Palladium catalysts for forming vinyl addition polymers with improved film-forming properties - Patents.com

Abstract

The series of palladium compounds described herein have been found to be excellent vinyl addition polymerization catalysts. Specifically, the compounds of formula (I) and (II) described herein surprisingly exhibit higher reactivity in the vinyl addition polymerization of various cycloolefinic monomers than compounds known in the art, and can form very high molecular weight polymers. Formation of various solid objects, such as, for example, solution extrusion of polymer solutions formed from the vinyl addition polymerization of various cycloolefinic monomers utilizing very low concentrations of the palladium compounds of formula (I) or (II) described herein, has also been disclosed. Polymer films formed from the polymerization compositions exhibit previously difficult to achieve properties, such as, for example, excellent transparency, high thermal and mechanical properties, among other improved properties. Thus, the films so formed are useful in various optoelectronic applications.

Description

[Technical field]

[0001] Cross-reference to related applications This application claims the benefit of U.S. Provisional Application No. 63 / 327,632, filed April 5, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] The present invention provides a series of palladium compounds. More specifically, the present invention provides a series of palladium compounds of formula (I) and (II). The present invention also relates to methods for making these compounds. The compounds of the present invention are found to be excellent vinyl addition polymerization catalysts for the formation of highly reactive, high molecular weight polycycloolefin-based polymers with excellent optical, thermal, and mechanical properties. More specifically, the polymers thus formed in solution can be easily extruded into transparent films that are useful for a variety of optoelectronic applications. [Background technology]

[0003] Cyclic olefin polymers such as polynorbornene (PNB) are widely used in various applications such as electronic, photoelectron, etc., and therefore methods for preparing such PNBs on an industrial scale are becoming increasingly important. It is well known in the literature that various functionalized PNBs can be synthesized by vinyl addition polymerization using various transition metal catalysts and procatalysts by employing suitable starting norbornene monomers. See, for example, U.S. Pat. No. 7,910,674, the relevant portions of which are incorporated herein by reference.

[0004] PNB is commonly used as a coating composition in various applications, as mentioned above. One possible use of these materials is for the formation of films, either by solution casting or extrusion of PNB in ​​a suitable solvent. The films thus formed are expected to exhibit good optical properties and low dielectric properties, as well as thermomechanical properties. However, the excessive use of solvents in such operations is problematic in large-scale commercial operations. The use of various transition metals in vinyl addition polymerization is also problematic, since in many optoelectronic applications it is desirable to obtain substantially metal-free polymers. Removal of residual metals from the polymer is also very difficult. There is also a need for the development of highly active catalysts so that PNB can be produced with very high molecular weights while employing smaller amounts of catalyst.

[0005] PNB made from various palladium catalysts appears to provide better quality polymers and address some of the problems encountered in the prior art. However, various palladium catalysts used to form PNB result in hazy polymer films. Some of these catalysts are also not very active, leading to low conversions (<90%) and requiring additional steps to purify the polymer to remove residual monomers and oligomers. See, for example, U.S. Patent Application Publication No. 2005 / 0187398, which reports a series of single-component cationic palladium proinitiators. However, some of these proinitiators were either inactive and / or produced poor quality polymer films. Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, it is an object of the present invention to provide a highly active palladium catalyst for the formation of very high molecular weight PNB with excellent optical, thermal, mechanical and electrical properties.

[0007] It is also an object of the present invention to provide a series of PNBs that are useful in a variety of optoelectronic applications.

[0008] It is a further object of the present invention to provide a highly concentrated PNB solution for forming films having heretofore difficult to achieve optical, thermal, mechanical and electrical properties.

[0009] Further objects and scope of applicability of the present invention will be set forth in the detailed description below. [Means for solving the problem]

[0010] Surprisingly, it has now been found that various palladium compounds of formula (I) and (II) described herein are highly active in the vinyl addition polymerization of various norbornene-type monomers of formula (IV) described herein. The polynorbornenes formed using the palladium compounds of formula (I) or (II) exhibit very high molecular weights with narrow polydispersities. Thus, it is now possible to form very high molecular weight polynorbornenes using lesser amounts of the palladium compounds of formula (I) or (II). Furthermore, the conversion of monomer to polymer is so high, ranging from 99.5 percent to 99.9 percent or more, that no concern is ever needed to remove residual monomer or oligomers. More importantly, it is important to note that high conversions, up to 99 percent or more, can be achieved in less than 30 minutes to 60 minutes. The polymers are soluble in various solvents to form very concentrated clear polymer solutions, 10 percent to 50 percent by weight solutions. The polymer solutions can then be readily cast into films using a variety of methods, including, but not limited to, solution casting and extrusion. The films thus formed exhibit improved optical, thermal, mechanical, and electrical properties and therefore have a variety of optoelectronic applications. [Brief description of the drawings]

[0011] Embodiments according to the present invention will now be described with reference to the accompanying figures and / or images. Where figures are provided, they are simplified portions of various embodiments of the present invention and are provided for illustrative purposes only. [Figure 1] FIG. 1 shows a diagram of the molecular structure of palladium diacetate diadamantyl-(n-butyl)phosphine (H2O) (Pd601), an illustrative example of a palladium compound of formula (I) according to the present invention and exemplified in Example 1. [Diagram 2] FIG. 2 shows the 1H NMR of palladium diacetate diadamantyl-(n-butyl)phosphine (H2O) (Pd601), an illustrative example of a palladium compound of formula (I) according to the present invention and exemplified in Example 1. [Diagram 3] FIG. 3 shows the 1H NMR of palladium diacetate di-t-butyl-(n-butyl)phosphine (H2O) (Pd445), an illustrative example of a palladium compound of formula (I) according to the present invention and exemplified in Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] As used herein, the articles "a," "an," and "the" are deemed to include plural referents unless expressly limited to one referent.

[0013] All numbers, values ​​and / or formulas expressing quantities of ingredients, reaction conditions and the like described in this specification and the claims appended hereto reflect various uncertainties in the measurements performed to arrive at such numbers, values ​​and / or formulas, and therefore are deemed to include the term "about" unless otherwise indicated.

[0014] When a numerical range is disclosed herein, such range is continuous, including both the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Furthermore, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. Also, when multiple ranges are provided to describe a feature or characteristic, such ranges can be combined. That is, unless otherwise stated, all ranges disclosed herein should be understood to include any and all subranges contained therein. For example, a specified range of "1-10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1-10 include, but are not limited to, 1-6.1, 3.5-7.8, and 5.5-10.

[0015] The term "alkyl" as used herein means a straight or branched chain saturated hydrocarbon substituent having the specified number of carbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyl, tert-butyl, and the like. Derived expressions such as "alkoxy", "thioalkyl", "alkoxyalkyl", "hydroxyalkyl", "alkylcarbonyl", "alkoxycarbonylalkyl", "alkoxycarbonyl", "diphenylalkyl", "phenylalkyl", "phenylcarboxyalkyl", and "phenoxyalkyl" should be construed accordingly.

[0016] The term "cycloalkyl" as used herein includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. Derived expressions such as "cycloalkoxy", "cycloalkylalkyl", "cycloalkylaryl", "cycloalkylcarbonyl", etc. should be construed accordingly.

[0017] The expression "perhaloalkyl" as used herein refers to an alkyl as defined above, in which all hydrogen atoms of the alkyl group are replaced by halogen atoms selected from fluorine, chlorine, bromine or iodine. Illustrative examples include, for example, trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, as well as linear or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, etc. The derived expression "perhaloalkoxy" should be interpreted accordingly. Furthermore, some of the alkyl groups described herein, such as "alkyl", may be partially fluorinated, i.e., only a portion of the hydrogen atoms of the alkyl group are replaced by fluorine atoms, and should be interpreted accordingly.

[0018] The term "acyl" as used herein has the same meaning as "alkanoyl" and may also be structurally represented as "R-CO-", where R is "alkyl" as defined herein having the specified number of carbon atoms. Additionally, "alkylcarbonyl" has the same meaning as "acyl" as defined herein. Specifically, "(C1-C4)acyl" means formyl, acetyl or ethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as "acyloxy" and "acyloxyalkyl" should be construed accordingly.

[0019] As used herein, the term "aryl" refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or naphthyl include, for example, o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, and the like. "Substituted phenyl" or "substituted naphthyl" includes any of the possible substituents further defined herein or known in the art.

[0020] The term "arylalkyl" as used herein means an aryl, as defined herein, further linked to an alkyl, as defined herein. Representative examples include, for example, benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

[0021] The term "alkenyl" as used herein means an acyclic linear or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, including ethylidene, vinyl, ethenyl, and linear or branched propenyl, butenyl, pentenyl, hexenyl, and the like. The derived expressions "arylalkenyl" and 5- or 6-membered "heteroarylalkenyl" should be construed accordingly. Illustrative examples of such derived expressions include, for example, 2-ethylidenebicyclo[2.2.1]heptane or 2-ethylidenenorbornene, 2-vinylnorbornene, phenylethenyl, 4-methoxyphenylethenyl, and the like.

[0022] The term "heteroaryl" as used herein includes all known heteroatom containing aromatic radicals. Representative 5-membered heteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like. Representative 6-membered heteroaryl radicals include pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like. Representative bicyclic heteroaryl radicals include, for example, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, and the like.

[0023] The term "heterocycle" as used herein includes all known heteroatoms including cyclic radicals. Representative 5-membered heterocycle radicals include tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like. Representative 6-membered heterocycle radicals include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like. Other miscellaneous heterocycle radicals include, but are not limited to, aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hept-2-yl, triazocanyl, and the like.

[0024] "Halogen" or "halo" means chloro, fluoro, bromo and iodo.

[0025] In its broadest sense, the term "substituted" is intended to include all permissible substituents of organic compounds. In some of the specific embodiments disclosed herein, the term "substituted" refers to substituted with one or more substituents independently selected from the group consisting of (C1-C6) alkyl, (C2-C6) alkenyl, (C1-C6) perfluoroalkyl, phenyl, hydroxy, -CO2H, ester, amide, (C1-C6) alkoxy, (C1-C6) thioalkyl, and (C1-C6) perfluoroalkoxy. However, any of the other suitable substituents known to those skilled in the art may also be used in these embodiments.

[0026] Any atom in the text, illustrations, examples, and tables of the specification with unsatisfied valences is presumed to have the appropriate number of hydrogen atoms to satisfy such valences.

[0027] It will be understood that, as used herein, the terms "dielectric" and "insulating" are used interchangeably. Thus, a reference to an insulating material or layer includes a dielectric material or layer, and vice versa. Furthermore, it will be understood that, as used herein, the term "organic electronic device" includes the term "organic semiconductor device" and certain specific embodiments of these devices that are known in the art.

[0028] As used herein, the dielectric constant (Dk) of a material is the ratio of the charge stored in an insulating material placed between two metal plates to the charge that could be stored if the insulating material were replaced with a vacuum or air. It is also called the electrical permittivity or simply the dielectric constant. And since it is measured relative to the dielectric constant of free space, it is sometimes called the relative permittivity.

[0029] "Low loss" as used herein is the dissipation factor (Df), which is a measure of the rate at which a mode of oscillation (mechanical, electrical or electromechanical) loses energy in a dissipative system. It is the inverse of the quality factor and describes the "quality" or durability of the vibration.

[0030] By the term "derived from" herein is meant that the polymer repeat unit is polymerized (formed) from polycyclic norbornene-type monomers, for example according to formula (I), where the resulting polymer is formed by 2,3 sequence of norbornene-type monomers, as shown below: [ka]

[0031] Such polymerizations are also commonly known as vinyl addition polymerizations, which are typically carried out in the presence of organometallic compounds such as palladium or nickel compounds, as will be described in more detail below.

[0032] Thus, in accordance with the practice of the present invention, there is provided a palladium compound selected from the group consisting of: [ka] Here, L is selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (CHCN), 2,4,6-trimethylbenzonitrile, phenylacetonitrile (CHCHCN), 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, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran and benzophenone; Z - is BF4 -, tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyl tris(perfluorophenyl)borate, ethyl tris(perfluorophenyl)borate, phenyl tris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1- propylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, PF6 - , SbF6 - , n-C4F9SO3 - , CF3SO3 - and p-CH3(C6H4)-SO3 - is selected from the group consisting of At least two of R1, R2 and R3 are the same or different and are tert-(C4-C 12 ) alkyl, 1-(C1-C5) alkyl, (C3-C8) cycloalkyl, 1-(C5-C 12 )bicycloalkyl and 1-(C8-C 12 )tricycloalkyl, (C6-C 10)Aryl and (C6-C 10 )aryl(C1-C3)alkyl; and the remaining R1, R2 or R3 are methyl, ethyl, linear or branched (C3-C 12 )Alkyl, (C6-C 10 )Aryl and (C6-C 10 )aryl(C1-C3)alkyl; R4, R5 and R6 are the same or different and each independently represents methyl, ethyl, and linear or branched (C3-C 20 ) alkyl, trifluoromethyl, pentafluoroethyl, and linear or branched (C3-C 20 ) perfluoroalkyl.

[0033] The compound of formula (I) may contain other suitable solvents as coordinating solvents instead of water. Therefore, the compound of formula (I) may also contain other solvents exemplified by formula (IA). [ka]

[0034] wherein R1, R2, R3, R4 and R5 are as defined herein. S is any suitable coordinating solvent. Such solvents include, for example, alcohols including methanol, ethanol, n-propanol, isopropanol, butanols, etc.; ketones including acetone, methyl ethyl ketone, etc.; and nitriles including acetonitrile, propionitrile, etc. In the broad sense, any of the Ls defined for compounds of formula (II) may be used as a suitable coordinating S for compounds of formula (I).

[0035] Advantageously, it has been found that the phosphines linked to compounds of either formula (I) or (II) must contain at least two of R1, R2 or R3 that are tertiary alkyl groups. That is, the carbon attached to phosphorus should be a tertiary carbon that is attached to three other carbon atoms and / or equivalent groups. Such tertiary carbon groups include, without limitation, for example, a carbon atom to which three other linear or branched alkyl groups are attached, a carbon atom that is part of a cycloalkyl and is attached to other linear or branched alkyl groups, the apex carbon of a bicyclic or tricyclic hydrocarbon such as 1-adamantyl, 1-norbornyl, etc. Coordination of such phosphines to palladium provides previously unseen catalytic activity for compounds of formula (I) or (II) as further exemplified below, particularly for vinyl addition polymerization catalysts.

[0036] In a further aspect of the present invention, it has been found that compounds of formula (II) having a counter anion that is a weakly coordinating anion (WCA) provide better catalytic (i.e., initiator) activity. That is, WCA is an anion that only weakly coordinates to the cation complex. It is sufficiently unstable to be displaced by a neutral Lewis base, solvent, or monomer. More specifically, the WCA anion serves as a stabilizing anion to the cation complex and does not form a covalent bond with the metal atom M. The WCA anion is relatively inert in that it is non-oxidizing, non-reducing, and non-nucleophilic.

[0037] In general, the WCA may be selected from borates, phosphates, arsenates, antimonates, aluminates, boratobenzene anions, carboranes, halocarborane anions, sulfonamidates or sulfonates.

[0038] Broadly speaking, suitable borate anions can be represented by formula A, phosphate, arsenate and antimonate anions can be represented by formula B, and aluminate anions can be represented by formula C. [M a (R a )(R b )(Rc )(R d )] A [M b (R a )(R b )(R c )(R d )(R e )(R f )] B [M c (OR a )(OR b )(OR c )(OR d )] C

[0039] In this case, in formula A, M a is boron, and in formula B, M b is phosphorus, arsenic or antimony, and in formula C, M c is aluminum. a , R b , R c , R d , R e and R f are independently fluorine, linear or branched C1-C 10 Alkyl, linear or branched, C1-C 10 Alkoxy, linear or branched C3-C5 haloalkenyl, linear or branched C3-C 12 Trialkylsiloxy, C 18 -C 36 Triarylsiloxy, substituted or unsubstituted C6-C 30 Aryl or substituted or unsubstituted C6-C 30 represents an aryloxy group, where R a -R f cannot all simultaneously represent an alkoxy or aryloxy group. Substituted aryl groups can be mono- or polysubstituted, where the substituents are independently selected from linear or branched C1-C5 alkyl, linear or branched C1-C5 haloalkyl, linear or branched C1-C5 alkoxy, linear or branched C1-C5 haloalkoxy, linear or branched C1-C5 aryl ... 12 Trialkylsilyl, C6-C 18It is selected from triarylsilyl, or a halogen selected from chlorine, bromine, or fluorine.

[0040] Representative borate anions of formula A include tetrafluoroborate, tetraphenylborate, tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate, phenyltris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, and the like. tetrakis(4-tri-iso-propylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate.

[0041] Representative phosphates, arsenates, and antimonates of formula B include, but are not limited to, hexafluorophosphate, hexaphenylphosphate, hexakis(pentafluorophenyl)phosphate, hexakis(3,5-bis(trifluoromethyl)phenyl)phosphate, hexafluoroarsenate, hexaphenylarsenate, hexakis(pentafluorophenyl)arsenate, hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate, hexafluoroantimonate, hexaphenylantimonate, hexakis(pentafluorophenyl)antimonate, hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate, and the like.

[0042] Representative aluminate anions of formula C include, but are not limited to, tetrakis(pentafluorophenyl)aluminate, tris(nonafluorobiphenyl)fluoroaluminate, (octyloxy)tris(pentafluorophenyl)aluminate, tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, and methyltris(pentafluorophenyl)aluminate.

[0043] In one embodiment of the present invention, Z - is B(C6F5)4 - , B[C6H3(CF3)2]4 - , B(C6H5)4 - , [Al(OC(CF3)2C6F5)4] - , BF4 - , PF6 - , AsF6 - , SbF6 - , (CF3SO2)N - and CF3SO3 - is selected from.

[0044] In some embodiments of the compound of Formula (II), L is selected from acetonitrile and propionitrile.

[0045] In still other embodiments, in the compound of formula (II), Z - is selected from the group consisting of tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, and tetrakis(3,4,5-trifluorophenyl)borate.

[0046] In still some other embodiments, the compound of formula (I) or (II) has at least two of R1, R2 and R3 that are identical and selected from the group consisting of tert-butyl, tert-pentyl (2-methylbut-2-yl or tert-amyl), 2-ethylbutyl, tert-hexyl (2-methylpentyl), tert-heptyl (2-methylhexyl), 2,3,3-trimethylbut-2-yl, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methylcycloheptyl, 1-bicyclo[2,2,1]heptyl, 1-bicyclo[2,2,2]octyl and 1-adamantyl, and the remaining R1, R2 or R3 are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 3-methylbutyl (iso-amyl) and 2,2-dimethylpropyl (neopentyl). Additionally, all of the alkyl groups defined above for R1, R2 and R3 are numbered and attached to the phosphine through a tertiary substituted carbon, i.e., for example, 2-methylbutyl means that the second carbon atom of the butyl is attached to the phosphorus substituted with a methyl.

[0047] In some other embodiments, R4, R5, and R6 are the same or different and are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, trifluoromethyl, pentafluoroethyl, and heptafluoropropyl.

[0048] Non-limiting representative examples of compounds of formula (I) may include: [ka]

[0049] Non-limiting representative examples of compounds of formula (II) may include: [ka]

[0050] The compounds of the present invention may be synthesized by any procedure known to those skilled in the art. In particular, some of the starting materials used in the preparation of the compounds of the present invention are known or are themselves commercially available. The compounds of the present invention and some precursor compounds may be prepared by methods used to prepare similar compounds as reported in the literature and further described herein. Furthermore, it should be emphasized that the compounds of formula (I) or (II) can be very easily synthesized, even on an industrial scale, using simple methods, as further illustrated by the specific examples below. Thus, the present invention provides a cost-effective method for forming the compounds of formula (I) or (II), thus providing an additional advantage in their utility as vinyl addition polymerization catalysts.

[0051] More specifically, the compounds disclosed herein can be synthesized according to the procedures of Scheme 1 and Scheme 2 below, where R1, R2, R3, R4, R5, R6, L and Z are defined as in Formulas I and II, respectively, unless otherwise specified.

[0052] In scheme 1, a suitable phosphine (IC) is reacted with a suitable palladium compound (IB) in the presence of water to form a compound of formula (I). This reaction can be carried out by any procedure known in the art. For example, a solution of a suitable palladium compound (IB) is reacted with a solution of a suitable phosphine (IC) under subambient reaction conditions. Typically, such reactions are carried out under an inert atmosphere in the presence of water. Reaction temperatures employed range from -78°C to 25°C, generally subambient to ambient temperatures. Any solvent that dissolves the palladium compound (IB) and the phosphine (IC) can be used. Such solvents include, for example, toluene, other hydrocarbon solvents, and mixtures thereof in any combination. [ka]

[0053] As shown in Scheme 1, the synthesis of the compound of formula (I) requires only a simple one-step reaction. Quantitative conversion to the compound of formula (I) can be achieved with yields generally ranging from about 90% or more. As will be described later, the compound of formula (I) is a highly active catalyst in vinyl addition polymerization even at very low catalyst amounts, and the monomer conversion is generally about 99% or more in short reaction times of 30 minutes to 1 hour. Furthermore, the polymers thus formed exhibit excellent optical, thermal and mechanical properties, as demonstrated in some specific examples below.

[0054] The synthesis of a compound of formula (II) is shown in Scheme 2. As shown in step 1 of Scheme 2, a palladium compound (IIA) is reacted with a suitable phosphine (IIB) in a suitable solvent under suitable reaction conditions to obtain a compound of formula (IIC). Typically, such reactions are carried out in a chlorinated solvent, such as dichloromethane, at sub-ambient to ambient temperatures ranging from -78°C to 25°C. In step 2 of Scheme 2, a compound of formula (IIC) is reacted with a suitable compound of formula (III) to form a compound of formula (II). For example, a compound of (IIC) may be reacted with a suitable salt of a weakly coordinating anion, such as a lithium salt, LiZ, to form a compound of formula (II). Typically, these reactions are carried out at room temperature in a suitable solvent capable of coordinating with palladium. Such coupling solvents include those mentioned above, such as acetonitrile. It should be noted that all of these reaction steps are carried out under an inert atmosphere, such as nitrogen, helium or argon. [ka]

[0055] Thus, in yet another aspect of the present invention, there is provided a vinyl addition polymerization catalyst comprising a compound of formula (I) according to the present invention. In yet another aspect of the present invention, there is also provided a vinyl addition polymerization catalyst comprising a compound of formula (II) according to the present invention.

[0056] In a further aspect of the invention, there is also provided a polymeric composition comprising: a) a palladium compound selected from the group consisting of a compound of formula (I) as described herein and a compound of formula (II) as described herein. b) A compound of formula (III): M d + Z - (III) Here, M d +is a cation selected from lithium, sodium, potassium, cesium, barium, ammonium, linear or branched tetra(C1-C4) alkylammonium, and dialkylanilinium; Z - is B(C6F5)4 - , B[C6H3(CF3)2]4 - , B(C6H5)4 - , [Al(OC(CF3)2C6F5)4] - , BF4 - , PF6 - , AsF6 - , SbF6 - , (CF3SO2)N - and CF3SO3 - The anion is a weakly coordinating anion selected from the group consisting of: c) at least one monomer of formula (IV): [ka] Here, m is an integer of 0, 1 or 2; R7, R8, R9 and R 10 are the same or different and each independently represent a hydrogen atom, a linear or branched (C1-C 16 )Alkyl, Hydroxy(C1-C 16 )Alkyl, Perfluoro(C1-C 12 )Alkyl, (C3-C 12 )Cycloalkyl, (C6-C 12 )bicycloalkyl, (C7-C 14 )tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 )Aryl(C1-C3)alkyl, perfluoro(C6-C 10 )Aryl, Perfluoro(C6-C 10 )aryl(C1-C3)alkyl, di(C1-C2)alkylmaleimide(C3-C6)alkyl, di(C1-C2)alkylmaleimide(C2-C6)alkoxy(C1-C2)alkyl, hydroxy, (C1-C 12 )Alkoxy, (C3-C 12)Cycloalkoxy, (C6-C 12 )bicycloalkoxy, (C7-C 14 )tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl, (C5-C 10 )heteroaryloxy(C1-C3)alkyl, (C6-C 10 )aryloxy, (C5-C 10 )heteroaryloxy or (C1-C6)acyloxy, each of said substituents being optionally substituted with halogen or hydroxy.

[0057] It should be noted that either the compound of formula (I) or (II) can be employed in the polymerization composition of the present invention. The polymerization reaction can be carried out neat (bulk polymerization) or in solution. That is, by the practice of the present invention, various polymers can be made that contain at least one functionalized norbornene monomer (i.e., the compound of formula (IV)) in the presence of the compound of formula (I) or (II) as a catalyst in combination with the compound of formula (III) described herein. In general, the combination of the compound of formula (I) or (II) is also called a two-component catalyst because it is used with the compound of formula (III). In general, the compound of formula (I) or (II) is called the procatalyst, and the compound of formula (III) is called the activator.

[0058] As mentioned above, compounds of formula (I) or (II) in combination with one or more compounds of formula (III) have been found to be highly active as vinyl addition polymerization catalysts. Thus, it is possible to produce high quality polymers by employing small amounts of catalyst. Thus, in one embodiment, vinyl addition polymerization can be effectively carried out by a molar ratio of monomer to procatalyst relative to the total moles of monomer and catalyst employed of at least 10,000:1. That is, 10,000 moles of monomer are used for each mole of catalyst. In other embodiments, the molar ratio of monomer:procatalyst can be 1,000,000:1, 500,000:1, 100,000:1, 50,000:1, 20,000:1, 15,000:1, etc. In some other embodiments, the molar ratio of monomer:procatalyst:activator can be at least 10,000:1:1. In other embodiments, the molar ratio of monomer:procatalyst:activator can be 1,000,000:1:1, 500,000:1:1, 100,000:1:1, 50,000:1:1, 20,000:1:1, 15,000:1:1, etc. In some embodiments, activator is used in excess of the molar amount of procatalyst, e.g., the molar ratio of procatalyst:activator can be from 1:1 to 1:6.

[0059] Thus, by employing the compound of formula (I) or (II) in the polymerization composition of the present invention, it becomes possible to form higher molecular weight polymers at very high conversion rates, which are characterized by superior properties compared to those formed according to conventional palladium compounds.See, for example, U.S. Patent Application Publication No. 2005 / 0187398.

[0060] As already mentioned, the bulk polymerization reaction of the catalyst and the monomers may be carried out without a solvent. Advantageously, such a polymerization reaction may also be carried out in a mold at a suitable temperature to form a three-dimensional polymeric product. In general, the reaction temperature may range from subambient temperature, e.g., below 0°C, to the boiling point of the monomers, although it is recommended that the components of the reaction vessel or mold are not heated above one or more flash points of the monomers. Generally, the bulk polymerization is carried out at a temperature range of about 10°C to 200°C, but in some other embodiments, it may be carried out at a temperature range of about 15°C to 150°C, or about 20°C to 100°C.

[0061] Since the polymerization reaction is exothermic, the temperature in the mold during the polymerization is usually higher than the temperature of the feed material unless a cooled mold is employed. Thus, the initial mold temperature can generally be in the range of about -20°C to 200°C, or about 0°C to 150°C, or 20°C to 100°C. The temperature distribution in the mold is influenced by factors such as the mold shape, the properties of the mold as a heat sink or heat supply means, the reactivity of the catalyst and monomers, etc. To some extent, the selection of suitable temperatures and heat exchange conditions will have to be based on experience with a given system of mold, feed material, and catalyst.

[0062] After the polymerization reaction is completed, the molded product may be subjected to an additional post-cure treatment at a temperature in the range of about 100° C. to 250° C. for about 15 minutes to 24 hours or 1 to 2 hours. Such a post-cure treatment can lower the glass transition temperature (T g Polymer properties including viscosity, melt strength, and heat distortion temperature (HDT) may be enhanced. Post-curing is also desirable, but not required, to bring the sample to a final, stable dimensional state, minimize residual odor, and improve final physical properties.

[0063] Vinyl addition polymerizations may also be carried out in solution employing a compound of formula (I) or (II) in combination with a compound of formula (III), as described herein. In this embodiment, a solution of the catalyst may be suitably mixed with a desired solution of one or more monomers (i.e., compounds of formula (IV)) under conditions known in the art to form a polymer of the invention. Suitable polymerization solvents include, without limitation, alkane and cycloalkane solvents such as pentane, hexane, heptane, and cyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; ethers such as THF and diethyl ether; aromatic solvents such as benzene, xylene, toluene, mesitylene, chlorobenzene, and o-dichlorobenzene; halocarbon solvents such as Freon™ 112; and mixtures in any combination thereof.

[0064] It has further been found that advantageously, the compounds of formula (I) or (II) can be prepared in situ. The vinyl addition polymerization with one or more olefinic monomers of formula (IV) can then be carried out in the same reaction vessel by adding the compound of formula (III). Thus, the present invention provides unique advantages for the industrial scale production of polymers. Most advantageously, this approach eliminates the preparation and storage of the compounds of formula (I) or (II), among many other advantages afforded by the practice of the present invention.

[0065] Solution polymerization temperatures may range from subambient, e.g., below 0°C, to the boiling point of the solvent employed. However, it should be noted that such solution polymerizations may be carried out in sealed pressurized vessels at temperatures above the boiling point of the solvent. Generally, solution polymerizations are carried out at temperatures ranging from about 10°C to 150°C, but in some other embodiments may be carried out at temperatures ranging from about 30°C to 125°C, or from about 50°C to 100°C. Additionally, solution polymerizations are carried out using anhydrous solvents under an inert atmosphere, e.g., under a nitrogen, helium, or argon atmosphere.

[0066] The polymers formed according to the present invention generally have a weight average molecular weight (M w In another embodiment, the polymer of the present invention has the formula M w In another embodiment, the polymer of the present invention has an M w In another embodiment, the polymer of the present invention has an M w In yet another embodiment, the polymer of the present invention has an M w In some other embodiments, the polymers of the present invention have an M w In another embodiment, the polymer of the present invention has an M w The weight average molecular weight (M) of the polymer is greater than 200,000, and in some other embodiments, may be greater than 500,000. n The number average molecular weight (M) can be determined by any known technique, such as gel permeation chromatography (GPC), using a suitable detector and calibration standard, such as a refractive index detector calibrated with narrow molecular weight distribution polystyrene or polybutadiene (PBD) standards. The polymers of the invention are typically characterized by a number average molecular weight (M n ) to the weight average molecular weight (M w) is greater than 3. Generally, the PDI of the polymers of the present invention ranges from 3 to 5. In some embodiments, the PDI can be greater than 3.5, greater than 4, greater than 4.5, or greater than 5. However, in some embodiments, the PDI can still be less than 3, e.g., 2.5.

[0067] Advantageously, compositions comprising vinyl addition polymers formed from palladium compounds of formula (I) or (II) at very high conversions at low (e.g., 25,000-50,000 to 1) catalyst loadings, where the molecular weight of the polymer is controlled using a chain transfer agent such as, for example, triethylsilane (TES), provide very clear polymer solutions which can then be extruded with the aid of a polymerization solvent to provide a clear film and stretched to produce films with previously difficult to achieve properties, such as, for example, very low coefficient of thermal expansion (CTE), where the CTE can be as low as 200 ppm / °K, less than 150 ppm / °K, 100 ppm / °K, 50 ppm / °K, or even 40 ppm / °K or less. Other chain transfer agents, such as, for example, bicyclo[4.2.0]oct-7-ene (BCO), formic acid, other silanes, and mixtures in any combination thereof, can also be used to control the molecular weight of the resulting polymers described herein. The use of various CTAs in vinyl addition polymerizations to control the properties of the resulting polymer is known in the art, see, for example, U.S. Patent No. 9,771,443, the relevant portions of which are incorporated herein by reference.

[0068] In some embodiments, the polymerization composition according to the present invention includes a solvent. Suitable solvents that may be employed in this embodiment may be selected from the group consisting of, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentane, hexane, heptane, octane, decane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 1-chloropentane, benzene, toluene, o-, m- or p-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, tetrahydrofuran (THF), diethyl ether, petroleum ether, and mixtures thereof in any combination.

[0069] Any of the compounds of formula (I) exemplified herein may be used, if employed, in the polymeric composition of the present invention.Similarly, any of the compounds of formula (II) exemplified herein may be used, if employed, in the polymeric composition of the present invention.

[0070] Non-limiting examples of activators, i.e., compounds of formula (III) that may be employed in the polymeric compositions of the present invention, may be illustrated below. Lithium tetrafluoroborate; Lithium triflate; Lithium tetrakis(pentafluorophenyl)borate (LiFABA); Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexakis(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexakis(pentafluorophenyl)arsenate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexakis(pentafluorophenyl)antimonate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; Lithium tetrakis(pentafluorophenyl)aluminate; Lithium tris(nonafluorobiphenyl)fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl)aluminate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; Lithium methyltris(pentafluorophenyl)aluminate; and N,N-Dimethylanilinium tetrakis(pentafluorophenyl)-borate (DANFABA).

[0071] Any olefin monomer known in the art may be employed in the polymerization composition of the present invention that will provide the intended benefits. Non-limiting examples of monomers of formula (IV) that may be employed in the polymerization composition of the present invention may be illustrated below. Bicyclo[2.2.1]hept-2-ene (NB); 5-Ethylbicyclo[2.2.1]hept-2-ene (EtNB); 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB); 5-Hexylbicyclo-[2.2.1]hept-2-ene (HexNB); 5-Octylbicyclo[2.2.1]hept-2-ene (OctNB); 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB); 5-perfluorobutylbicyclo[2.2.1]hept-2-ene (C4F9NB); 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); 5-benzylbicyclo[2.2.1]hept-2-ene (BnNB); 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB); 5-vinylbicyclo[2.2.1]hept-2-ene (VNB); and 5-Ethylidenenorbornene or 2-Ethylidenebicyclo[2.2.1]hept-2-ene (ENB).

[0072] Still further, more than one monomer of formula (IV) may be used in the polymeric composition of the present invention. Thus, the molar ratio of the first monomer of formula (IV) to the second monomer of formula (IV) may be 1:99 to 99:1. In some embodiments, the molar ratio of the first monomer of formula (IV) to the second monomer of formula (IV) ranges from 5:95 to 95:5, and in other embodiments, it is 10:90 to 90:10; 15:85 to 85:15; 20:80 to 80:20; 30:70 to 70:30; 60:40 to 40:60; 50:50; and the like. All such combinations are part of the present invention. Still further, various other olefinic monomers may also be used in the polymeric composition of the present invention in amounts intended for the end use.

[0073] It should be noted that more than two different monomers of formula (IV) can be employed in the polymerization composition of the present invention.Thus, in some embodiments, three different monomers of formula (IV) are employed in any molar ratio.In some other embodiments, four or five different monomers of formula (IV) can be used in any molar ratio.

[0074] Another aspect of the present invention provides a polymer solution obtained by polymerizing at least one polycycloolefin monomer in the presence of the palladium compound according to the present invention. As mentioned above, the compounds of formula (I) or (II) are highly active catalysts, which allows the formation of very concentrated polymer solutions. That is, the polymer solution formed by the present invention contains more than 20 weight percent solid polymer. In some other embodiments, the polymer solution is more than 30 weight percent, more than 40 weight percent, or even more than 50 weight percent. Because the catalyst loading is very low, the polymer thus formed is generally pure and can be used as is for the intended application. However, the polymer solution can also be purified using any method known in the art, i.e., some traces of catalyst impurities can be removed.

[0075] In a further aspect of the present invention, there is also provided a polymer solution according to the present invention that can be extruded into a film. As mentioned above, the polymer solution formed according to the present invention has a very high polymer content of up to 50 weight percent polymer. This allows the polymer solution to be employed in an extruder to form a film. Any technique known in the art for film formation with thermoplastic film can be employed herein. Such techniques include, without limitation, extrusion, calendaring, and casting. However, it should be emphasized that such extrusion techniques generally involve melt processing of the polymer. Since the polymers formed according to the present invention exhibit high glass transition temperatures that can exceed 300° C., melt processing of the polymer at such high temperatures is very difficult because the polymer also begins to decompose at such high processing temperatures.

[0076] Advantageously, it has been found that the polymer solution formed according to the present invention can be directly employed in an extruder using a process similar to the conventional techniques for melt extruding polymers, albeit at a much lower temperature. Thus, by implementing the present invention, the polymer solution can be extruded into a film using any extruder known in the art. In this method, the polymer solution is fed into a suitable extruder, melt mixed at a suitable temperature, then passed through a suitable die to form a film of a desired thickness, and cooled to form a membrane. Such polymer solution extrusion methods are advantageous over melt extrusion methods because they are performed at low temperatures, and therefore yellowing, curling, polymer degradation (i.e., molecular weight loss) and other defects during film formation are minimized or eliminated compared to melt extrusion methods.

[0077] Thus, another aspect of the present invention provides a film formed from the polymer solution according to the present invention. The film thus formed is free of yellowing, molecular weight loss and curl. Most importantly, the films formed according to the present invention have a high glass transition temperature (T g ) are low-cost and have high T values ​​above 200°C. g and can be readily formed into a film having an average thickness of greater than about 20 μm and less than about 500 μm.

[0078] More specifically, the film according to the present invention is produced by the following steps. The solution is kneaded and heated to a temperature lower than the softening temperature of the polymer, i.e., the glass transition temperature (T g extruding a polymer solution according to the present invention through an extruder while heating to a temperature below 100° C.; forming a film of desired thickness while extruding through a suitable film mold attached to the extruder; and Drying the extruded film at a suitable temperature to remove the solvent. Drying the film to remove any remaining solvent and / or other volatile impurities may be performed at a temperature that depends on the type of solvent used to extrude the film. Typically, such drying temperatures range from about 50°C to 280°C under an inert atmosphere or under vacuum. In some embodiments, drying of the film is performed at a temperature in the range of about 100°C to 250°C under vacuum for about 30 minutes to 4 hours; around 150°C to 220°C under vacuum for about 1 hour to 3 hours; or at 170°C to 200°C under vacuum for about 1 hour to 2 hours.

[0079] Any of the solvents described herein that dissolve the polymer can also be used to dissolve the polymer to form a polymer solution if the polymer is already isolated as a solid as described herein. The concentration of the polymer in the solution can range from 5 to 30 percent by weight. In some embodiments, the polymer content in the solution is about 10 percent, 15 percent, 18 percent, 20 percent, or 25 percent. In some embodiments, the polymer content in the solution can be greater than 30 percent by weight, greater than 40 percent by weight, or greater than 50 percent by weight.

[0080] The extruder employed can be any of those known in the art that can be employed in such film extrusion processes. Typically, single screw or twin screw extruders are employed. The screw can be composed of several elements, including mixing elements, kneading elements, etc., as is well known in the art.

[0081] As is well known in the art of film extrusion, the thickness of the film is controlled by employing a desired mold attached to the extruder. The extruded film sheet is wound by a roller and dried at a temperature ranging from 50°C to 250°C to remove any remaining solvent in the film. The film thus formed is substantially transparent to visible light. That is, most of the visible light is transmitted through the film. In some embodiments, such films formed from the polymeric composition of the present invention exhibit a visible light transmittance of 90 percent or more. In some other embodiments, such films formed from the polymeric composition of the present invention exhibit a visible light transmittance of 95 percent or more.

[0082] The film thus formed is then evaluated for its optical properties using any of the methods known in the art. For example, the refractive index of the film across the visible spectrum can be measured by ellipsometry. The optical quality of the film can be determined by visual observation. Quantitative percent transparency can be quantitatively measured by visible spectroscopy. Generally, films formed according to the present invention exhibit excellent optical clarity and can be tailored to the desired clarity described herein.

[0083] Finally, the film may be uniaxially or biaxially stretched to obtain improved thermal and mechanical properties. For example, biaxial stretching of the film thus formed has been found to reduce the coefficient of thermal expansion (CTE) of the film by up to 10 percent. A similar reduction in CTE has been observed for uniaxially stretched films. Generally, such biaxial and / or uniaxial stretching also results in higher tensile and flexural moduli.

[0084] In another aspect of the present invention, there is further provided an article comprising an optical layer comprising an optical polymer obtained by polymerizing at least one polycycloolefin monomer of formula (IV) in the presence of a palladium compound of formula (I) or (II).

[0085] Yet another aspect of the present invention provides a film formed from a polymer solution obtained by a polymerization composition comprising: a) a palladium compound selected from the group consisting of a compound of formula (I) as described herein and a compound of formula (II) as described herein; b) a compound of formula (III) as described herein; and c) at least one monomer of formula (IV) as described herein.

[0086] Advantageously, films formed according to the extrusion process of the present invention have been found to exhibit excellent optical, thermal and mechanical properties. For example, films formed by the extrusion process of the present invention have a glass transition temperature (T g ), and at least 1 × 10 4 The storage modulus in Pascals at 100°C is shown.

[0087] In another aspect of this embodiment, the vinyl addition polymers formed from the palladium compounds of formula (I) or (II) and suitable olefinic monomers of formula (IV) can be readily processed into a variety of solid forms, such as, for example, films. In one aspect of the invention, compositions comprising the vinyl addition polymers of the invention in a suitable solvent can be used for solvent assisted extrusion of films.

[0088] The present invention is further described by the following examples, which are provided for illustrative purposes and are not intended to limit the scope of the invention. (General) Example

[0089] The following abbreviations have been used herein to describe some of the compounds, devices, and / or methods employed to describe certain embodiments of the present invention. Pd601: Palladium diacetate diadamantyl(n-butyl)phosphine(HO), Pd445: Pd(OAc)2(P(t-butyl)2(n-butyl))(H2O), Pd1602:[Pd(OAc)(MeCN)(PAd2-n-Bu)2]B(C6F5)4, Pd942: Pd(OAc)2(PAd2-n-Bu)2, Pd785: Pd(OAc)2(PCy3)2, Pd613: N,N-bis((2,6-diisopropylphenyl)-imidazol-2-ylidene)Pd(OAc) 2、 LiFABA: Lithium(diethyl ether)tetrakis(pentafluorophenyl)borate ([Li(OEt2) 2.5 ][B(C6F5)4]), NB: Norbornene, HexNB: 5-hexylbicyclo-[2.2.1]hept-2-ene; Ad: adamantane, Cy: cyclohexyl, Bu: butyl, BCO: bicyclo[4.2.0]oct-7-ene, TES: triethylsilane, EtOH: ethanol, CTA: chain transfer agent, IPA: isopropanol, DCM: dichloromethane, THF: tetrahydrofuran, GPC: gel permeation chromatography, HPLC: high performance liquid chromatography, M w :Weight average molecular weight, M n : number average molecular weight, PDI: polydispersity, GC-MS: Gas Chromatography Mass Spectrometry; NMR: Nuclear magnetic resonance, FT-IR: Fourier transform infrared spectroscopy.

[0090] All palladium compounds described herein were prepared using standard Schlenk or drybox techniques unless otherwise noted. Anhydrous toluene and pentane were purchased from Aldrich, sparged with N2, and used without further purification. Palladium acetate (Pd(OAc)2) was purchased from Johnson Matthey. Di-tert-butyl (n-butyl)phosphine was obtained from Solvay and di-adamantyl (n-butyl)phosphine was purchased from Strem.

[0091] Example 1 Palladium diacetate diadamantyl-(n-butyl)phosphine(H2O)(Pd601) A solution of palladium acetate (0.7 g, 3.12 mmol) in anhydrous toluene (20 mL) mixed with deionized water (0.112 mL, 6.14 mmol) was placed in a nitrogen purged Schlenk flask and cooled to -78 °C (dry ice / IPA bath) with stirring. n-Butyl-di-1-adamantylphosphine (1.12 g, 3.12 mmol) was dissolved in anhydrous toluene (8 mL) under N2 atmosphere and added dropwise to the stirred palladium acetate solution. Stirred at -78 °C for an additional 15 min. Then warmed to ambient temperature and stirred overnight. The yellow solution became a yellow suspension overnight. The yellow precipitate was collected by filtration. The resulting solid was washed with toluene (15 mL x 3) and pentane (15 mL x 3) to give a yellow solid, which was dried under vacuum. Yield 1.54 g (82%).

[0092] Crystals of the title compound were grown in a solvent mixture of DCM / pentane and characterized by X-ray diffraction crystallography. X-ray intensity data were measured on a Bruker CCD diffractometer (Mo Kα radiation, λ=0.71073 Å) with dual Mo ImuS microfocus optics. The crystal was mounted in a cryoloop using paratone oil and placed under a nitrogen gas stream at 171 K (Oxford Cryosystems). The detector was placed at a distance of 5.00 cm from the crystal. Data were absorbance corrected with the SADABS program. The structure was refined using the Bruker SHELXTL software package (version 6.1) and F 2 The structure was solved by direct methods until convergence with a final anisotropic full-matrix least-squares refinement of . The crystal structure is shown in Figure 1. Additionally, for the compound, 1 H-NMR and 31 The results are shown in Figure 2. 1 The H-NMR spectrum is shown. 1H-NMR: (CDCl3,500MHz):d 0.93(t,3H), 1.32(q,2H), 1.42(q,2H), 1.66-1.80(m,14H), 1.86(s,6H), 2.01(s,6H), 2.28(m,12H), 5.97(br,2H). 31 P NMR(CDCl3,202MHz):d 52.46.

[0093] Example 2 Pd(OAc)2(P(t-butyl)2(n-butyl))(H2O)(Pd445) Palladium acetate (1 g, 4.4 mmol) was charged into a Schlenk flask fitted with a stir bar and purged with nitrogen. Deionized water (0.16 mL, 8.9 mmol) was then added and dissolved in anhydrous toluene (20 mL). The reaction mixture was cooled to -15°C (dry ice and 85 / 15 water / IPA). Di-t-butyl(n-butyl)phosphine (0.9 g, 4.4 mmol) was dissolved in anhydrous toluene (8 mL). The phosphine solution was slowly added dropwise over 10 minutes to the stirring palladium acetate solution. The reaction mixture was stirred at -15°C for an additional 15 minutes before warming to room temperature and stirring overnight. The resulting suspension was filtered and the collected solid was washed with pentane (15 mL x 3). The pale orange-yellow solid was dried under reduced pressure to give 1.8 g (90%) of the desired material (Pd445). Additionally, the title compound was 1 H-NMR and 31 The compound was characterized by P-NMR and FT-IR. 1 The H-NMR spectrum is shown. 1 H-NMR: (CDCl3, 500MHz):d 0.93(t,3H), 1.34(q,2H), 1.42(d,20H), 1.65-1.75(m,2H), 1.85(s,6H), 5.96(br,s,2H). 31 P NMR(CDCl3,202MHz):d 60.08. FT-IR(NEET):ν(cm -1) 3194(br), 2966(m), 2874(m), 1628(vs), 1465(m), 1384(s), 1328(s), 1183(m), 1018(m), 935(w), 900(w), 812(w), 720(m), 687(m), 618(m).

[0094] Example 3 [Pd(OAc)(MeCN)(PAd2-n-Bu)2]B(C6F5)4(Pd1602) A solution of PAd2-n-Bu (0.48 g, 1.34 mmol) in DCM (5 mL) was added dropwise to a red-brown suspension of palladium acetate (Pd(OAc)2) (0.12 g, 0.53 mmol) at -78 °C with stirring. After stirring for an additional 10 min, the reaction mixture was warmed to room temperature and stirred for an additional 2 h. The suspension became an orange solution. The solvent was removed under vacuum to give a yellow oily residue. The residue was dissolved in pentane and stirred to precipitate a yellow precipitate. The precipitate was collected by filtration and washed with pentane (5 mL x 3). The resulting yellow powder was dried under vacuum. Yield 0.37 g (73%).

[0095] To a suspension of the yellow solid obtained above (0.3 g, 0.32 mmol) in acetonitrile (20 mL) was added a solution of LiFABA (0.28 g, 0.32 mmol) in acetonitrile (15 mL) dropwise with stirring at room temperature. The mixture was stirred at room temperature for 5 h. The resulting yellow suspension was diluted with DCM (15 mL) and stirred for 1 h. The suspension was filtered through a syringe filter (0.2 μm PTFE) to remove the precipitated LiCl. The filtrate was concentrated under reduced pressure to give a golden syrup. The residue was washed with 1:5 diethyl ether:pentane (v:v, 5 mL x 3) and pentane (5 mL x 3). The residue was dried under reduced pressure to give the title compound as a yellow solid. Yield 0.35 g (68%).

[0096] Example 4 Homopolymer of HexNB using Pd601 HexNB (4.5 g, 25 mmol) and BCO (0.022 g, 0.187 mmol) were dissolved in toluene (17 mL). The mixture was purged with nitrogen for 1 h and then heated to 80° C. To this stirred solution, a mixture of the palladium compound of Example 1, Pd601 (0.001 mmol) and LiFABA (0.026 g, 0.003 mmol) in anhydrous THF (0.77 mL) was added at 80° C. under N2 atmosphere. The reaction mixture was sampled at 30, 60, 120 and 240 min for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. The results are summarized in Table 1. The resulting polymer solution was clear.

[0097] [Table 1]

[0098] Example 5 Homopolymer of HexNB using Pd1602 In this Example 5, the procedure of Example 4 was substantially repeated, except that the palladium compound of Example 3, Pd1602, was used. The reaction mixture was sampled at 60, 120 and 240 minutes for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. The results are summarized in Table 2. The resulting polymer solution was clear.

[0099] [Table 2]

[0100] Example 6 Copolymer of NB / HexNB (80 / 20 molar ratio) using Pd601 with BCO as CTA NB (1.9 g, 20 mmol), HexNB (0.9 g, 5 mmol), BCO (0.022 g, 0.19 mmol) were dissolved in toluene (10 mL). The mixture was purged with N2 for 1 h and then heated to 80 °C. To this stirred solution, a mixture of Pd601 (0.001 mmol) and LiFABA (0.0261 g, 0.003 mmol) in anhydrous THF (0.8 mL) was added at 80 °C under N2 atmosphere. The reaction mixture was sampled at 30, 60 and 120 min for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. The results are summarized in Table 3. The polymer formed was a clear solution. The results further demonstrate that the use of the palladium compound, Pd601, made according to the present invention provides not only high conversion but also polymers with higher molecular weight and excellent optical properties.

[0101] [Table 3]

[0102] Example 7 Homopolymer of HexNB using Pd601 with TES as CTA HexNB (4.5 g, 25 mmol), TES (0.022 g, 0.19 mmol) and EtOH (0.12 g, 2.5 mmol) were dissolved in toluene (10.4 mL). The mixture was purged with N2 for 1 h and then heated to 80° C. To this stirred solution, a mixture of Pd601 (0.001 mmol) and LiFABA (0.026 g, 0.003 mmol) in anhydrous THF (0.77 mL) was added at 80° C. under N2 atmosphere. The reaction mixture was sampled at 30, 120 and 240 min for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. The results are summarized in Table 4. The polymer formed was a clear solution. The results further demonstrate that the use of the palladium compound, Pd601, made according to the present invention provides not only high conversion but also polymers with higher molecular weight and excellent optical properties.

[0103] [Table 4]

[0104] Example 8 Copolymer of NB / HexNB (80 / 20 molar ratio) using Pd601 with TES as CTA NB (1.9 g, 20 mmol), HexNB (0.9 g, 5 mmol), TES (0.022 g, 0.19 mmol) and EtOH (0.12 g, 2.5 mmol) were dissolved in toluene (10.4 mL). After purging with N2 for 1 h, the temperature was raised to 80 °C. To this stirred solution, a mixture of Pd601 (0.001 mmol) and LiFABA (0.026 g, 0.003 mmol) in anhydrous THF (0.8 mL) was added at 80 °C under N2 atmosphere. The reaction mixture was sampled at 30, 60, 120 and 240 min for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. The results are summarized in Table 5. The polymer formed was a clear solution. The results also demonstrate that the use of the palladium compound, Pd601, made in accordance with the present invention provides not only high conversion rates, up to 100 percent, but also polymers with higher molecular weight and excellent optical properties.

[0105] [Table 5]

[0106] Example 9 Copolymer of NB / HexNB (80 / 20 molar ratio) with Pd601 In a nitrogen filled glove box, a catalyst solution was prepared by mixing Pd601 (0.0044 g, 0.007 mmol) and LiFABA (0.019 g, 0.022 mmol) in a 1:3 molar ratio in a septum bottle. Anhydrous THF (0.87 g) was transferred airlessly to the septum bottle and mixed. NB was previously dissolved in toluene to form a 75 wt% solution of NB in ​​toluene. To a stirred glass vessel, the monomer, NB solution (13.7 g, 0.144 mol) and HexNB (6.5 g, 0.036 mol) were added as well as BCO (0.167 g, 1.54 mol) as the CTA. Toluene (80.2 g) was added to the stirred glass vessel to make a 20 wt% solution of the monomer. The glass vessel was purged with nitrogen while stirring at room temperature. The contents were heated to 80 °C. Once at temperature, the catalyst & cocatalyst solution was transferred airlessly to a stirred glass vessel. The mixture was stirred for a total of 2 hours. The resulting polymer had a M w The conversion was 99.1% as determined by residual monomer using GC-MS.

[0107] Example 10 Copolymer of NB / HexNB (80 / 20 molar ratio) with Pd445 In a nitrogen filled glove box, a catalyst solution was prepared by mixing Pd445 (0.0032 g, 0.007 mmol) and LiFABA (0.019 g, 0.022 mmol) in a 1:3 molar ratio in a septum bottle. Anhydrous THF (0.87 g) was transferred airlessly to the septum bottle and mixed. NB was previously dissolved in toluene to form a 75 wt% solution of NB in ​​toluene. To a stirred glass vessel, the monomer, NB solution (13.65 g, 0.144 mol) and HexNB (6.46 g, 0.036 mol) were added as well as BCO (0.167 g, 0.00154 mol) as the CTA. Toluene (80.2 g) was added to the stirred glass vessel to make a 20 wt% solution of the monomer. The glass vessel was purged with nitrogen while stirring at room temperature. The contents were heated to 80 °C. Once at temperature, the catalyst & cocatalyst solution was transferred airlessly to a stirred glass vessel. The mixture was stirred for a total of 2 hours. The resulting polymer had a M w The conversion was 99.5% as determined by residual monomer using GC-MS.

[0108] Example 11 Copolymer of NB / HexNB (80 / 20 molar ratio) with Pd1602 In a nitrogen-filled glove box, a catalyst solution was prepared by mixing Pd1602 (0.0116 g, 0.007 mmol) and LiFABA (0.019 g, 0.022 mmol) in a 1:3 molar ratio in a septum bottle. Anhydrous THF (0.87 g) was transferred airlessly to the septum bottle and mixed. NB was previously dissolved in toluene to form a 75 wt% solution of NB in ​​toluene. To a stirred glass vessel, the monomer, NB solution (13.65 g, 0.144 mol) and HexNB (6.46 g, 0.036 mol) were added as well as BCO (0.147 g or 1.36 mol) as the CTA. Toluene (91.4 g) was added to the stirred glass vessel to make an 18 wt% solution of the monomer. The glass vessel was purged with nitrogen while stirring at room temperature. The contents were heated to 80 °C. Once at temperature, the catalyst & cocatalyst solution was transferred airlessly to a stirred glass vessel. The mixture was stirred for a total of 4 hours. The resulting polymer had a M w The conversion was 99.6% as determined by residual monomer using GC-MS.

[0109] Example 12 Copolymer of NB / HexNB (90 / 10 molar ratio) with Pd601 In this Example 12, the procedure of Example 4 was essentially repeated, except that a 90 / 10 molar ratio mixture of NB and HexNB was used. The resulting polymer had an M w The NA was 69,920, the PDI was 2.8, and the conversion was 99% as determined by residual monomer using GC-MS.

[0110] Examples 13 and 14 Copolymer of NB / HexNB (95 / 5 molar ratio) In Example 13, the procedure of Example 7 was substantially repeated, except that a 95 / 5 molar ratio mixture of NB and HexNB was used. In Example 14, the palladium compound Pd1602 from Example 3 was used instead of Pd601 from Example 1 to form a 95 / 5 molar ratio NB / HexNB copolymer. The M of the resulting polymer was w The PDI and yield are summarized in Table 6. w and PDI were measured by HPLC using a mixture of cyclohexane / decalin as the solvent and polybutadiene standards, and the conversion was measured by residual monomer using GC-MS.

[0111] [Table 6]

[0112] Example 15 Film formation from NB / HexNB (90 / 10 molar ratio) copolymer prepared with Pd601 The pre-precipitated copolymer from Example 12 was dissolved in toluene to form a 20 wt% solution of the polymer. A bar coater was used to produce a wet film with a thickness of 50 mm. A two-stage drying process was used to evaporate the solvent. First, the wet film was heated at 80°C for 5 minutes and then at 110°C for 10 minutes. After drying, the tensile modulus, elongation at break (ETB) and CTE were measured to be 2192 MPa tensile modulus, 4.6% ETB, and 80 ppm CTE.

[0113] Example 16 Film formation from NB / HexNB copolymer The various polymers formed in Examples 9, 11, 13, and 14, respectively, were dissolved in toluene to form solutions of approximately 18 weight percent polymer. Each of these polymer solutions was then processed into films using a solvent casting process. The films thus formed were dried in vacuum at 250° C. for 3 hours. Thermomechanical properties were measured as summarized in Table 7. Glass transition temperature (T g) was measured in multi-frequency strain temperature ramp mode using a DMA Q800 (TA Instruments, TX, USA) from 30 to 320 °C under nitrogen atmosphere at a rate of 5 °C / min, a frequency of 1 Hz, a strain of 0.1%, and a preload force of 0.001 N. The length and width of the specimen were 35 mm and 8 mm, respectively, and the thickness of the rectangular film was 0.1 mm. The coefficient of thermal expansion (CTE) was measured using an Olympus OLS4000 laser microscope equipped with a Linkam hot stage at a temperature ramp of 10 °C / min from 50 to 150 °C in 5 °C increments. Strain ε xx and ε yy was calculated by digital image correlation method (DICM). Dielectric constant (Dk) and dielectric loss (Df) measurements were performed using copolymer (NB / HexNB) films cut to a size of approximately 3.5 mm wide and 80 mm long using a dicing saw. The diced films were dried at 100 °C for 3 h under vacuum. The relative permittivity (Dk) and dielectric loss tangent (Df) of the films were measured at 10 GHz using a resonant cavity microwave dielectric constant meter (ADMS010c, JIS C2565). The elongation at break (ETB) was calculated from stress-strain curves generated using a film stack of 30 mm wide x 60 mm long x 0.1 mm thick using a Shimadzu AG-500kNIS, with a chuck distance of 30 mm and a tensile speed of 1 mm / min. Tensile tests were performed using an Instron following the test protocol described in ASTM D638. From the data presented in Table 7, it is apparent that both of the palladium compounds of the present invention, specifically the compounds of Examples 1 and 3, are similarly active in forming films exhibiting superior properties. Furthermore, the observed thermomechanical properties summarized in Table 7 were unattainable from any other palladium catalyst known in the art.

[0114] [Table 7]

[0115] Comparative Example 1 Pd(OAc)2(PAd2-n-Bu)2(Pd942) Palladium acetate (0.1 g, 0.445 mmol) was placed in a nitrogen purged Schlenk flask. It was then dissolved in anhydrous toluene (3 mL) and the mixture was cooled to -78 °C (dry ice, IPA bath). n-Butyldi-1-adamantylphosphine (0.327 g, 0.913 mmol) was dissolved in anhydrous toluene (2 mL) under N2 atmosphere. The phosphine solution was added dropwise to the stirred palladium acetate solution at -78 °C under N2 atmosphere. The mixture was stirred at -78 °C for an additional 15 min. It was then allowed to warm to ambient temperature and stirred overnight. The yellow solution became a yellow suspension. The suspension was diluted with anhydrous pentane (5 mL) and the precipitate was collected by filtration. The resulting solid was washed with pentane (5 mL x 3) and the resulting yellow solid was dried in vacuum. Yield 0.25 g (60%). 1 H NMR (CDCl3,500MHz):d 1.02(t,6H), 1.38(q,4H), 1.54(q,4H), 1.75-1.78(m,12H), 1.88(m,22H), 2.06(m,12H), 2.31(m,12H), 2.43(m,12H), 31 P NMR (CDCl3, 202 MHz): d 26.8.

[0116] Comparative Example 2 Pd(OAc)2(PCy3)2(Pd785) In this Comparative Example 2, the procedure set forth in Comparative Example 1 was followed, except that tricyclohexylphosphine was used instead of n-butyldi-1-adamantylphosphine to obtain the title compound. The following Comparative Examples 3 and 4 show that the art-known palladium compounds of Comparative Examples 1 and 2 do not provide polymers of superior quality as shown in Examples 4 and 5. That is, the palladium compounds of the present invention provide polymers of superior properties. Specifically, Comparative Example 3 shows that the polymer made with Pd942, Comparative Example 1, has low conversion and variable dispersity, as summarized in Table 8. The polymer made with Pd785, Comparative Example 2, provides a hazy polymer solution even after 30 minutes and a low molecular weight polymer, as summarized in Table 9.

[0117] Comparative Example 3 Homopolymer of HexNB with Pd942 In this Comparative Example 3, the procedure of Example 4 was substantially repeated, except that the palladium compound of Comparative Example 1, Pd942, was used. The reaction mixture was sampled at 30, 60, 120 and 240 minutes for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. The results are summarized in Table 8. Although the resulting polymer solutions were clear, the conversion was generally low, even after 4 hours, as summarized in Table 8.

[0118] [Table 8]

[0119] Comparative Example 4 Homopolymer of HexNB with Pd785 In this Comparative Example 4, the procedure of Example 4 was substantially repeated, except that the palladium compound of Comparative Example 2, Pd785, was used. The reaction mixture was sampled at 60, 120, and 240 minutes for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. The results are summarized in Table 9. The resulting polymer solution was hazy even at 30 minutes of polymerization, even though the conversion was about 99.8 percent or more, as summarized in Table 9.

[0120] [Table 9]

[0121] Comparative Example 5 Homopolymer of NB using Pd942 with TES / EtOH as CTA In this Comparative Example 5, the procedure of Example 7 was substantially repeated, except that the palladium compound of Comparative Example 1, Pd942, was used. The reaction mixture was sampled at 30, 60, 120, and 240 minutes for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. Even after 4 hours the reaction mixture remained liquid, and the viscosity of the reaction mixture did not change significantly. The conversion at 2 hours was determined to be only about 30 percent, and the resulting polymer had low M as measured by GPC. w 293186, M n The index was 142,545 and the PDI was 2.1.

[0122] Comparative Example 6 Copolymer of NB / HexNB (80 / 20 molar ratio) using Pd942 with TES / EtOH as CTA In this Comparative Example 6, the procedure of Example 8 was substantially repeated, except that the palladium compound of Comparative Example 1, Pd942, was used. The reaction mixture was sampled at 30, 60, 120, and 240 minutes for evaluation of molecular weight and conversion by GPC and GC-MS, respectively. Since the reaction mixture remained liquid even after 4 hours and the viscosity of the reaction mixture did not change significantly, Pd942 was considered to be ineffective as a vinyl addition polymerization catalyst under these conditions. No polymerization of monomer had occurred even after 4 hours.

[0123] Comparative Example 7 Copolymer of NB / HexNB (80 / 20 molar ratio) with Pd613 In a nitrogen filled glove box, a catalyst solution was prepared by mixing Pd613 (0.0044 g, 0.007 mmol) and LiFABA (0.019 g, 0.022 mmol) in a 1:3 molar ratio in a septum bottle. Anhydrous THF (0.87 g) was transferred airlessly to the septum bottle and mixed. NB was previously dissolved in toluene to form a 75 wt% solution of NB in ​​toluene. To a stirred glass vessel, the monomer, NB solution (13.65 g, 0.145 mol) and HexNB (6.46 g, 0.036 mol) were added as well as BCO (0.167 g, 1.54 mol) as the CTA. Toluene (80.2 g) was added to the stirred glass vessel to make a 20 wt% solution of the monomer. The glass vessel was purged with nitrogen while stirring at room temperature. The contents were heated to 80 °C. Once at temperature, the catalyst & cocatalyst solution was transferred airlessly to a stirred glass vessel. The mixture was stirred for a total of 2 hours. The resulting polymer had an M w was 70,647 and the conversion was 74% as determined by residual monomer using GC-MS.

[0124] This Comparative Example 7 clearly demonstrates that commonly used conventional palladium catalysts, such as N-heterocyclic carbene (NHC)-linked palladium compounds, are not effective in the vinyl addition polymerization of olefins of formula (IV) described herein. For example, the NHC-linked palladium catalyst Pd613, as used in this Comparative Example 7, resulted in a low conversion of only 74% as well as a lower molecular weight polymer of 70,647 under similar reaction conditions as employed in Examples 4-14, in accordance with the practice of the present invention. [ka]

[0125] Although the present invention has been described with reference to the above examples, the present invention is not limited to the examples, but generally encompasses the general scope set forth hereinabove. Various modifications and embodiments may be made without departing from the spirit and scope thereof.

Claims

【Request 1】 【Chemistry 1】 A palladium compound selected from the group consisting of: L is acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C ６ H ５ CN), 2,4,6-trimethylbenzonitrile, phenylacetonitrile (C ６ H ５ CH ２ CN), 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, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran and benzophenone; Z － But BF ４ － , tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyl tris(perfluorophenyl)borate, ethyl tris(perfluorophenyl)borate, phenyl tris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1 tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, PF ６ － , SbF ６ － , n-C ４ F ９ SO ３ － , C.F. ３ SO ３ － and p-CH ３ (C ６ H ４ ) -SO ３ － is selected from the group consisting of R １ , R ２ and R ３ At least two of the tert-(C ４ -C １２ ) alkyl, 1-(C １ -C ５ ) alkyl(C ３ -C ８ ) cycloalkyl, 1-(C ５ -C １２ ) bicycloalkyl and 1-(C ８ -C １２ ) tricycloalkyl, (C ６ -C １０ ) aryl and (C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl, and the remaining R １ , R ２ Or R ３ is methyl, ethyl, linear or branched (C ３ -C １２ ) alkyl, (C ６ -C １０ ) aryl and (C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl; R ４ , R ５ and R ６ are the same or different, and each independently represents methyl, ethyl, and linear or branched (C ３ -C ２０ ) alkyl, trifluoromethyl, pentafluoroethyl, and linear or branched (C ３ -C ２０ ) perfluoroalkyl.

2. L is acetonitrile or propionitrile; Z － is selected from the group consisting of tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, and tetrakis(3,4,5-trifluorophenyl)borate; R １ , R ２ and R ３ at least two of R are the same and selected from the group consisting of tert-butyl, 2-methylbutyl, 2-ethylbutyl, 2-methylpentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methylcycloheptyl, 1-bicyclo[2,2,1]heptyl, 1-bicyclo[2,2,2]octyl, and 1-adamantyl; and the remaining R １ , R ２ Or R ３ is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 3-methylbutyl (isoamyl) and 2,2-dimethylpropyl (neopentyl); R ４ , R ５ and R ６ 2. The compound of claim 1, wherein: are the same or different and each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, trifluoromethyl, pentafluoroethyl, and heptafluoropropyl.

3. The compound of formula (I) 【Chemistry 2】 2. The compound of claim 1 selected from the group consisting of:

4. The compound of formula (II) 【Chemistry 3】 2. The compound of claim 1 selected from the group consisting of:

5. A vinyl addition polymerization catalyst comprising a compound of formula (I) according to claim 1.

6. A vinyl addition polymerization catalyst comprising a compound of formula (II) according to claim 1.

7. A polymer solution obtained by polymerizing at least one polycycloolefin monomer in the presence of the palladium compound according to claim 1.

8. 8. The polymer solution of claim 7 extruded into a film.

9. A film formed from the polymer solution of claim 7.

10. 13. An article comprising an optical layer comprising an optical polymer obtained by polymerizing at least one polycycloolefin monomer in the presence of the palladium compound according to claim 1.

11. 1. A polymeric composition comprising: a) 【Chemistry 4】 A palladium compound selected from the group consisting of: L is acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C ６ H ５ CN), 2,4,6-trimethylbenzonitrile, phenylacetonitrile (C ６ H ５ CH ２ CN), 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, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran and benzophenone; Z － But BF ４ － , tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyl tris(perfluorophenyl)borate, ethyl tris(perfluorophenyl)borate, phenyl tris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1 tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, PF ６ － , SbF ６ － , n-C ４ F ９ SO ３ － , C.F. ３ SO ３ － and p-CH ３ (C ６ H ４ ) -SO ３ － is selected from the group consisting of R １ , R ２ and R ３ At least two of the tert-(C ４ -C １２ ) alkyl, 1-(C １ -C ５ ) alkyl(C ３ -C ８ ) cycloalkyl, 1-(C ５ -C １２ ) bicycloalkyl and 1-(C ８ -C １２ ) tricycloalkyl, (C ６ -C １０ ) aryl and (C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl, and the remaining R １ , R ２ Or R ３ is methyl, ethyl, linear or branched (C ３ -C １２ ) alkyl, (C ６ -C １０ ) aryl and (C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl; R ４ , R ５ , and R ６ are the same or different, and each independently represents methyl, ethyl, and linear or branched (C ３ -C ２０ ) alkyl, trifluoromethyl, pentafluoroethyl, and linear or branched (C ３ -C ２０ ) a palladium compound selected from the group consisting of perfluoroalkyl; b) A compound of formula (III): M ｄ ＋ Z － (III) And, M ｄ ＋ Lithium, sodium, potassium, cesium, barium, ammonium, and linear or branched tetra(C １ -C ４ ) alkylammonium; Z － But B (C ６ F ５ ) ４ － , B[C ６ H ３ (CF ３ ) ２ ] ４ － , B(C ６ H ５ ) ４ － , [Al(OC(CF ３ ) ２ C ６ F ５ ) ４ ] － , B.F. ４ － , P.F. ６ － , AsF ６ － , SbF ６ － , (CF ３ SO ２ ) N － and C.F. ３ SO ３ － and a compound, the compound being a weakly coordinating anion selected from the group consisting of: c) at least one monomer of formula (IV): 【Chemistry 5】 And, m is an integer of 0, 1 or 2; R ７ , R ８ , R ９ and R １０ are the same or different and each independently represent hydrogen, linear or branched (C １ -C １６ ) alkyl, hydroxy (C １ -C １６ ) alkyl, perfluoro(C １ -C １２ ) alkyl, (C ３ -C １２ ) cycloalkyl, (C ６ -C １２ ) bicycloalkyl, (C ７ -C １４ ) tricycloalkyl, (C ６ -C １０ ) aryl, (C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl, perfluoro(C ６ -C １０ ) aryl, perfluoro(C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl, di(C １ -C ２ ) Alkylmaleimide (C ３ -C ６ ) alkyl, di(C １ -C ２ ) Alkylmaleimide (C ２ -C ６ ) Alkoxy (C １ -C ２ ) alkyl, hydroxy, (C １ -C １２ ) alkoxy, (C ３ -C １２ ) cycloalkoxy, (C ６ -C １２ ) bicycloalkoxy, (C ７ -C １４ ) tricycloalkoxy, (C ６ -C １０ ) aryloxy (C １ -C ３ ) alkyl, (C ５ -C １０ ) Heteroaryloxy (C １ -C ３ ) alkyl, (C ６ -C １０ ) aryloxy, (C ５ -C １０ ) heteroaryloxy or (C １ -C ６ ) acyloxy, each of said substituents being optionally substituted with halogen or hydroxy.

12. The polymeric composition of claim 11 further comprising a solvent.

13. 13. The polymeric composition of claim 12, wherein the solvent is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentane, hexane, heptane, octane, decane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 1-chloropentane, benzene, toluene, o-, m-, or p-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, tetrahydrofuran (THF), diethyl ether, petroleum ether, and mixtures thereof in any combination.

14. The compound of formula (I) 【Chemistry 6】 12. The polymeric composition of claim 11, selected from the group consisting of:

15. The compound of formula (II) 【Chemistry 7】 12. The polymeric composition of claim 11, selected from the group consisting of:

16. The compound of formula (III) Lithium tetrafluoroborate; Lithium triflate; Lithium tetrakis(pentafluorophenyl)borate; Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexakis(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexakis(pentafluorophenyl)arsenate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexakis(pentafluorophenyl)antimonate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; Lithium tetrakis(pentafluorophenyl)aluminate; Lithium tris(nonafluorobiphenyl)fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl)aluminate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; Lithium methyltris(pentafluorophenyl)aluminate; and N,N-Dimethylanilinium tetrakis(pentafluorophenyl)-borate (DANFABA) 12. The polymeric composition of claim 11, selected from the group consisting of:

17. The monomer of formula (IV) Bicyclo[2.2.1]hept-2-ene (NB); 5-Hexylbicyclo-[2.2.1]hept-2-ene (HexNB); 5-Octylbicyclo[2.2.1]hept-2-ene (OctNB); 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB); 5-perfluorobutylbicyclo[2.2.1]hept-2-ene (C ４ F ９ N.B.); 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); 5-benzylbicyclo[2.2.1]hept-2-ene (BnNB); 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB); 5-vinylbicyclo[2.2.1]hept-2-ene (VNB); and 5-Ethylidenenorbornene or 2-Ethylidenebicyclo[2.2.1]hept-2-ene (ENB) 12. The polymeric composition of claim 11, selected from the group consisting of:

18. A film formed from a polymer solution obtained by a polymerization composition, a) 【Chemistry 8】 A palladium compound selected from the group consisting of: L is acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C ６ H ５ CN), 2,4,6-trimethylbenzonitrile, phenylacetonitrile (C ６ H ５ CH ２ CN), 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, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran and benzophenone; Z － is BF ４ － , tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyl tris(perfluorophenyl)borate, ethyl tris(perfluorophenyl)borate, phenyl tris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1 tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, PF ６ － , SbF ６ － , n-C ４ F ９ SO ３ － , C.F. ３ SO ３ － and p-CH ３ (C ６ H ４ ) -SO ３ － is selected from the group consisting of R １ , R ２ and R ３ At least two of the tert-(C ４ -C １２ ) alkyl, 1-(C １ -C ５ ) alkyl(C ３ -C ８ ) cycloalkyl, 1-(C ５ -C １２ ) bicycloalkyl and 1-(C ８ -C １２ ) tricycloalkyl, (C ６ -C １０ ) aryl and (C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl, and the remaining R １ , R ２ Or R ３ is methyl, ethyl, linear or branched (C ３ -C １２ ) alkyl, (C ６ -C １０ ) aryl and (C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl; R ４ , R ５ , and R ６ are the same or different, and each independently represents methyl, ethyl, and linear or branched (C ３ -C ２０ ) alkyl, trifluoromethyl, pentafluoroethyl, and linear or branched (C ３ -C ２０ ) a palladium compound selected from the group consisting of perfluoroalkyl; b) A compound of formula (III): M ｄ ＋ Z － (III) And, M ｄ ＋ Lithium, sodium, potassium, cesium, barium, ammonium, and linear or branched tetra(C １ -C ４ ) alkylammonium; Z － But B (C ６ F ５ ) ４ － , B[C ６ H ３ (CF ３ ) ２ ] ４ － , B(C ６ H ５ ) ４ － , [Al(OC(CF ３ ) ２ C ６ F ５ ) ４ ] － , B.F. ４ － , P.F. ６ － , AsF ６ － , SbF ６ － , (CF ３ SO ２ ) N － and C.F. ３ SO ３ － and a compound, the compound being a weakly coordinating anion selected from the group consisting of: c) at least one monomer of formula (IV): 【Chemistry 9】 And, m is an integer of 0, 1 or 2; R ７ , R ８ , R ９ and R １０ are the same or different and each independently represent hydrogen, linear or branched (C １ -C １６ ) alkyl, hydroxy (C １ -C １６ ) alkyl, perfluoro(C １ -C １２ ) alkyl, (C ３ -C １２ ) cycloalkyl, (C ６ -C １２ ) bicycloalkyl, (C ７ -C １４ ) tricycloalkyl, (C ６ -C １０ ) aryl, (C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl, perfluoro(C ６ -C １０ ) aryl, perfluoro(C ６ -C １０ ) Aryl (C １ -C ３ ) alkyl, di(C １ -C ２ ) Alkylmaleimide (C ３ -C ６ ) alkyl, di(C １ -C ２ ) Alkylmaleimide (C ２ -C ６ ) Alkoxy (C １ -C ２ ) alkyl, hydroxy, (C １ -C １２ ) alkoxy, (C ３ -C １２ ) cycloalkoxy, (C ６ -C １２ ) bicycloalkoxy, (C ７ -C １４ ) tricycloalkoxy, (C ６ -C １０ ) aryloxy (C １ -C ３ ) alkyl, (C ５ -C １０ ) Heteroaryloxy (C １ -C ３ ) alkyl, (C ６ -C １０ ) aryloxy, (C ５ -C １０ ) heteroaryloxy or (C １ -C ６ ) acyloxy, each of said substituents being optionally substituted with halogen or hydroxy.

19. 20. The film of claim 18 obtained by extrusion of the polymer solution.

20. A glass transition temperature (Tg) of at least 200° C. and a viscosity of at least 1×10 at 100° C. ４ 20. The film of claim 18 exhibiting a storage modulus in Pascals.

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