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  • 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
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  • C08F132/00—Homopolymers 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
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  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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  • C08F2/00—Processes of polymerisation
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  • C08F4/00—Polymerisation catalysts
  • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/70—Iron group metals, platinum group metals or compounds thereof
  • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
  • C08F4/7003—Bidentate ligand
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  • C08F4/7027—OO
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/70—Iron group metals, platinum group metals or compounds thereof
  • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
  • C08F4/708—Tetra- or multi-dentate ligand
  • C08F4/7088—Dianionic ligand
  • C08F4/7091—OOOO
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
  • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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  • 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
• • 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
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  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
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  • C08J2345/00—Characterised by the use 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; Derivatives of such polymers

Definitions

• 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 in the presence of derivatives of Pd(AcAc) 2 L when photolyzed to form optical layers having utility in a variety of opto-electronic applications including as encapsulants, coatings, and fillers.
• NB norbomene
• 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
• 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 ethos, 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 a two 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.
• organic filler materials that complement the refractive index of OLEDs and yet exhibit high transparency and good thermal properties, among other desirable properties.
• 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.
• an OLED device having a transparent optical layer which features 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 ⁇ m 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.
• a transparent optical layer which features 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 ⁇ m but can be tailored to lower or higher film thickness depending upon the intended application, compatible with the OLED stack, particularly the cath
• 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.
• the 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.
• 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 to weeks 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 and generally the compositions become solid objects in few minutes, i.e., within 1-10 minutes and more generally in less than one hour.
• 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. Even more advantageously, the present invention overcomes the deficiencies faced by the prior art in that a tingle component composition is much more convenient than employing a two component system especially in an ODF method.
• a single component composition encompassing a) one or more olefinic monomers; b) an organopalladium compound of formula (I) or an organopalladium compound of formula (IA) as described herein; c) a photoacid generator as described herein; and d) a photosensitizer.
• kit encompassing the composition of this invention fin ⁇ forming a three dimensional object, such as for example, a transparent film.
• 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.
• hydrocaityl refers to a group that contains carbon and hydrogen atoms, non-limiting examples being alkyl, cycloalkyl aryl, aralkyl, alkaryl, and alkenyl.
• t hat theocarbyl refers to a hydrocaibyl group where at least one hydrogen has been replaced by a halogen.
• perhalocarbyl refers to a hydrocaibyl group where all hydrogens have been replaced by a halogen.
• (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 )thioalkyP ‘XC 1 -C 4 )alkoxy(C 1 -C 4 )alkylq “hydroxy(C 1 -C 4 )alkyl”, “(C 1 -C 4 )alkylcarbonyll “(C 1 -C 4 )alkoxycarbonyl(C 1 -C 4 )alkll, “(C 1 -C 4 )alkoxycarbonyl "
• cycloalkyl includes all of the known cyclic groups.
• Representative examples of “cycloalkyl” indudes without any limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
• Derived expressions such as “cycloalkoxy”, “cycloalky lalkyl”, “cycloalkylaryl” “cycloalky lcarbonyl” are to be construed accordingly .
• (C 1 -C4 ) perfiuoroaIkyl meats 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.
• (C 1 - C 6 )perfluoroalkoxy is to be construed accordingly, ft should further be noted dial certain of the alkyl groups as described herein, such as for example, “(C 1 -C 6 )alkyl” may partially be fluorinated, that is, only portions of the hydrogen atoms in said alkyl group are replaced wife fluorine atoms and shall be construed accordingly.
• (C 6 -C 10 )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
• (C 6 -C 10 )aryl(C 1 -C4) means that the (C 6 -C 10 )aryl as defined herein is further attached to (C 1 -C 4 )alky as defined herein.
• Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmetihyl and the like.
• Halogen or “halo” means chloro, fluoro, bromo, and iodo.
• substituted is contemplated to include ail permissible substituents of organic compounds, hi a few of the specific embodiments as disclosed herein, ehe term “substituted” means substituted with one or more substituents independently selected from the group consisting of (C 1 -C 6 )alkyl, (C 2 -C 6 )alkeyn l (C 1 -C 6 )perfluoroalkyl, phenyl, hydroxy, -CO2H, an ester, an amide, (C1 -C 6 )alkoxy, (C 1 -C 6 )thioalkyi and
• polymeric repeating units are polymerized (formed) from, for example, polycyclic norbornee-type monomers in accordance with formulae (I) to (IV) wherein the resulting polymers are formed by 2,3 enchainment of norbornene-type y monomers as shown below:
• a single component composition encompassing a) one or more olefinic monomers; b) an organopalladium compound selected from the group consisting of a compound of formula (I) and a compound of formula (IA):
• L is a ligand selected from the group consisting of P(R) 3 P(OR) 3, O-PR) 3 , RCN and substituted or unsubstituted pyridines, where R is selected from the group consisting of linear or branched alkyl and Ffuoroalkyl having the formula C q H x F y , where q is an integer from 1 to 16, x and y are integers from 0 to 2q+1 and the sum of x and y is 2q+1 (C3-Cio)cycloalkyl, (C6-Cio)aiyl(C 1 -Ci6)alkyl and substituted or unsubstituted (C 6 -C 10 )aryl; each A independentiy isabidentate monoanionic ligand of formula ( ⁇ ): ; wherein: 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 R 7 are the same or different and each independently selected from the group consisting of hydrogen, linear or branched alkyl and fluoroalkyl having the formula CqH*F y , where q is an integer from 1 to 16, x and y are integers from 0 to 2qH, and the sum of x and y is 2q+l, (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 Rs, respectively, do not exist; c) a photoacid generator selected from the group consisting of: a compound of the formula ( ⁇ ): (iii) a compoundnd of the formula (IV): wherein: a is an integer from 0 to 5; An ⁇
• Rs, R3 ⁇ 4 Rio, R11 and R are the same or different and each independently selected from the group consisting of halogen, methyl, ethyl, linear or branched (C3-Ca))alkyl, (C3-Ci2)cydoalkyl, (C6-Ci2)bicycloalkyl, (C7-Cu)tricycloalkyl, (Ce-Cio)aiyl, (Ce-Cio)aryl(C 1 -C3)alkyl, (C 1 -Cujalkoxy, (C3-Ci2)cycloelkaxy, (C6-Ci2)bicycloalkoxy, (CrCi4)tricycloalkoxy, (Ce-Cio)afyk «y(C 1 -C3)alkyi, (OCio)aryk>xy, (C3 ⁇ 4-Cio)thioaiyi, (C 1 -Ce)alkanoyl(C
• the ligand, L of the otganopalladium compounds of formulae (I) or (IA) can generally be a Lewis Base, which is coordinately bonded to palladium. That is, the Lewis Base is bonded to palladium by sharing both of its lone pair of electrons. Accordingly, any of the Lewis Base known in the art can be used for fob purpose.
• a Lewis Base which can dissociate readily under foe polymerization conditions as described further in detail below generally provides more suitable compounds of formula (0 or (IA) as polymerization catalysts, Le., initiators.
• judicious selection of the Lewis Base (LB) will provide a modulation of foe catalytic activity of the compounds of fob invention.
• suitable LBs include without any limitation substituted and unsubstituted nitriles, including alkyl nitrile, aryl nitrile or aralkyl nitrile; phosphine oxides, including substituted and unsubstituted trialkyl phosphine oxides, triaiyl phosphine oxides, triaiylalkyl phosphine oxides, and various combinations of alkyl, aryl and aralkyl phosphine oxides; substituted and unsubstituted pyrazines; substituted and unsubstituted pyridines; phosphites, including substituted and unsubstituted trialkyl phosphites, triaryl phosphites, triaiylalkyi phosphites, and various combinations of alkyl, aryl and aralkyl phosphites; phosphines, including substituted and unsubstituted nitrile
• the LB is selected from acetonitrile, propkxiitrile, n-butyronitrile, tert-butyronitrile, benzonhrile (CeHsCN), 2,4,6-trimethylbezomtrile, phenyl acetonitrile (CsHsCHaCN) » pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 2,6-di-t-butylpyridine, 2,4-di-t-butylpyridine,
• PRs include without any limitation trimethyl phosphine, tricthyl phosphine, tri-n-propyl phosphine, tri-iso-propyl phosphine, tri-n-butyl phosphine, tri-iso-butyl phosphine, tri-teit-butyl phosphine, tricyctopentylphosphine, triallylphosphine, tricyclohexylphosphine, triphenyl phosphine, trimethyl phosphite, triethyl phosphite, trifluoroethyl phosphite, tii-n-propyl phosphite, tri-iso-propyl phosphite, tri-n-butyl phosphite, tri-iso-butyl phosphite, tri-tert-butyl phosphite, tricyclopen
• olefinic monomers which undergo vinyl addition polymerization can be employed in the composition of this invention.
• Such olefinic monomers include without any limitation alfcyclic olefins, such as ethylene, propylene, butylene, styrene, and the like.
• Other olefinic monomers include cyclo-olefins and bkyclo-olefins, and soon.
• the olefinic monomers which are suitable in the composition of this invention are of the formula (V): wherein: m is an integer 0, 1 or 2; is a single bond or a double bond;
• Ri3 ⁇ 4 Ri4, RIS and Ri6 are the same or different and each independently selected from the group consisting of hydrogen, halogen, a hydrocaifayl or halohydrocarbyl group selected from linear or branched alkyl and fluoroalkyl having the formula CqHxFy, where q is an integer from 1 to 20, x and y are integers from 0 to 2q+l , and the sum of x and y is 2q+l , (C3-Cu)cycloaIkyl, (C6-Ci2)bicycloalkyl, (C7-C u)tricycloalkyl, (OCio)aiyl, (C6-Cio)aryl(C 1 -Ce)alkyl, perfluoro(C6-Cio)aryl, perfluoro(Ce-Cio)Biyl(C 1 -Ce)alkyl, methoxy, ethoxy, linear or branched (C
• Z is selected from the group consisting of:
• Ri7 and Rig are the same or different and each independently selected from hydrogen, methyl, ethyl, linear or branched (C3-Cn)alkyl, substituted or unsubstituted (Ce-CuXuyl, methoxy, ethoxy, linear or branched (Ci-CeXdkyknqr, (C2-Ce)acyl, (C2-Ce)acyloxy, and substituted or unsubstituted (Ce-CwXuyloxy; and b is 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 anthracenyl substituted or unsubstituted fluorenyl, wherein said substituents are selected from the group consisting of halogen, methyl, ethyl, linear or branched (C3-Ce)alkyl, perfluoro(C 1 -Ci2)alkyl, (C3-Ciz)cycloalkyl, (Ce-Cio)aryl, (Ce-Cio)aiyl(C 1 -C6)alkyl, perfluoro(C6-Cio)aryl, perflutHo(C6-C]o)aryl(C 1 -C6)alkyl, methoxy, ethoxy,
• Raa, R24 and Ras are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, line» or branched (C3-Cu)alkyl, perfluoro(C 1 -Ci2)aIkyl, methoxy, ethoxy, line» or branched (C3-Ci2)alkoxy, (C3-Ci2>cycloalkyi, (Ce-Ci2)bicycloaIkyl, (C7-Ci4)tricycloalkyl, (C6-Cio)aryl, (Ce-Cio)aiyl(C 1 -C6)alkyl, perfluoro(C6-Cio)aryl and perfluoro(Ce-Cio)aiyl(C 1 -C6)atiyl; or
• R23 andRat taken together with the intervening carbon atoms to which they are attached to form a substituted or unsubstituted (Cs-CiOcyclic, (Cs-Ci4)bicyclic or (Cs-Cu)tricyclic ring; and Aiylene is substituted or unsubstituted bivalent (Ce-Ci4)aryl; or one of Ri3 and Ru taken together with one of Rn and Ris and the carbon atoms to which they are attached to form a substituted or unsubstituted (Cs-Ci4)cyclic, (Cs-Cujbicyclic or (Cs-Ci4)tricyclic ring.
• Aryl as defined herein is substituted or unsubstituted biphenyl of formula: substituted or unsubstituted naphthyl of formula; substituted or unsubstituted terphenyl of formula:
• R* in each occurrence is independently selected from methyl, ethyl, linear or branched (C3-Cu)alkyl or (Ce-Cio)aiyl;
• the monomers as described herein readily undergo mass vinyl addition polymerization, i.e, in their neat form without use of any solvents by vinyl addition polymerization using transition metal procatalysts, such as for example, oganopalladium compounds as described heron. See for example, U. S. Patent Nos.7,442,800 B2; and 7,759,439 B2; pertinait 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.
• 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.
• 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 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 generate or photosensitizer and/or monomers can be employed in this invention.
• solvents examples include alkanes, cycloalkanes, aromatics, such as toluene, ester solvents such as ethyl acetate, THF, dichkxomethane, dichloroethane, and the like.
• one or more of the monomers themselves can be used to dissolve the organopalladium compound of formula (I) or a photoacid generate or photosensitizer and thus avoiding the need for the use of solvents.
• one monomer can itself serve as a sol vent fix the other monomer and thus eliminating the need for an additional solvent.
• a first monomer of fbrmula (V) is a solid at room temperature
• a second monomer of formula (V) which is a liquid a! room temperature can be used as a solvent fix ⁇ 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.
• 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.
• the monomers of fbrmula (V) which are suitable in this invention feature a refractive index of at least 1.5.
• the refractive index of the monomers of formula (V) is higher than 15.
• the refractive index of the monomers of formula (V) is in the range from about 1.5 to 1.6.
• the refractive index of the monomers of formula (V) is in the range from about 1.5 to 1.6.
• (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.
• ft is generally contemplated that monomer of fbrmula (V) may also be used as a viscosity modifier. Accordingly, in general, such a monomer of fbrmula (V) is a liquid at room temperature and can be used in conjunction with another monomer of formula (V) which is a solid or a high viscosity liquid.
• the composition of this invention encompasses at least two different monomers of formula (V) and is in a clear liquid state having a viscosity below 100 centipoise.
• the composition ofthis invention exhibits low viscosity, which can be below 100 centipoise.
• the viscosity of the composition of this invention is less than 90 centipoise.
• the viscosity of the composition ofthis invention is in the range from about 10 to 100 centipoise.
• the viscosity of the composition ofthis invention is lower than 80 cP, lower than 60 cP, lower than 40 cP, lower than 20 cP, . In some other embodiments it may even be lower than 20 cP.
• 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)tosecondmonomerofformula(V)canbefrom 0:l()0to l00:0. That is, only one monomer of formula (V) cm be employed in certain applications.
• 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 sane other embodiments it is from 5:95 to 95:5; it is from 10:90 to 90:10; it is from 20:80 to 8020; it is from 30:70 to 70:30; h is from 60:40 to 40:60; and it is 50:50, and so on.
• compositions in accordance with the present invention encompass the above described one or mot 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).
• compositions of tills invention can also include other high refractive polymeric materials which will bring about such intended benefit
• polymers include without any limitation, poly(a-methylstyre ⁇ X polyvinyl-toluene), copolymers of a-methybtyrene and vinyl-toluene, and the like.
• compositions of this invention can also contain additional monomers different from the monomer of formula (V).
• the composition according to this invention may further contain one or more monomers selected from momma- of formula (VI) or monoma of formula (VII).
• 0 is an intega from 0 to 2, inclusive
• D is S1R 29 R 30 R 31 or a group selected from:
• R26, R27 and R28 are the same or different and independently of each otha selected from hydrogen, halogen and hydrocarbyl, where hydrocarbyl is selected from methyl, ethyl, linear or branched (C3-C «)alkyl, (C3-Ci2)cycloalkyl, (C ⁇ s-Ci2)bicycloelkyl, (C?-Ci4)tricycloaIkyl, (Ce-Cio)aryl, (Ce-Cio>uyl(C 1 -C3)alkyl, (C 1 -Cujalkoxy, (C3-Ci2)cycloalkoxy, (OCi2)bicycloalkoxy, (C7-Ci4)tricycloalkoxy, (C 6 -Cio)aryloxy(C 1 -C3)alkyl or (Ce-Cio)aiylaxy; and
• R29, Rso and R31 are each independently of one anotha methyl, ethyl, linear or branched (C3-C»)alkyl, substituted or unsubstituted (C «-Ci4)aryl, methoxy ethoxy, linea or branched (C3-C9)aIkoxy or substituted or unsubstituted (Ce-Ci4)aiyloxy.
• monomers of formula (VI) provides fintiia advantages. Namely, the monomers of formula (VI) deposing upon the nature of the monoma 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 modifies.” 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: m wherein:
• Z ⁇ is selected from the group consisting of substituted or unsubstituted (C 1 -Ci 2 )alkylene, -(CH2)dO(CH2)e-, - ⁇ CHzMSiRasRjiKOsiR ⁇ iMCHaV where d, e and fare independently integers from 0 to 6, inclusive, Ras, R», R «o and R*i are the same or different and independently of each other selected from methyl, ethyl, linear or branched (Ca-Ci2)alkyl, and an arylene selected from the following:
• Ra3 ⁇ 4 Ra3 ⁇ 4 R 34 , R 35 , R 36 and R 37 are the same or different and independently of each other selected from hydrogen, halogen and hydrocarbyl, where hydrocarbyi is selected from methyl, ethyl, linear or branched (Ca-Cu)alkyi, (Ca-Ci2)cycloalkyl, (Ce-C ia)bicycloalkyl,
• the monomers of formula (VII) are bifunctional monomers and may exhibit high refractive index eqiecially when Zi is an arylene 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 crosslinkabilhy 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 moth» 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).
• any (Me of the monomers of formulae (V) to (VII) may be sufficient to form a composition of this invention.
• the composition of this invention encompasses any two monomers of formulae (V) to (VII) and in any desirable proportions.
• 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.
• any of the monomers within the scope of monomer of formula (V) can be employed in the composition of the inventkm.
• Representative examples of monomer of formula (V) are
• NBDHNMI bicyclo[2.2. l]hcpt-5-cn-2-ylmethyl 4-methoxy-cinnamate (NBMcMeOCmn); bicyck>[2.2.1]hept-5-en-2-ylmdhyI cinnamate (NBMeCinn); bicyclo[22.1 ]hept-S-en-2-ylethyl 4-mcthoxy-cmnamate (NBEtMeOCmn);
• monomer of formula (VII) to form the composition of this invention it is contemplated that any monomer within the scope of monomer of formula (VII) can be employed.
• exemplary monomers of such type include but not limited to those selected from the group consisting o£ l,4-di(bicyclo[22.1 ]hept-5-en-2-yl)benzene;
• composition of this invention encompasses one or more monomers of formula (V) and at least one monomer of formula (VI).
• 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).
• 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).
• composition of this invention encompasses one monomer of formula (VI), optionally one or more monomers of formula (V) or monomer of formula (VII).
• composition of this invention may indude one or more monomers selected from the following: dicyclopentadiene (DCPD);
• the composition contains any of the organopalladium compounds of formula (I) dial would bring about the mass polymerization as described haem.
• suitable organopalladium compound of formula (I) contains a bidentate monoanionic ligand which is selected from the group consisting of:
• organopalladium compounds of formula (I) that are suitable to be employed in the compositions of this invmtion are known in the literature or can be readily made by any of the known procedures in tiie 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.
• organopalladium compounds of formula (I) or organopalladium compounds of formula (IA) that can be employed in foe composition of this invention without any limitation include foe following; palladium (acetylacetonateh tri-isopropylphosphine;
• composition of this invention ftrther contains a photoadd generator which when combined with the organopalladium compound of formula (I) and a photosensitizer will cause mass polymerization of the monomers contained therein when exposed to suitable radiation as described herein.
• a photoadd generator which when combined with the organopalladium 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 hakmium salts.
• the photoacid generator of the formula (TV.) are employed in the composition of this invention:
• Aiyli aid 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.
• the WCA can be selected from borates, phosphates, arsenates, antimonates, aluminates, boratobenzenc anions, carbonate, halocarborane anions, sulfonamidate and sulfonates
• Rii and Rn are as defined herein.
• various sulfonium salts can be used as photoacid generators, which include broadly compounds of formula (III) as described herein.
• Non-limiting examples of suitable photoacid generators of formula (IV) that may be employed in the composition of this invention are listed below: tolylcumyliodoniiHn-tetrakis pcntafluorophenylborate, commercially available under the tradename Bluesil PI 2074* from Elkem Silicones;
• exemplaiy PAGs that may be suitable in the composition of this invention include the following: triphenylsulfbnium 4 l 4,5 ⁇ ,6,6-hexafluoro-l ⁇ > 2-dithiazinan-2-ide 1,1,33-tetraoxkie; tris(4-(tert-butyl)phenyl)sulfotiium 4,4,53,6,6-hexafluoro-133-dithiazinen-2-ide 1,133- tetraoxidc;
• any of the 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 tills invention.
• the composition of this invention additionally contains a photosensitizer compound which Anther facilitates the formation of the active catalyst when the composition is exposed to suitable radiation in the presence of the photoacid generator as employed herein.
• a photosensitizer compound which Anther facilitates the formation of the active catalyst when the composition is exposed to suitable radiation in the presence of the photoacid generator as employed herein.
• any suitable sensitizer compound can be employed in the compositions of the present invention, which activates the photoacid generator and/or the organopalladium compound of formula (I).
• suitable sensitizer compounds include, anthracenes, phenanthrenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes, xanthones, indanthrenes, thioxanthen-9-ones, and mixtures thereof.
• suitable sensitizer components include a compound of formula (Vni) or a compound of formula
• R44, Ris and Ru are the same or different and independently of each other selected from the group consisting of hydrogen, halogen, hydroxy, NQ3 ⁇ 4 NH3 ⁇ 4 methyl, ethyl, linear or branched (C3-Ci2)alkyl, (C3-Ci2)cycloaIkyl, (C6-Ci2)bicycloalkyl, (C7-C u)tricycloalky 1, (C6-Cio)aryl, (Ce-Cio)aryl(C 1 -C3)alkyl, (C 1 -Cujalkoxy, (C 3 -Ci2)cycloalkoxy, (Ci-Ci2)bicycloelkoxy, (C7-C lOtricycloalkoxy, (C6-Cm)aryloxy(Ci -C3)alkyl, (C6-Cio)aryloxy, C(OXC 1 -C6)alkyl, COOH, C(0)0(C 1
• R47 and R41 are the same or different and independently of each other selected from the group consisting of methyl, ethyl, linear or branched (C3-Ci2>alkyl, (C3-Ci2)cycloalkyl, (C6-Ci2)bicycloalkyl, (CT-C I 4)tricycloalkyl, (Ce-Cio)aiyl and (C6-Cio)aiyl(C 1 -C3)alkyl.
• DBA 9,10-di-n-butaxyanforacene
• Suitable photosensitizer compounds include various substituted and unsubstituted phenothiazine derivatives, such as for example: phenothiazine.
• photosensitizers absorb energy from foe radiated light source and transfers that energy to foe desirable substrate/reactant, which in foe present invention is the photoacid generator employed in the composition of this invention.
• the compounds of formula ( ⁇ ) or the compounds of formula (IV) can be activated at certain wavelength of the electromagnetic radiation which can generally range from about 240 nm to 410 nm.
• any of foe 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 fabrication methods.
• foe wavelength of the radiation to activate the compounds of formulae (III) or (IV) is 260 nm.
• the wavelength of the radiation to activate the compounds of formula (V) is 310 nm. In sane other embodiments the wavelength of the radiation to activate the compounds of formula (V) is 365 nm. In yet sane other embodiments the wavelength of the radiation to activate foe compounds of formula (V) is 395 nm.
• any amount of organopaUadium compound of formula (I), the photoadd generator of formulae (III) or (IV) and the photosensitizer of formulae (VIII) or (IX) can be employed in foe composition of this invention which will bring about the intended result
• foe 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.
• monomer of formula (V)xompound of formula (I) is 10,000:1, 15,000:1, 20,000:1 or higher than 30,000:1.
• 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.
• the molar ratio of organopalladium compound of formula (I).1he photoecid generator of formulae (DO) or (IV):fte photosensitizer of formulae (VIII) or (IX) is in foe range ofhliOJ to 1:2:2 or 1:2:1 or 1:4:1, 1:2:4, 1:1:2, 1:43 or such ranges which will bring about the intended benefit
• foe composition according to ft is invention forms a substantially transparent film when exposed to a suitable actinic radiation (UV irradiation). That is to say that when foe composition of this invention is exposed to certain actinic radiation, foe 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.
• a suitable actinic radiation UV irradiation
• such film formed from the composition of this invention exhibits a transmission of equal to or higher than 90 percent of the visible light
• such film formed from foe composition of this invention exhibits a transmission of equal to or higher than 95 percent of foe visible light
• any actinic radiation that is suitable to cany 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.
• any radiation higher than 400 nm can also be employed.
• the wave length of the actinic radiation employed is 250 nm, 295 nm, 360 nm, 395 nm or higher than 400 nm.
• composition of this invention undergoes mass polymerization when exposed to suitable actinic radiation and heat to form a substantially transparent film.
• suitable actinic radiation and heat to form a substantially transparent film.
• foe 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.
• compositions of this invention without any limitation may be enumerated as follows:
• kits fix ⁇ faming a substantially transparent film There is dispensed in this kit a composition of this invention. Accordingly, in some embodiments there is provided a kit in which there is dispensed one or more olefinic monomers; an organopalladium compound of formula (I) or an organopalladium compound of formula (IA) as described herein; a photoacid generator of formulae ( ⁇ ) or (IV) as described herein and a photosensitizer of formulae (VIE) 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.
• the aforementioned kit encompasses one or more monomers of formula (V) and one or more monomers of formulae (VI) or (VII).
• the 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.
• the kit may encompass a composition wherein dispensed two monomers which could be one monomer of formula (V) and another monomer 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 this 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.
• composition of this invention is poured onto a surface or onto a substrate which needs to be encapsulated and exposed to suitable radiation in order for the monomers to undergo polymerization to form a solid trmsparent polymer which could be in the form of a transparent film.
• suitable radiation such as for example, at 265 nm 315 nm 365 nm or 395 nm and so on.
• the mass polymerization may further be accelerated by heating, which can also be to stages, fix ⁇ example heating to 40 0 C or 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.
• heating can also be to stages, fix ⁇ example heating to 40 0 C or 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.
• the kit as described herein encompasses a composition which further contains one or more monomers selected from monomer of formula ( ⁇ ) or monomer of formula (IV) as described hereinabove.
• monomers of formula (III) or (TV) as described hereto can be used to this embodiment, and in any desirable amounts dependmg on the nature of the intended use.
• the kit as described herein encompasses various exemplary compositions as described hereinabove.
• a method of forming a substantially transparent film for the 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 formula (I) or an organopalladium compound of formula (IA); a photoacid generator of formulae (III) or (IV); and a photosensitizer of formulae (VIII) or
• 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 to 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 mature can also be poured onto a substrate to form a film.
• Suitable substrate includes any appropriate substrate as is, or may be used fix- electrical, electronic or optoelectronic devices, fix- example, a semiconductor substrate, a ceramic substrate, a glass substrate.
• the coated substrate is bated, i A, heated to facilitate the mass polymerization, for example to a temperature from 50°C to 100°C fix ⁇ about 1 to 60 minutes, although other appropriate temperatures and times can be used.
• the substrate is bated at a temperature of from about 60°C to about 90°C fix 2 minutes to 10 minutes. In some other embodiments the substrate is bated at a temperature of from about 60°C to about 90°C fix 5 minutes to 20 minutes.
• the films thus formed are then evaluated for their optical properties using any of the methods known in the at
• 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. Quantitatively foe percent transparency can be measured by visible spectroscopy.
• the films framed according to this invention exhibit excellent optical transparent properties and can be tailored to desirable refractive index as described herein.
• an 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.
• the composition of this invention can also be used in a variety of photo induced nanoimprint lithography (NIL), such as for example, UV-NIL.
• NIL photo induced nanoimprint lithography
• tiie compositions of this invention can be used in a variety of photocurable imprint technology.
• the composition of this invention is suitably placed ⁇ xi a substrate (fix example by coating or similar means), which is then covered by a suitable stamp and exposed to radiation so as to allow foe composition of this invention to cure to a solid. The stamp is then released to obtain the nano-imprinted film.
• substrates can include for example a master digital video disk (DVD).
• composition comprising: a) one or more monomers of formula (VA): wherein: m is an integer 0, 1 or 2; at least one of Ria, R14, Ris and Rie is O-Aiyl; and the remaining Ri3 ⁇ 4 R14, Ris and Rie 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 (CyCieXdkyl, perfluoro(C 1 -Ci2)aIkyl, (C3-Ci2)cycloalkyl, (Ce-Ci2)bicycloalkyl, (CT-C i4>tricycloalkyl, (C6-Cm)aiyl, (Ce-Cio)aiyl(C 1 -C6)alkyl, perfluoro(C 6 -Cio)ai
• 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 anthracenyl substituted or unsubstituted fluorenyl, wherein said substituents are selected from the group consisting of halogen, methyl, ethyl, linear or branched (C3-Ce)alkyl, perfluoro(C 1 -Ci2)alkyl, (C3-Ci2)cycloaIkyl, (Ce-CioXuyl, (C6-Cio)aryl(C 1 -C6)alkyl, perfluoro(C6-Cio)aryl, perfluoro(C6-Cio)aryl, perfluoro(C6-Cio)aryl, perfluoro(
• R23, *24 and R25 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-Cn)alkyl, perfluoro(C 1 -Ci2)alkyl, methoxy, ethoxy, linear or branched (C3-Cu)alkaxy, (Cs-Ci2)cycloeIkyl, (Ce-Ci2)bicycloaIkyl, (C?-Ci4)tricycloelkyl, (C3 ⁇ 4-Cio)aiyl, (C6-Cio)aryl(C 1 -C6)alkyl, perfluoro(C6-Cio)atyl and perfluoro(C6-Cio)aryl(C 1 -C6)alkyl; or
• R23 and R24 taken together with the intervening carbon atoms to which they are attached to form a substituted or imsubstituted (Cs-Ci4)cyclic, (Cs-Ci4)bicyclic or (Cs-Ci4)tricyclic ring; and Aiylene is substituted or imsubstituted bivalent (C6-Ci4)aiyl; or one of Ri3 and Ru taken together with one of Ris and Rie and the carbon atoms to which they are attached to form a substituted or imsubstituted (Cs-Cujcyclic, (Cs-Ci4)bicyclic or (C5-Ci4)tricyclic ring; a) cme or more monomers of formula (VB): wherein: p is an integer 0, 1 or 2;
• Rsi, R52, Rj3 and R54 are the same or different and each independently of one another is selected from hydrogen, linear or branched alkyl and fluoroalkyl having the formula CqH*F y , where q is an integer from 1 to 16, x and y are integers from 0 to 2qH , and the sum of x and y is 2q+l, hydroxy(C 1 -Ci6>3 ⁇ 4l, (C3-Ci2)cycloelkyl, (C6-Ci2)bicycloaIkyl, (Cr-Ci4)tricycloalkyl, (Ce-CioXnyl, (OCio)aiyl(C 1 -C3)alkyl, perfluoro(C6-Cio)aiyl, perfluoro(Ce-Cio)aiyl(Ci ⁇ C 6 )alkyl, di(C 1 -C2)alkylmalcimide(C3-C6)
• X and Y are independently of each other selected from 0, N and S;
• R 1 , R3 ⁇ 4 R3 ⁇ 4 Ra, Rs, Re and R? are the same or dif&rent and each independently selected from the group consisting of hydrogen, linear or branched alkyl and fluoroalkyl having the formula CqHxFy, where q is an integer from 1 to 16, x and y are integers from 0 to 2qH, and the sum of x and y is 2qH, (C3-C 1 o)cycloalkyl, (C*-Cio)aiyl(Ci ⁇ €i6)alkyl and substituted or unsubstituted (Ce-Cio)aryl; provided when either X or Y is 0 or S, R 1 and R5, reflectively, do not exist; d) a photoacid generator selected from the group consisting oft a compound of the formula ( ⁇ ): (in); a compound of the formula (IV): wherein: a is an integer from 0 to 5;
• An 0 is selected from the group consisting of C tetrakis(pentafhiorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2- fluorophenyI)borate, tetrakis(3-fluoro
• R3 ⁇ 4 R3 ⁇ 4 Rio, Rii and Ri2 are the same or different and each independently selected from the group consisting of halogen, methyl, ethyl, linear or branched (C3-C»)alkyl,
• compositions in accordance with this aspect of the invention which feature unique properties. Accordingly, in some embodiments of this aspect of the invention the compositions thus formed exhibit longer storage stabilities, which can extend up to four months at ambient temperatures or temperatures up to 40 °C.
• the compositions of this aspect of the invention are more readily ink jettable as well as spreadable on suitable substrates using any of the known procedures including ink jetting, among other coating methods.
• composition in accordance with this aspect of foe invention include monomers of formulae (VA) which include foe following without any limitations;
• NBEtOPhPh 5-(2-([l , 1 ’-triphenyl]-2-yloxy)ethyl)bicyclo[2.2.1 ]hept-2-ene; PENB - 5- phenethylbicyclo[22.1]hept-2-aie; DecNB - 5-decylbicyclo[2.2.1]hept-2-ene; HexNB-5- hexylbicyclo[22.1 ]hept-2-ene; TD - tctracyclododecene; DCPD - dicyclopentadiene; Pd304 - palladium acctylacetonatc; Pd520 - palladium hexafluoroacetylacetonate; Pd465 - palladium (acetylacetonate)] tri-isopropylphosphine; Pd585 - Pd(acac)2Pcy3; Pd680 - palla
• organopalladrum compounds of formula (I) or (IA) are known in the literature and can be readily prepared following the procedures as described in the literature. Examples A - F illustrate preparation of a few of the organopalladium compounds of formulae (I) or (IA) as described herein.
• Tri-isopropylphosphtoe (0.16 g, 1 mmol) and palladium acetylacetonate (0.3 g, 1 mmol) were dissolved in toluene (5 mL) and stirred for 2 hours at room temperature under nitrogen. The orange solution was concentrated and recrystallized from petroleum ether to obtain pale yellowish crystal. The final product (Pd465) was dried in vacuum at room temperature. Yield: 65%. *H NMR (CD2CI2, 500 MHz): 65.41 (s, 1H), 3.45 (s, 1H), 2.62-2.63 (m, 3H), 2.29 (s, 6H), 2.00 (s, 3H), 1.91 (s, 3H), 1.2- 1.4 (m, 18H).
• Triphenyl phosphine (0.26 g, 1 mmol) and palladium hexafluoroacetylacetonate (0.52 g, 1 mmol) were dissolved in toluene (5 mL) and stirred for 2 hours at room temperature under nitrogen. The orange solution was concentrated and recrystallized from pentane to obtain orange crystals. The final product (Pd782) was dried in vacuum at room temperature. Yield: 70%. ‘H NMR (CD2CI2, 500 MHz): 56.3-6.S (m, 15H), 5.36 (s, 2H); l9 F NMR (CD2CI2, 470 MHz): ⁇ (s, -73.6).
• Examples 1-5 demonstrate that the composition of this invention is quite stable at room temperature for at least up to two months 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) or(IA), a photoacid generator of formula (III) and a photosensitize ⁇ of formula (V).
• Example 1 The procedures of Example 1 were substantially followed in these Examples 2-5 except that Example 3 contained no photosensitizer; Example 4 contained no photoacid generator, and Example 5 contained no organopalladium compound, as summarized in Table 1. All of the compositions were prepared in a glass bottle, and UV light exposed for 4 sec (4J/cm 2 , 395nm) at room temperature. It is quite evident from the results presented in Table 1 , only the composition ofExample 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 olefinic monomers of this invention.
• the unexposed solution was free flowing even after 4 months at room temperature and the measured viscosity of the compositions respectively at 0, 14, 28, 70 and 120 days remained same at 8 cP as in Example 6.
• the compositions stored at each of these intervals were also tested their reactivity by UV-DSC, and the measured heat of polymerization was again same during this time intervals at around 360-380 J/g and the composition turned solid within minutes upon UV exposure.
• Example 10 The procedures of Example 10 were substantially repeated in this Example 11, except that the glass bottle A was not exposed to UV irradiation as follows.
• Pd680 (1 molar part)
• ITX (1 molar part)
• PENB 2500 molar part
• PENB 2500 molar part
• Bluesil PI 2074 (2 molar part)
• ⁇ (1 molar part
• PENB 2500 molar part
• DecNB/NBEtOPhPh/Pd680 Composition
• ITX (2 molar parts) and Pd680 (1 molar part) were dissolved in DecNB (9,000 molar parts) via sonication at 40 °C for 1 hour to form a clear solution.
• Bluesil PI 2074 (2 molar part) was dissolved in NBEtOPhPh (1,000 molar parts) via sonication at 40 e C for 1 hour to form a clear solution. Both solutions were mixed together thoroughly to form a clear solution, which was then stored at 40 °C for several days.
• the viscosity (at 25 °C) and the reactivity of this composition were monitored at regular intervals and the results are summarized in Table 3.
• the reactivity was measured by UV-DSC as heat of polymerization and by UV light exposure (250 mW/cm 2 ) at 400nm for 4 secs, in each interval the composition became solid within minutes upon UV exposure.
• Pd465, Pd585, and Pd782 (1 molar part) were each mixed with Bluesil PI 2074 (2 molar parts), ITX (1 molar part), and dissolved in PENB (5000 molar parts) under sonication to form a clear solution. Each of these solutions were then UV light exposed separately for 4 sec (4J/cm 2 , 395 nm) at room temperature.
• Pd722 (1 molar part), UV CATA 243 (4 molar parts), ⁇ (2 molar parts) were dissolved in PENB (5000 molar parts) under sonication to form a clear solution.

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