of formula (III) or monomer of formula (IV).
• o is an integer from 0 to 2, inclusive;
• D is S1R14R15R16 or a group of formula (C): -(CH 2 ) c -OSiRi 4 Ri5Ri6 (C); wherein
• c is an integer from 1 to 10, inclusive, and where one or more of CH 2 is optionally substituted with (Ci-Cio)alkyl or (Ci-Cio)perfluoroalkyl;
• Rii, Ri 2 and Rn 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 (C3-Ci 2 )alkyl, (C3-Ci 2 )cycIoalkyl, (C6-Ci 2 )bicycloalkyl, (C7-Ci 4 )tricycloalkyl, (Cs-Cio)aryl, (C 6 -Cio)aryl(Ci-C 3 )alkyl, (Ci-Ci 2 )alkoxy, (C 3 -Ci 2 )cycloalkoxy,
• RH, Ri5 and R 16 are each independently of one another methyl, ethyl, linear or branched (C 3 -C9)alkyl, substituted or unsubstituted (C6-Ci 4 )aryl, methoxy ethoxy, linear or branched (C 3 -C9)alkoxy or substituted or unsubstituted (C6-Ci 4 )aryloxy.
• monomers of formula (III) provides further advantages. Namely, the monomers of formula (III) 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 (III) are generally improve the adhesion properties and thus can be used as "adhesion modifiers.” Finally, the monomers of formula (III) may exhibit low viscosity and good solubility for the procatalyst and/or activator, among various advantages.
• the monomer of formula (IV) is:
• Z is an arylene selected from the following:
• Ri7, Ri8, Ri9, R20, R21 and R 22 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 (C3-Ci2)alkyl, (C3-O 2 )cycloalkyl, (C6-Ci 2 )bicycloalkyl,
• the monomers of formula (IV) are bifunctional monomers expected to exhibit high refractive index. Accordingly, it is contemplated that incorporation of monomers of formula (IV) 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 (IV) into the composition of this invention my increase compatibility with other materials depending upon the intended application thereby enhancing the properties of the composition of the invention.
• any of the monomers within the scope of monomer of formula (I) can be employed in the composition of the invention as either Component A or Component B or in both Components A and B.
• Representative examples of monomer of formula (I) include the following without any limitations:
• NBMeOCPh 3 5-((trityloxy)methyl)bicyclo[2.2.1]hept-2-ene
• DoDecNB -dodecylbicyclo[2.2.1]hept-2-ene
• monomer of formula (III) to form the composition of this invention it is contemplated that any monomer within the scope of monomer of formula (III) can be employed.
• exemplary monomers of such type include but not limited to those selected from the group consisting of:
• NBMeOSiPh 3 bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)triphenylsilane
• TESNB bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane
• monomer of formula (IV) to form the composition of this invention it is contemplated that any monomer within the scope of monomer of formula (IV) can be employed.
• exemplary monomers of such type include but not limited to those selected from the group consisting of:
• composition of this invention encompasses one or more monomers of formula (I) and at least one monomer of formula (II).
• composition of this invention encompasses one or more monomers of formula (II) and at least one monomer of formula (III) and optionally one monomer of formula (I) and one monomer of formula (IV).
• the composition of this invention encompasses one monomer of formula (I), one or more monomers of formula (II) and at least one monomer of formula (III), and optionally one monomer of formula (IV).
• the composition contains any of the procatalyst that would bring about the mass polymerization as described herein.
• suitable procatalysts include a number of known neutral salts of transition metals, such as palladium or platinum, among others.
• Exemplary procatalysts without any limitation maybe selected from the group consisting of:
• composition of this invention contains an activator which when combined with the procatalyst will cause mass polymerization of the monomers contained therein at a desirable temperature as described herein.
• activators Any of the known activators can be employed for this purpose.
• Exemplary activators without any limitation maybe selected from the group consisting of:
• lithium inflate lithium tetrakis(pentafluorophenyl)borate
• lithium tetrakis(pentafluorophenyl)borate isopropanolate lithium tetrakis(pentafluorophenyl)borate isopropanolate
• the composition of this invention contains in each of the Component A and Component B 5-(2-([l,l'-biphenyl]-4-yl)ethyl)bicyclo[2.2.1]hept- 2-ene (NBEtPhPh), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB) and (bicyclo[2.2.1]hept-5-en- 2-ylmethoxy)(methyl)diphenylsilane (NBCH 2 OSiMePh 2 ).
• the Component A further contains palladium (II) bis(tricyclohexyl-phosphine) diacetate as procatalyst and Component B contains lithium tetrakis(pentafluorophenyl)borate etherate as an activator.
• a kit for forming a substantially transparent film There is dispensed in this kit two components designated as a Component A and a Component B. In each of these Component A and Component B there is dispensed one or more monomers of formula (I), formula (II), formula (III) or formula (IV) and wherein Component A further comprises a procatalyst and Component B further comprises an activator.
• the monomers of formula (I) to formula (IV) are the ones as described hereinabove.
• the Component A and Component B of the aforementioned kit can encompass one or more monomers of formula (I), one or more monomers of formula (II), one or more monomers of formula (III) and one or more monomers of formula (IV).
• the kit of this invention encompasses Component A and Component B containing at least two monomers wherein first monomer is of formula (I) and second monomer is of formula (II). Any of the monomers of formula (I) or (II) as described herein can be used in this embodiment.
• the molar ratio of monomers of formula (I) and formula (II) contained in these components 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.
• the kit may encompass Component A and Component B wherein dispensed only one monomer which could be monomer of formula (I), monomer of formula (II), monomer of formula (III) or monomer of formula (IV). Further, the monomers of formulae (I) to (IV) are completely miscible with each other to form a clear solution at room temperature.
• two or more monomers of formulae (I) to (IV) can be mixed together with a solvent to form a clear solution as described herein.
• the monomer mixture may become a clear solution at slightly elevated temperature, such as for example, 30 °C or 40 °C or 50 °C, or at higher than 50 °C, before they undergo mass polymerization.
• the Component A and Component B are mixed together at a temperature of from 50 °C to 100 °C for a sufficient length of time to form a polymeric film.
• the Component A and Component B are mixed and poured onto a surface or onto a substrate which needs to be encapsulated, and heated to a temperature of 50 °C to 100 °C in order for the monomers to undergo polymerization to form a solid transparent polymer which could be in the form of a transparent film.
• a temperature of 50 °C to 100 °C in order for the monomers to undergo polymerization to form a solid transparent polymer which could be in the form of a transparent film.
• such polymerization can take place at 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C or higher.
• the heating can also be carried out in stages to trigger the polymerization, for example to 60 °C for 5 minutes, and then heating to 70 °C for 15 minutes and so on.
• substantially transparent film means that the films formed from the composition of this invention are optically clear in the 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 the films formed from the composition of this invention exhibit at least 95 percent of visible light transmission.
• the kit as described herein encompasses Component A and Component B which further contain one or more monomers selected from monomer of formula (III) or monomer of formula (IV) as described hereinabove.
• monomers of formula (III) or (IV) as described herein can be used in this embodiment, and in any desirable amounts depending on the nature of the intended use.
• the kit as described herein encompasses Component A and Component B, each of which contains 5-(2-([ 1 , 1 '-biphenyl]-4-yl)ethyl)bicyclo[2.2.1 ]hept-2-ene (NBEtPhPh), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB) and (bicyclo[2.2.1]hept-5-en-2- yImethoxy)(methyI)diphenylsiIane (NBCH 2 OSiMePh 2 ); and wherein Component A further contains palladium (II) bis(tricyclohexyl-phosphine) diacetate and Component B contains lithium tetrakis(pentafluorophenyl)borate etherate.
• Component A further contains palladium (II) bis(tricyclohexyl-phosphine) diacetate and Component B contains lithium tetrakis(p
• composition comprising a Component A and a Component B, wherein each of the Component A and the Component B comprises one or more monomers of formula (I) or formula (II) and wherein the Component A further comprises a procatalyst and the Component B further comprises an activator.
• Any of the monomers of formula (I) or formula (II) as described hereinabove can be used in this aspect of the invention.
• the monomer of formula (I) is having a refractive index greater than or equal to 1.6.
• the monomer of formula (II) is having a refractive index less than 1.6 and viscosity below 100 centipoise.
• the monomer of formula (I) is completely miscible with said second monomer of formula (II) and forms a clear solution.
• the Component A and the Component B are mixed together and exposed to a temperature in the range of from 50 °C to 100 °C forms a substantially transparent film having a transmission higher than 90 percent of the visible light.
• a method of forming a substantially transparent film for the fabrication of a variety of optoelectronic device comprising: forming a Component A and a Component B, wherein each of the Component A and the Component B comprises one or more monomers of formula (I) or formula (II) and wherein the Component A further comprises a procatalyst and the Component B further comprises an activator;
• the coating of the desired substrate to form a film with the mixture of Component A and Component B 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, ink jet 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 for electrical, electronic or optoelectronic devices, for example, a semiconductor substrate, a ceramic substrate, a glass substrate.
• the coated substrate is baked, i.e., heated to facilitate the mass polymerization, for example to a temperature from 50°C to 100°C for from about 1 to 30 minutes, although other appropriate temperatures and times can be used.
• the substrate is baked at a temperature of from about 60°C to about 90°C for 2 minutes to 10 minutes.
• the films thus formed are then evaluated for their optical properties using any of the methods known in the art.
• 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. Quantitatatively the percent transparency can be measured by visible spectroscopy.
• the films formed according to this invention exhibit excellent optical transparent properties and can be tailored to desirable refractive index as described herein.
• a optically transparent film obtained by the mass polymerization of the composition as described herein.
• an optoelectronic device comprising the transparent film of this invention as described herein.
• NBEtPhPh 5-(2-([l,l'-biphenyl]-4-yl)ethyl)bicyclo[2.2.1]hept-2-ene;
• NBMeOSiPh 3 (bicyclo[2.2.1 ]hept-5-en-2-ylmethoxy)triphenylsilane
• NBMeOCPh 3 5-((trityloxy)methyl)bicyclo[2.2.1]hept-2-ene
• LiFABA lithium tetrakis(pentafluorophenyl)borate etherate; THF - tetrahydrofuran;
• the mixture was sonicated and gave ⁇ 750 mL solution. This was transferred by cannula and vacuum into the other addition funnel.
• the BrPhPh THF solution was added dropwise to the Mg. After 7 minutes, the temperature rose from 14 °C to 27 °C, but the mixture was starting to reflux. The liquid level had not reached the tip of the thermowell. Five hundred mL of THF was added quickly. The temperature rose to 59 °C after another ten minutes. When the temperature dropped to 53 °C, the addition rate of the BrPhPh THF solution was increased. Addition of BrPhPh solution was completed after 2.25 h with the temperature reaching a maximum of 64 °C. The reaction was heated at 60 °C for 5 h and the title compound was formed as a solution.
• the reaction was cooled to 4 °C. Five hundred mL of saturated aqueous NH 4 C1 was added, causing the temperature to rise to 26 °C. Another 500 ml saturated aqueous NH4CI was added. The mixture was stirred vigorously to thoroughly mix all solids. The mixture was filtered. The flask and filter cake were rinsed with 250 mL MTBE. The blue aqueous phase was separated from the green organic phase. The aqueous phase was extracted with 3 x 500 mL MTBE. The MTBE extracts were combined with the green organic phase. The combined mixture was washed with 4 x 500 mL brine to bring the pH to 7 from 10 and until the brine wash was no longer blue.
• a 500 mL reactor equipped with a septum and a magnetic stirbar was charged with a solution of 9-fluorenylmethoxycarbonyl chloride (50 g, 193.8 mmol, 1 eq) in THF (250 mL).
• the reactor was sealed and vented with three 16G needles and placed in a water bath at room temperature.
• To this stirred solution was added 5-norbornene-2-methanol (24.6 g, 198.6 mmol, 1.03 eq) along with pyridine (15.7 g, 198.6 mmol, 1.03 eq) simultaneously over 20 minutes. After addition the reaction mixture was allowed to stir at room temperature for 4 days.
• the reaction mixture became a slurry with white solid and a light yellow reaction liquid.
• reaction mixture was filtered through a coarse glass frit and the solids were washed with THF (100 mL). The organics were removed by rotary evaporation to dryness resulting in a light yellow solid.
• NBSi(CH 3 ) 2 OSiPh 3 Into a 500 mL reactor purged with dry nitrogen and equipped with septum, dropping funnel, thermocouple and a magnetic stirbar was charged with a solution of 5- (ethoxydimethylsilyl)bicyclo[2.2.1]hept-2-ene (27.1 g, 138.4 mmol) in 100 mL of toluene. The reactor was sealed and vented with three 16G needles and placed in a water bath at room temperature.
• Example 2A The procedures of Example 2A were substantially repeated in this Example 2B except for employing diphenylmethylsilane in place of triphenylsilane to obtain the title compound (89% yield).
• Example 2A The procedures of Example 2A were substantially repeated in this Example 2C except for employing 5-norbornene-2-methanol in place of 5-(ethoxydimethylsilyl)bicyclo[2.2.1]hept- 2-ene to obtain the title compound (82% yield).
• reaction mixture was then filtered through a coarse glass frit and the solids were washed with toluene (50 mL).
• the filtrate was rotary evaporated to dryness to obtain a pale yellow solid, which was washed thrice with acetone and dried under vacuum, to obtain the title compound as a white solid, 25.2 g (96% yield).
• Example 2E The procedures of Example 2E were substantially repeated in this Example 2F except for employing 2-naphthol in place of 1-naphthol to obtain the title compound as a crystalline solid (36% yield).
• Example 2E The procedures of Example 2E were substantially repeated in this Example 2G except for employing 2-phenylphenol in place of 1-naphthol to obtain the title compound (91% yield).
• Example 3 illustrates the homopolymerization of the monomer of Example 1 by solution vinyl addition polymerization.
• NBEtPhPh (5.07 g, 18.5 mmol), toluene (11.4 g), and ethyl acetate (3.04 g).
• the reactor was sealed and sparged with N 2 for 10 minutes.
• the reactor was brought to temperature (60 °C) with stirring and catalyst solution (NiARF (0.09 g, 0.185 mmol) in toluene (0.77 g), prepared in a glove box) was added in one shot.
• the reaction was allowed to stir overnight.
• the reaction mixture was cooled to room temperature followed by addition of acetic acid (2 g), hydrogen peroxide 30% in water (4 g), and water (4 g).
• the bottle was resealed and vented with two 16 gauge needles and the mixture was allowed to stir overnight at room temperature.
• the reaction mixture was then transferred to a separatory funnel.
• the mixture separated into two phases.
• the organic phase was added to stirring hexanes (1 L) in order to precipitate the polymer.
• the resulting mixture was filtered to collect the solids which were dried overnight at 50 °C under vacuum.
• the polymer was isolated as a white powder (4 g, 80 % yield) with M w : 50,000 and PDI: 2.09 as determined by GPC.
• lithium tetrakis(pentafluorophenyl)-borate etherate (1.5 mg, 0.0017 mmol) was weighed.
• NBCH 2 OSiMePh 2 1. g, 4.4 mmol
• the Components A and B were mixed together.
• the mixture was swirled for a few minutes to aid dissolution.
• the mixture was filtered through a 0.2 ⁇ PTFE syringe filter into a clean room bottle.
• the solution was then poured onto a 2 inch bare silicon wafer.
• the wafer was spun at 500 rpm for 10 sec, then 4000 rpm for 30 sec.
• the wafer was then baked on a hotplate set at 80 °C for 50 min to initiate polymerization.
• the above procedure was repeated on a 2 inch quartz wafer using a spin speed of 500 rpm for 40 sec. Visual inspection of the resulting wafer confirmed that the polymer film is transparent in the visible spectrum.
• the polymer film thickness was determined to range from 6 to 11 microns.
• Example 4 Mass polymerization of NBEtPhPh PENB/ NBCH 2 OSiMePh 2 (60/20/20 molar ratio) The procedures of Example 4 were substantially repeated in Example 5, except that a different ratio of monomers was used: NBEtPhPh (3 g, 10.9 mmol), PENB (0.7 g, 3.5 mmol), and NBCH 2 OSiMePh 2 (1.15 g, 3.6 mmol); the amount of catalyst and activator used were: palladium bis(tricyclohexylphosphine)diacetate (0.15 mg, 0.00019 mmol) and lithium tetrakis(pentafluorophenyi)-borate etherate (0.5 mg, 0.00057 mmol).
• Example 4 both two inch silicon and quartz wafers were coated with a mixture of Components A and B as described in Example 3, and heated to initiate polymerization. Visual inspection of the resulting quartz wafer confirmed that the polymer film is transparent in the visible spectrum. The polymer film thickness was measured and it ranged from 20 to 50 microns. Using ellipsometry as described in Example 4, the refractive indices were determined and are summarized in Table 2. Table 2
• the viscosity of the combined monomer mixture of Component A and Component B was determined to be 50-60 cP at 25 °C using a Brookfield DV-I Prime viscometer.
• the homopolymer of NBEtPhPh of Example 2 was dissolved in 2-heptanone (0.5 g of polymer in 4.5 g of solvent). The solution was filtered through a 0.2 ⁇ PTFE syringe filter into a clean room bottle. The solution was then poured onto a 2 inch bare silicon wafer. The wafer was spun at 500 rpm for 10 sec, then 4000 rpm for 30 sec. The wafer was then baked on a hotplate set at 120 °C for 2 min to remove residual solvent.
• the refractive indices of the film were determined by ellipsometry as described in Example 4 and are summarized in Table 3.
• Example 7 demonstrates that a single monomer, such as for example, monomer of formula (II) can be used alone in the composition of this invention to form a transparent film.
• PENB (5 g, 15.6 mmol) was weighed into a vial.
• lithium tetrakis(pentafluorophenyl)borate etherate (4.4 mg, 0.0051 mmol) was weighed.
• the catalyst and activator were dissolved into about 0.1 mL of dichloroethane.
• the PENB was added to the dichloroethane mixture and swirled to dissolve. The solution was filtered through a 0.2 ⁇ PTFE syringe filter into a clean room bottle.
• the solution was then poured onto a 2 inch bare silicon wafer.
• the wafer was spun at 500 rpm for 10 sec, then 4000 rpm for 30 sec.
• the wafer was then heated on a hotplate set at 85 °C for 50 min to initiate polymerization.
• Example 7 The procedures of Example 7 were substantially repeated in Example 8 except NBCH 2 OSiMePh 2 (1.15 g, 3.6 mmol) was used instead of PENB.
• Example 4 Mass Polymerization of NBEtPhPh PENB/NBSi(OC 2 H 5 ) 3 (24/67/9 molar ratio) The procedures of Example 4 were substantially repeated in Example 9 except that a different ratio of the title monomers was used: NBEtPhPh (1.5 g, 5.5 mmol), PENB (3.04 g, 15.4 mmol), and NBSi(OC 2 H 5 )3 (0.52 g, 2 mmol).
• the amount of catalyst and activator used were: palladium bis(tricyclohexyIphosphine)diacetate (3.8 mg, 0.00048 mmol) and lithium tetrakis(pentafluorophenyl)-borate etherate (12 mg, 0.0014 mmol).
• Example 4 As described in Example 4, a two inch silicon wafer was coated with a mixture of Components A and B, and baked to initiate polymerization.
• the refractive indices of the film were determined by ellipsometry as described in Example 4 and are summarized in Table 6.
• This Example 10 illustrates the mass polymerization of PENB/ NBCH20SiMePh 2 monomers blended with poly(vinyltoluene-co-a-methylstyrene).
• Poly(vinyltoluene-co-a-methylstyrene) (Sigma-Aldrich, 1.2 g) was dissolved in PENB (5 g, 25.3 mmol) using a Thinky ARE-310 mixer (2000 rpm for 30 min).
• the activator, LiFABA (0.0065 g, 0.0075 mmol) was dissolved in NBCH 2 OSiMePh 2 (0.1 g, 0.30 mmol). This mixture was added to the procatalyst, palladium bis(tricyclohexylphosphine)diacetate (0.002 g, 0.0025 mmol).
• the mixture of poly(vinyltoluene-co-a-methylstyrene) and PENB was added to NBCH 2 OSiMePh 2 solution and swirled to ensure good mixing.
• Example 4 As described in Example 4, a two inch silicon wafer was coated with a mixture and baked to initiate polymerization.
• the refractive indices of the film were determined by ellipsometry as described in Example 4 and are summarized in Table 7.
• the film formed from the composition of Example 10 with a film thickness of 1.27 mm exhibited percent transmission of >93 percent between 400 and 700 nm (visible light).
• Example 4 As described in Example 4, a two inch silicon wafer was coated with a mixture and baked to initiate polymerization.
• the refractive indices of the film were determined by ellipsometry as described in
• DecNB/NBCH 2 OSiMePh 2 (50/50 molar ratio) DecNB (3.52 g, 15 mmol) was dispensed into a vial. To this monomer was added palladium bis(tricyclohexylphosphine)diacetate (2 mg, 0.003 mmol), which dissolved to form a clear solution, and was designated as Component A. Into a separate vial, designated as Component B, lithium tetrakis(pentafluorophenyl)borate etherate (2 mg, 0.009 mmol) was weighed. To this vial was added NBCH 2 OSiMePh 2 (4.81 g, 15 mmol). With slight heating, the solid lithium tetrakis(pentafluorophenyl)borate etherate dissolved.
• the Components A and B were mixed together.
• the mixture was swirled for a few minutes to aid dissolution.
• the mixture was filtered through a 0.2 ⁇ PTFE syringe filter into a clean room bottle.
• the solution was then poured onto a 2 inch bare silicon wafer.
• the wafer was spun at 500 rpm for 10 sec, then 4000 rpm for 30 sec.
• the wafer was then baked on a hotplate set at 80 °C for 60 min to initiate polymerization.
• the above procedure was repeated on a 2 inch quartz wafer using a spin speed of 500 rpm for 40 sec. Visual inspection of the resulting wafer confirmed that the polymer film is transparent in the visible spectrum.
• the polymer film thickness was determined to be 8.8 microns by profilometry.
• the above procedure was repeated on a 2 inch quartz wafer using a spin speed of 500 rpm for 40 sec. Visual inspection of the resulting wafers confirmed that the polymer film in each of the Examples 13 to 17 was transparent in the visible spectrum.
• the polymer film thickness was determined to range from 6 to 1 1 microns.
• the refractive indices of the films were determined by ellipsometry as described in Example 12 and are summarized in Table 1 1.

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