Palladium catalyst for vinyl addition polymer formation with improved film forming properties

Abstract

A series of palladium compounds described in the specification are excellent vinyl addition polymerization catalysts. Specifically, compounds represented by general formulae (I) and (II) described in the specification unexpectedly exhibit much higher reactivity than compounds known in the art in the vinyl addition polymerization of various cycloolefin monomers, and thus can form a polymer having an extremely high molecular weight. The present specification also discloses methods of forming various solid three-dimensional articles, such as solution extrusion of a polymer solution formed by vinyl addition polymerization of various cycloolefin monomers using very low amounts of a palladium compound of general formula (I) or (II) as described in the specification. Polymer films formed from the polymerizable composition exhibit unprecedented properties, such as excellent transparency properties, higher thermal and mechanical properties, and other improved properties. Thus, the films so formed can be used in a variety of optoelectronic applications. # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 327,632, filed on April 5, 2022, the entire contents of which are incorporated by reference into this specification. Technical Field

[0003] The present invention relates to a series of palladium compounds. More specifically, the present invention relates to a series of palladium compounds of the general formula (I) and (II). The present invention also relates to a process for the preparation of these compounds. The compounds of the present invention are extremely reactive and are excellent vinyl addition polymerization catalysts for the formation of high molecular weight polycycloolefin polymers having excellent optical, thermal and mechanical properties. More specifically, the polymers so formed in solution can be easily extruded into transparent films that can be used in various optoelectronic applications. Background Art

[0004] Cyclic olefin polymers such as polynorbornene (PNB) are widely used in various electronic, optoelectronic and other applications, and therefore, methods for preparing such PNBs on an industrial scale are becoming increasingly important. It is known from the literature that various functionalized PNBs can be synthesized by vinyl addition polymerization using appropriate starting norbornene monomers with various transition metal catalysts and procatalysts. For example, reference is made to U.S. Pat. No. 7,910,674 B2, the relevant portions of which are incorporated herein by reference.

[0005] As mentioned above, PNB is usually used as coating composition in various applications. One of the possible methods of using these materials is to form a film by solution casting or extrusion in a suitable solvent. The film formed in this way is expected to show excellent optical and low dielectric properties, as well as thermomechanical properties. However, the use of excessive solvents in such operations can cause problems in large-scale commercial operations. In addition, since it is necessary to obtain substantially metal-free polymers in various optoelectronic applications, the use of various transition metals in vinyl addition polymerization will also become a problem. It is also very difficult to remove residual metals from polymers. And, it is necessary to develop a highly active catalyst so that a smaller amount of catalyst can be used when manufacturing extremely high molecular weight PNBs.

[0006] PNBs made from various palladium catalysts can provide better quality polymers and solve some of the problems faced in the field. However, the use of various palladium catalysts to form PNBs can cause opacity in the polymer film. In addition, some of these catalysts are not very active, which leads to low conversion (<90%) and requires additional steps to purify the polymer to remove residual monomers and oligomers. For example, refer to U.S. Patent Application Publication No. 2005 / 0187398A1, which describes a series of single-component cationic palladium proinitiators. However, some of these proinitiators are inactive and / or produce low-quality polymer films. Summary of the invention

[0007] Therefore, an object of the present invention is to provide a highly active palladium catalyst to form extremely high molecular weight PNBs with excellent optical, thermal, mechanical and electrical properties.

[0008] Another object of the present invention is to provide a series of PNBs that can be used in various optoelectronic applications.

[0009] Another object of the present invention is to provide a high concentration PNB solution for forming a film with unprecedented optical, thermal, mechanical and electrical properties.

[0010] Hereinafter, other objects and further applicable scope of the present invention will be described in detail.

[0011] Effects of the Invention

[0012] Unexpectedly, it has been found that the various palladium compounds of the general formula (I) and (II) described in this specification are highly active in the vinyl addition polymerization of the various norbornene-type monomers of the general formula (IV) described in this specification. The polynorbornene formed using the palladium compound of the general formula (I) or (II) exhibits extremely high molecular weight and narrow polydispersity. Therefore, a small amount of the palladium compound of the general formula (I) or (II) can be used to form a polynorbornene with an extremely high molecular weight. Furthermore, since the conversion rate of the monomer to the polymer is as high as 99.5% to 99.9% or more, all concerns about removing residual monomers or oligomers are eliminated. More importantly, a high conversion rate of more than 99% can be achieved in less than 30 to 60 minutes. The polymer is easily dissolved in various solvents to form a transparent polymer solution of extremely high concentration, i.e., a solution of 10% to 50% by weight. The polymer solution can then be cast into a film using various methods, including solution casting and extrusion methods, but not limited to this. The films thus formed exhibit improved optical, thermal, mechanical and electrical properties and thus have various optoelectronic applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Hereinafter, embodiments according to the present invention will be described with reference to the following drawings and / or images. When drawings are provided, they are simplified portions of various embodiments of the present invention and are for illustration purposes only.

[0014] Figure 1 is an illustrative example of the palladium compound of the general formula (I) according to the present invention, which is also illustrated in Example 1, namely, diadamantyl-(n-butyl)phosphine palladium diacetate (H 2 Diagram of the molecular structure of Pd601).

[0015] Figure 2 An illustrative example of the palladium compound of the general formula (I) according to the present invention, diadamantyl-(n-butyl)phosphine palladium diacetate (H 2 O)(Pd601) 1 H NMR.

[0016] Figure 3 An illustrative example of the palladium compound of the general formula (I) according to the present invention, which is also illustrated in Example 2, is di-tert-butyl-(n-butyl)phosphine palladium diacetate (H 2 O)(Pd445) 1 H NMR. DETAILED DESCRIPTION

[0017] As used in this specification, the articles "a / an" and "the" include plural referents unless otherwise specified to be limited to one referent.

[0018] Unless otherwise indicated, all numbers, values ​​and / or expressions relating to amounts of ingredients, reaction conditions, etc. used in this specification and the claims appended hereto are to be understood as being modified in all cases by the term "about" because they are subject to various measurement uncertainties encountered in obtaining the stated values.

[0019] The numerical ranges disclosed in this specification are continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. In addition, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. Moreover, when multiple ranges are provided to describe characteristics or features, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed in this specification should be understood to include any ranges and all sub-ranges thereof. For example, a specified range from "1 to 10" should be deemed to include any range and all sub-ranges between the minimum value 1 and the maximum value 10. Exemplary sub-ranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.

[0020] The expression "alkyl" as used in this specification refers to a saturated straight or branched hydrocarbon substituent having a specified number of carbon atoms. Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, tert-butyl, etc. Derivative expressions such as "alkoxy", "thioalkyl", "alkoxyalkyl", "hydroxyalkyl", "alkylcarbonyl", "alkoxycarbonylalkyl", "alkoxycarbonyl", "diphenylalkyl", "phenylalkyl", "phenylcarboxyalkyl" and "phenoxyalkyl" should be interpreted accordingly.

[0021] The expression "cycloalkyl" as used in this specification includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. For example, the derived expressions "cycloalkoxy", "cycloalkylalkyl", "cycloalkylaryl" and "cycloalkylcarbonyl" should also be interpreted accordingly.

[0022] The expression "perhaloalkyl" as used in this specification refers to the above alkyl groups, wherein all hydrogen atoms in the alkyl group are replaced by halogen atoms selected from fluorine, chlorine, bromine or iodine. Illustrative examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl and straight or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecylfluoropentyl, undecylchloropentyl, tridecafluorohexyl, tridecachlorohexyl and the like. The derived expression "perhaloalkoxy" should also be interpreted accordingly. Certain alkyl groups recorded in this specification, such as "alkyl" that may be partially fluorinated (i.e., only a portion of the hydrogen atoms in the alkyl group are replaced by fluorine atoms) should also be interpreted accordingly.

[0023] The expression "acyl" used in this specification shall have the same meaning as "alkanoyl", which can also be represented by the structure "R-CO-", where R is an "alkyl" with a specified number of carbon atoms. In addition, the meaning of "alkylcarbonyl" shall be the same as the "acyl" described in this specification. Specifically, "(C 1 -C 4 )acyl refers to formyl, acetyl / ethanoyl, propionyl, n-butyryl, etc. For example, the derived expressions "acyloxy" and "acyloxyalkyl" should also be interpreted accordingly.

[0024] The expression "aryl" used in this specification refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or substituted naphthyl include o-tolyl, p-tolyl, m-tolyl, 1,2-xylyl, 1,3-xylyl, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. "Substituted phenyl" or "substituted naphthyl" also includes any possible substituents further defined in this specification or known in the art.

[0025] The expression "arylalkyl" used in the present specification means that the above aryl group is further connected to the above alkyl group. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.

[0026] The expression "alkenyl" as used in this specification refers to a non-cyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and at least one carbon-carbon double bond, including ethylene, vinyl, ethenyl and straight or branched propenyl, butenyl, pentenyl and hexenyl. The derived expressions "arylalkenyl" and 5-membered or 6-membered "heteroarylalkenyl" should also be interpreted accordingly. Illustrative examples of such derived expressions include 2-ethylenebicyclo[2.2.1]heptane or 2-ethylidenenorbornane, 2-vinylnorbornane, phenylvinyl, 4-methoxyphenylvinyl, etc.

[0027] The expression "heteroaryl" used in this specification includes all known aromatic groups containing heteroatoms. Representative 5-membered heteroaryls include furanyl, thienyl or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, etc. Representative 6-membered heteroaryls include groups such as pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl. Representative examples of bicyclic heteroaryls include groups such as benzofuranyl, benzothienyl, indolyl, quinolyl, isoquinolyl, cinnolinyl, benzimidazolyl, indazolyl, pyridinylfuranyl, pyridinylthienyl.

[0028] The expression "heterocycle" used in this specification includes all known cyclic groups containing reduced heteroatoms. Representative 5-membered heterocyclic groups include tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, etc. Representative 6-membered heterocyclic groups include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, etc. Other various heterocyclic groups include, but are not limited to, aziridinyl, azepanyl, diazepanyl, diazabicyclo [2.2.1] hept-2-yl, triazocanyl, etc.

[0029] "Halogen" or "halo" refers to chlorine, fluorine, bromine and iodine.

[0030] In a broad sense, the term "substituted" is considered to include all permissible substituents of organic compounds. In some embodiments disclosed in this specification, the term "substituted" refers to substitution with one or more substituents independently selected from the group consisting of: (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C1 -C 6 )Perfluoroalkyl, phenyl, hydroxyl, -CO 2 H, ester, amide, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthioate and (C 1 -C 6 ) perfluoroalkoxy. However, any other suitable substituents known to those skilled in the art can also be suitable for use in these embodiments.

[0031] It should be noted that any atom with unsatisfied valences in the text, schemes, examples and tables of the specification is assumed to have the appropriate number of hydrogen atoms to satisfy the valences.

[0032] In this specification, the terms "dielectric" and "insulating" should be understood to be used interchangeably. Therefore, reference to an insulating material or insulating layer includes dielectric materials or dielectric layers, and vice versa. Furthermore, the term "organic electronic device" used in this specification should be understood to include the term "organic semiconductor device" and various examples of such devices that are well known in the art.

[0033] The dielectric constant (Dk) of a material as used in this specification is the ratio of the charge stored in an insulating material between two metal plates to the charge that can be stored if the insulating material is replaced by a vacuum or air. It is also called the electric permittivity or permittivity for short. It is sometimes called the relative permittivity because it is measured relative to the permittivity of free space.

[0034] As used in this specification, "low loss" refers to the loss factor (Df) which measures the rate of energy loss in an oscillating mode (mechanical, electrical or electromechanical) in a dissipative system. It is the inverse of the quality factor and represents the "quality" or durability of the oscillation.

[0035] The term "derived" means that the polymerizable repeating unit is obtained, for example, by polymerization (formation) of a polycyclic norbornene-type monomer based on the general formula (I), wherein the obtained polymer is formed by 2,3-matched linkage of the norbornene-type monomer as shown below.

[0036]

[0037] As described in further detail below, the above polymerization is also well-known as vinyl addition polymerization, which is usually carried out in the presence of an organometallic compound such as a palladium compound or a nickel compound.

[0038] Therefore, according to an embodiment of the present invention, there is provided a palladium compound selected from the group consisting of the following compounds:

[0039] Compounds of general formula (I):

[0040] and

[0041] Compounds of general formula (II):

[0042]

[0043] in,

[0044] L is selected from the group consisting of acetonitrile, propionitrile, n-butyl nitrile, tert-butyl nitrile, 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-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2,6-di-tert-butylpyridine, 2,4-di-tert-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;

[0045] Selected from including 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-trifluorovinyl)borate, tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate borate, tetrakis(3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, and Group;

[0046] R bonded to phosphorus via a tertiary carbon 1 , R 2 and R 3 At least two of which are the same or different and are selected from the group consisting of 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 group; and the remaining R 1 , R 2 or R 3 is methyl, ethyl, straight chain or branched (C 3 -C 12 ) alkyl, (C 6 -C 10 ) aryl and (C 6 -C 10)Aryl (C 1 -C 3 )alkyl; and

[0047] R 4 , R 5 and R 6 are the same or different and are independently selected from the group consisting of methyl, ethyl and straight or branched (C 3 -C 20 ) alkyl, trifluoromethyl, pentafluoroethyl and straight or branched chain (C 3 -C 20 ) a perfluoroalkyl group.

[0048] It should be noted that the compound of general formula (I) may contain other suitable solvents as coordinating solvents instead of water. Therefore, the compound of general formula (I) may also contain other solvents exemplified by general formula (IA):

[0049]

[0050] Among them, R 1 , R 2 , R 3 , R 4 and R 5 As described in this specification. S is any suitable coordination solvent. Examples of such solvents include, but are not limited to, alcohols (including methanol, ethanol, n-propanol, isopropanol, butanol, etc.), ketones (including acetone, methyl ethyl acetone, etc.), nitriles (including acetonitrile, propionitrile, etc.). In a broad sense, any L described in the compound of formula (II) can be used as a suitable coordination S for the compound of formula (I).

[0051] Advantageously, it has been found that the phosphine coordinated to the compound of the general formula (I) or (II) must contain R as a tertiary alkyl group. 1 , R 2 or R 3 At least two of them. That is, the carbon bonded to the phosphorus should be a tertiary carbon bonded to three other carbon atoms and / or equivalent groups. Examples of such tertiary carbon groups include, but are not limited to, carbon atoms bonded to three other straight or branched alkyl groups, carbon atoms that are part of a cycloalkyl group and bonded to other straight or branched alkyl groups, or apex carbons of bicyclic or tricyclic hydrocarbons such as 1-adamantyl, 1-norbornyl, etc. By making such phosphine coordinately bonded to palladium, unprecedented catalyst activity is provided for compounds of general formula (I) or (II) exemplified in further detail below as vinyl addition polymerization catalysts.

[0052] In another aspect of the present invention, it has been found that compounds of formula (II) have a relative anion It is a weakly coordinating anion (WCA) that provides better catalyst (i.e., initiator) activity. That is, WCA is an anion that is weakly coordinated to the cationic complex. It is quite unstable so that it is replaced by a neutral Lewis base, a solvent, or a monomer. More specifically, the WCA anion acts as a stabilizing anion to the cationic complex and does not form a covalent bond with the metal atom M. The WCA anion is relatively inert in terms of non-oxidizing, non-reducing, and non-nucleophilic properties.

[0053] Typically, the WCA can be selected from borates, phosphates, arsenates, antimonates, aluminates, boratabenzene anions, carboranes, halocarborane anions, sulfonamidates, or sulfonates.

[0054] In broad terms, suitable borate anions may be represented by the general formula A, phosphate, arsenate and antimonate anions may be represented by the general formula B, and aluminate anions may be represented by the general formula C:

[0055] [M a (R a )(R b )(R c )(R d )]A

[0056] [M b (R a )(R b )(R c )(R d )(R e )(R f )]B

[0057] [M c (OR a )(OR b )(OR c )(OR d )]C

[0058] Among them, in the general formula A, M a is boron, in the general formula B, M b is phosphorus, arsenic or antimony. In the general formula C, M c For aluminum. a , R b , R c , R d , R e and R f independently represents fluorine, straight or branched C 1 -C 10 Alkyl, linear or branched C 1 -C 10 Alkoxy, linear or branched C3 -C 5 Halogenated alkenyl, straight chain or branched C 3 -C 12 Trialkylsilyl, C 18 -C 36 Triarylsilyloxy, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 6 -C 30 Aryloxy, where R a ~R f cannot represent both alkoxy and aryloxy. When substituted, aryl can be monosubstituted or polysubstituted, wherein the substituents are independently selected from linear or branched C 1 -C 5 Alkyl, linear or branched C 1 -C 5 Halogenated alkyl, linear or branched C 1 -C 5 Alkoxy, linear or branched C 1 -C 5 Halogenated alkoxy, linear or branched C 1 -C 12 Trialkylsilyl, C 6 -C 18 triarylsilyl, or a halogen selected from chlorine, bromine or fluorine.

[0059] Representative borate anions of Formula A include, but are not limited to, 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-trifluorovinyl)borate , tetrakis(4-triisopropylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsilyloxy)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.

[0060] Representative phosphates, arsenates, and antimonates of general formula B include, but are not limited to, hexafluorophosphate, hexaphenylphosphate, hexa(pentafluorophenyl)phosphate, hexa(3,5-bis(trifluoromethyl)phenyl)phosphate, hexafluoroarsenate, hexaphenylarsenate, hexa(pentafluorophenyl)arsenate, hexa(3,5-bis(trifluoromethyl)phenyl)arsenate, hexafluoroantimonate, hexaphenylantimonate, hexa(pentafluorophenyl)antimonate, hexa(3,5-bis(trifluoromethyl)phenyl)antimonate, and the like.

[0061] 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.

[0062] In an embodiment of the present invention, suitable Selected from and

[0064] In some embodiments, the compound of formula (II) has L selected from acetonitrile or propionitrile.

[0065] In some other embodiments, the compound of formula (II) has It 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.

[0066] In some other embodiments, the compound of formula (I) or (II) has R 1 , R 2 and R 3 At least two of the R are the same and are selected from the group consisting of tert-butyl, tert-amyl (2-methylbutan-2-yl or tert-amyl), 2-ethylbutyl, tert-hexyl (2-methylpentyl), tert-heptyl (2-methylhexyl), 2,3,3-trimethylbutan-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 R 1 , R 2 or R 3is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 3-methylbutyl (isopentyl) and 2,2-dimethylpropyl (neopentyl). It should be further noted that for R 1 , R 2 and R 3 The two alkyl groups defined in the above are all bonded to the phosphine via the tertiary substituted carbon numbered for each of the alkyl groups. That is, for example, 2-methylbutyl means that the second carbon atom of the butyl group is bonded to the phosphorus which is also substituted with a methyl group.

[0067] In some other embodiments, R 4 , R 5 and R 6 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.

[0068] Non-limiting representative examples of compounds of formula (I) can be listed below:

[0069]

[0070] n-Butyldi-1-adamantylphosphine palladium diacetate (H 2 O)(Pd601);

[0071]

[0072] n-Propyldi-1-adamantylphosphine palladium diacetate (H 2 O);

[0073]

[0074] n-Pentyldi-1-adamantylphosphine palladium diacetate (H 2 O);

[0075]

[0076] n-Butyldi-tert-butylphosphine palladium diacetate (H 2 O)(Pd445);

[0077]

[0078] n-propyldi-tert-butylphosphine palladium diacetate (H 2 O);

[0079]

[0080] n-Pentyldi-tert-butylphosphine palladium diacetate (H 2 O);

[0081]

[0082] n-Butyldi-1-norbornylphosphine diacetate palladium (H 2 O); and

[0083]

[0084] n-Butyldi-1-bicyclo[2,2,2]octylphosphine palladium diacetate (H 2 O).

[0085] Non-limiting representative examples of compounds of formula (II) can be listed below:

[0086]

[0087] Bis(n-butyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(pentafluorophenyl)borate;

[0088]

[0089] Bis(n-butyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; and

[0090]

[0091] Bis(n-propyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(pentafluorophenyl)borate.

[0092] The compounds of the present invention can be synthesized by any steps known to those skilled in the art. Specifically, the various starting materials used in the preparation of the compounds of the present invention are known materials or are commercially available. The compounds of the present invention and various precursor compounds can be prepared by methods for preparing similar compounds described in the literature or further described in this specification. It should be further emphasized that the compounds of general formula (I) or (II) can be easily synthesized using simple methods further illustrated in the following specific examples, even if they are industrial scale. Therefore, the present invention provides a cost-effective method for forming compounds of general formula (I) or (II), thereby providing additional advantages in the utility as a vinyl addition polymerization catalyst.

[0093] More specifically, the compounds disclosed in this specification can be synthesized according to the steps of the following schemes 1 and 2, wherein if not otherwise specified, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , L and Z have the same meanings as in Formulas I and II, respectively.

[0094] In Scheme I, a suitable phosphine (IC) is reacted with a suitable palladium compound (IB) in the presence of water to form a compound of formula (I). The reaction can be carried out by any steps 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 sub-ambient reaction conditions. Typically, such reactions can be carried out in an inert environment in the presence of water. The reaction temperature used is typically from sub-ambient temperature to ambient temperature in the range of -78°C to 25°C. Any solvent that can dissolve the palladium compound (IB) and the phosphine (IC) can be used. Examples of such solvents include toluene and other hydrocarbon solvents, and mixtures of any combination thereof.

[0095] Solution 1

[0096]

[0097] As shown in Scheme 1, the synthesis of the compound of formula (I) requires only a simple step. Quantitative conversion to the compound of formula (I) can usually achieve a yield of more than 90%. As can be seen from the following description, the compound of formula (I) is a very active catalyst in vinyl addition polymerization, and even if the amount of catalyst used is very low, the conversion rate of monomer to polymer is usually about 99% or more within a short reaction time of 30 minutes to 1 hour. Furthermore, as demonstrated in the following specific examples, the polymers thus formed show excellent optical, thermal and mechanical properties.

[0098] Scheme 2 illustrates the synthesis of compounds of general formula (II). As shown in Scheme 2, in step 1, a palladium compound (IIA) is reacted with a suitable phosphine (IIB) in a suitable solvent under suitable reaction conditions to obtain a compound of general formula (IIC). Typically, such reactions are carried out in a chlorinated solvent such as dichloromethane at a subambient to ambient temperature in the range of -78°C to 25°C. In step 2 of Scheme 2, a compound of general formula (IIC) is reacted with a suitable compound of general formula (III) to form a compound of general formula (II). For example, a compound of (IIC) can be reacted with a suitable salt of a weakly coordinating anion such as a lithium salt LiZ to form a compound of general formula (II). Typically, such reactions are carried out at room temperature in a suitable solvent that can coordinate to palladium. Examples of such coordinating solvents are examples described in this specification such as acetonitrile. It should be noted that both reaction steps are carried out in an inert environment such as nitrogen, helium or argon.

[0099] Solution 2

[0100]

[0101] Therefore, in another aspect of the present invention, there is provided a vinyl addition polymerization catalyst comprising a compound of general formula (I) according to the present invention. In another aspect of the present invention, there is also provided a vinyl addition polymerization catalyst comprising a compound of general formula (II) according to the present invention.

[0102] In another aspect of the present invention, there is provided a polymerizable composition comprising:

[0103] a) a palladium compound selected from the group consisting of compounds of the general formula (I) described in the present specification and compounds of the general formula (II) described in the present specification;

[0104] b) Compounds of the general formula (III):

[0105]

[0106] in,

[0107] is selected from lithium, sodium, potassium, cesium, barium, ammonium, straight-chain or branched tetra(C 1 -C 4 ) cations in alkylammonium and dialkylanilinium;

[0108] is a weakly coordinating anion, selected from or and

[0110] c) at least one monomer of the general formula (IV):

[0111]

[0112] in,

[0113] m is an integer of 0, 1 or 2;

[0114] R 7 , R 8 , R 9 and R 10 are the same or different and are each independently selected from hydrogen, a straight chain or a branched chain (C 1 -C 16 ) alkyl, hydroxyl (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 )Alkyl maleimide (C 3 -C 6 ) alkyl, di(C 1 -C 2 )Alkyl maleimide (C 2 -C 6 ) alkoxy (C 1 -C 2 ) alkyl, hydroxyl, (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, wherein the above substituents may be substituted by halogen or hydroxy.

[0115] It should be noted that any compound of the general formula (I) or (II) can be used in the polymerizable composition of the present invention. The polymerization reaction can be carried out purely (bulk polymerization) or in solution. That is, through the embodiments of the present invention, in the presence of a compound of the general formula (I) or (II) as a catalyst, a compound of the general formula (III) is combined to produce various polymers containing at least one functionalized norbornene monomer (i.e., a compound of the general formula (IV)). Generally, the combination of compounds of the general formula (I) or (II) is used together with a compound of the general formula (III), and is therefore referred to as a two-component catalyst. The compound of the general formula (I) or (II) is generally referred to as a main catalyst, and the compound of the general formula (III) is generally referred to as an activator.

[0116] As mentioned above, it has been found that the combination of the compound of general formula (I) or (II) and one or more compounds of general formula (III) is very active as a vinyl addition polymerization catalyst. Therefore, a small amount of catalyst can now be used to produce high-quality polymers. Therefore, in one embodiment, a monomer and a primary catalyst having a molar ratio of at least 10,000:1 can be used to effectively carry out vinyl addition polymerization, and the molar ratio is based on the total moles of the monomers and catalysts used. That is, 10,000 moles of monomers and 1 mole of catalyst are used. In other embodiments, the molar ratio of monomer: primary catalyst can be 1,000,000:1, 500,000:1, 100,000:1, 50,000:1, 20,000:1, 15,000:1, etc. In other embodiments, the molar ratio of monomer: primary catalyst: 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, the amount of activator used exceeds the molar amount of the procatalyst used, for example, the molar ratio of procatalyst:activator can be 1:1 to 1:6.

[0117] Therefore, by using the compound of general formula (I) or (II) in the polymerizable composition of the present invention, a polymer having a high conversion rate and a higher molecular weight can be formed, which exhibits more excellent properties than polymers formed by conventional palladium compounds. For example, refer to U.S. Patent Application Publication No. 2005 / 0187398A1.

[0118] As described above, bulk polymerization can be carried out using a catalyst and monomers in the absence of a solvent. Advantageously, such polymerizations can also form three-dimensional polymer products in a mold at a suitable temperature. Typically, the reaction temperature range can be between sub-ambient temperatures such as below 0°C and the boiling point of the monomer, however, it is recommended that the components of the reaction vessel or mold should not be heated to more than the flash point of one or more monomers. Typically, bulk polymerization is carried out in a temperature range of about 10°C to 200°C, and in other embodiments, the temperature range can be about 15°C to 150°C, or about 20°C to 100°C.

[0119] Since the polymerization reaction is exothermic, the temperature in the mold is usually higher than the feed temperature during the polymerization process unless a cooled mold is used. Therefore, the initial temperature of the mold can usually range from about -20°C to about 200°C, or from about 0°C to about 150°C, or from 20°C to 100°C. The temperature distribution in the mold is affected by the geometry of the mold, the properties of the mold as a heat sink or heat supply, the reactivity of the catalyst and the monomer, etc. To some extent, the appropriate temperature and heat exchange conditions must be selected based on experience with the mold, feed and catalyst in a specified system.

[0120] After the polymerization reaction is completed, the molded article can be subjected to a post-curing treatment at a temperature range of about 100°C to 250°C for about 15 minutes to 24 hours or 1 to 2 hours. Such post-curing treatment can enhance the polymer properties, including the glass transition temperature (T g ) and heat distortion temperature (HDT). In addition, post-curing is desirable but not necessary to allow the sample to reach a final dimensional stability state, minimize residual odor, and improve final physical properties.

[0121] As described in this specification, vinyl addition polymerization can also be carried out in solution using a compound of formula (I) or (II) in combination with a compound of formula (III). In this embodiment, a solution of the catalyst is suitably mixed with a preferred solution of one or more monomers (i.e., a compound of formula (IV)) under conditions known in the art to form the polymer of the present 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; and halocarbon solvents, such as 112; and any combination thereof.

[0122] Advantageously, it has been further found that compounds of general formula (I) or (II) can be prepared in situ. Then, by adding compounds of general formula (III), vinyl addition polymerization of more than one olefin monomer based on general formula (IV) can be carried out in the same reaction vessel. Therefore, the present invention provides unique advantages for industrial-scale manufacturing of polymers. Most advantageously, among the many advantages provided by embodiments of the present invention, the method does not require the preparation and storage of compounds of general formula (I) or (II).

[0123] The temperature range of solution polymerization can be from sub-ambient temperature (such as below 0°C) to the boiling point of the solvent used. However, it should be noted that such solution polymerization can also be carried out in a sealed pressure vessel at a temperature above the boiling point of the solvent. Typically, solution polymerization is carried out in a temperature range of about 10°C to 150°C, and in other embodiments, the temperature range can be about 30°C to 125°C, or about 50°C to 100°C. Furthermore, solution polymerization is carried out using an anhydrous solvent in an inert environment such as nitrogen, helium or argon.

[0124] The polymers formed according to the present invention generally exhibit a weight average molecular weight (M w ) is at least about 20,000. In another embodiment, the polymer of the present invention has an M w is at least about 25,000. In another embodiment, the polymer of the present invention has an M w is at least about 40,000. In another embodiment, the polymer of the present invention has an M w is at least about 60,000. In another embodiment, the polymer of the present invention has an M w is at least about 80,000. In other embodiments, the polymers of the present invention have an M w is at least about 100,000. 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 embodiments may be greater than 500,000. n ) can be defined, for example, by any known technique such as gel permeation chromatography (GPC) with a suitable detector and calibration standards, such as a differential refractive index detector calibrated with narrow distribution polystyrene standards or polybutadiene (PBD) standards. The polymers of the present invention generally exhibit a polydispersity index (PDI) greater than 3, which is a function of the weight average molecular weight (M). w ) and number average molecular weight (M n ). Typically, the PDI of the polymer of the present invention ranges from 3 to 5. In some embodiments, the PDI is higher than 3.5, higher than 4, higher than 4.5 or higher than 5. However, it should be noted that in some embodiments, the PDI may be less than 3, for example, 2,5.

[0125] Advantageously, the compositions comprising the vinyl addition polymers formed from the palladium compounds of formula (I) or (II) have very high conversions (e.g., 25,000-50,000 to 1) at very low catalyst levels, wherein the molecular weight of the polymer is controlled using a chain transfer agent such as triethylsilane (TES), which can, for example, result in a clear, transparent polymer solution that can then be extruded with the aid of a polymerization solvent to form a transparent film that can be stretched to form a film having unprecedented properties, such as an extremely low coefficient of thermal expansion (CTE) that can be as low as 200 ppm / °K, less than 150 ppm / °K, 100 ppm / °K, 50 ppm / °K, or less than 40 ppm / °K. Various other chain transfer agents can also be used to control the molecular weight of the polymers obtained as described herein, including, for example, bicyclo[4.2.0]oct-7-ene (BCO), formic acid, various other silanes, and the like, as well as mixtures including any combination thereof. The use of various CTAs in vinyl addition polymerization to control the properties of the resulting polymer is well known in the art. For example, see U.S. Pat. No. 7,910,674 B2, the relevant portions of which are incorporated herein by reference.

[0126] In some embodiments, the polymerizable composition according to the present invention includes a solvent. Suitable solvents that can be used in this embodiment can be selected from the group including methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentane, hexane, heptane, octane, decane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 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 of any combination thereof without any limitation.

[0127] Any compound of the general formula (I) listed in this specification can be used in the polymerizable composition of the present invention if selected. Similarly, any compound of the general formula (II) listed in this specification can be used in the polymerizable composition of the present invention if selected.

[0128] Non-limiting examples of activators, ie compounds of formula (III), that can be used in the polymerizable composition according to the present invention can be listed as follows:

[0129] Lithium tetrafluoroborate;

[0130] Lithium trifluoromethanesulfonate;

[0131] Lithium tetrakis(pentafluorophenyl)borate (LiFABA);

[0132] Lithium tetraphenylborate;

[0133] Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

[0134] Lithium tetrakis(2-fluorophenyl)borate;

[0135] Lithium tetrakis(3-fluorophenyl)borate;

[0136] Lithium tetrakis(4-fluorophenyl)borate;

[0137] Lithium tetrakis(3,5-difluorophenyl)borate;

[0138] Lithium hexafluorophosphate;

[0139] Lithium hexaphenylphosphate;

[0140] Lithium hexa(pentafluorophenyl)phosphate;

[0141] Lithium hexafluoroarsenate;

[0142] Lithium hexaphenylarsenate;

[0143] Lithium hexa(pentafluorophenyl)arsenate;

[0144] Lithium hexa(3,5-bis(trifluoromethyl)phenyl)arsenate;

[0145] Lithium hexafluoroantimonate;

[0146] Lithium hexaphenylantimonate;

[0147] Lithium hexa(pentafluorophenyl)antimonate;

[0148] Lithium hexa(3,5-bis(trifluoromethyl)phenyl)antimonate;

[0149] Lithium tetrakis(pentafluorophenyl)aluminate;

[0150] Lithium tris(nonafluorobiphenyl)fluoroaluminate;

[0151] Lithium (octyloxy)tris(pentafluorophenyl)aluminate;

[0152] Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate;

[0153] Lithium methyl tris(pentafluorophenyl)aluminate; and

[0154] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)-borate (DANFABA).

[0155] Any olefin monomer known in the art that can bring the expected benefits can be used in the polymerizable composition of the present invention. Non-limiting examples of monomers of formula (IV) that can be used in the polymerizable composition according to the present invention can be listed as follows:

[0156] Bicyclo[2.2.1]hept-2-ene (NB);

[0157] 5-ethylbicyclo-[2.2.1]hept-2-ene (EtNB);

[0158] 5-Butylbicyclo-[2.2.1]hept-2-ene (BuNB);

[0159] 5-Hexylbicyclo-[2.2.1]hept-2-ene (HexNB);

[0160] 5-octylbicyclo-[2.2.1]hept-2-ene (OctNB);

[0161] 5-Decylbicyclo-[2.2.1]hept-2-ene (DecNB);

[0162] 5-Perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);

[0163] 5-Phenethylbicyclo[2.2.1]hept-2-ene (PENB);

[0164] 5-Benzylbicyclo[2.2.1]hept-2-ene (BnNB);

[0165] 2-(Bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB);

[0166] 5-vinylbicyclo[2.2.1]hept-2-ene (VNB); and

[0167] 5-Ethylene norbornene or 2-ethylidenebicyclo[2.2.1]hept-2-ene (ENB).

[0168] It should be further noted that more than one monomer of formula (IV) can be used in the polymerizable composition of the present invention. Thus, the molar ratio of the first monomer of formula (IV) to the second monomer of formula (IV) can be 1:99 to 99:1. In some embodiments, the molar ratio of the first monomer of formula (IV): the second monomer of formula (IV) is in the range of 5:95 to 95:5; in other embodiments, the molar ratio 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 and 50:50, etc. All of these combinations are part of the present invention. It should be further noted that in the polymerizable composition of the present invention, various other olefin monomers can be used in any desired amount depending on the intended end use application.

[0169] It should be further noted that in the polymerizable composition of the present invention, two or more different monomers of formula (IV) can be used. Therefore, in some embodiments, three different monomers of formula (IV) are used in any molar ratio. In other embodiments, four different monomers of formula (IV) or five different monomers of formula (IV) can be used in any molar ratio.

[0170] In another aspect of the present invention, a polymer solution is provided, which is obtained by polymerizing at least one polycyclic olefin monomer in the presence of a palladium compound according to the present invention. As mentioned above, since the compound of general formula (I) or (II) is a highly active catalyst, it can form a polymer solution with extremely high concentration. That is, the solid polymer included in the polymer solution formed according to the present invention is higher than 20 weight %. In other embodiments, the solid polymer included in the polymer solution is higher than 30 weight %, higher than 40 weight % or even higher than 50 weight %. Because the catalyst usage is very low, therefore, the polymer purity formed in this way is usually high, and it can be directly used for expected applications. However, the polymer solution can also be purified by any known method in the art, i.e., remove any trace catalyst impurities.

[0171] In another aspect of the present invention, a polymer solution according to the present invention that can be extruded into a film is also provided. As mentioned above, the polymer solution formed according to the present invention contains a polymer content of up to 50% by weight. Therefore, it is now possible to use the polymer solution in an extruder to form a film. Any technique known in the art for forming a film using a thermoplastic film can be used in this specification. Such techniques include extrusion, calendering and casting methods, etc. without any limitation. However, it should be emphasized that such extrusion techniques generally include melt processing of polymers. The polymers formed according to the present invention show a high glass transition temperature above 300° C., and it is difficult to melt process the polymers at such high temperatures because, in fact, at such high processing temperatures, the polymers will also begin to decompose.

[0172] Advantageously, it has been found that, although being carried out at very low temperatures, the polymer solution formed according to the present invention can also be directly used in an extruder using a process similar to that used for melt extrusion polymers in the art. Therefore, according to an embodiment of the present invention, any extruder known in the art can be utilized to extrude the polymer solution into a film. In this method, the polymer solution is supplied to a suitable extruder and is melt-kneaded at a suitable temperature before passing through a suitable die to form a film of desired thickness and cooling the film. Due to the use of lower temperatures in such polymer solution extrusion methods, yellowing, curling, degradation (i.e., molecular weight reduction) and other defects of the polymer produced during film formation can be minimized or eliminated, thereby being more advantageous than the melt extrusion method.

[0173] Therefore, in yet another aspect of the present invention, there is provided a film formed from a polymer solution according to the present invention. The film so formed shows no yellowing, no decrease in molecular weight or curling. Most importantly, it has a high glass transition temperature (T g ) can be easily formed into a film at low cost, and the film still shows a high T above 200°C. g , and has an average film thickness greater than about 20 μm and less than about 500 μm.

[0174] More specifically, the production of a membrane according to the present invention comprises the following steps:

[0175] The polymer solution according to the present invention is extruded by an extruder while kneading the solution and heating it to a temperature lower than the softening temperature of the polymer, that is, lower than the glass transition temperature (T g ) temperature;

[0176] forming a film of desired thickness while extruding through a suitable film die connected to an extruder; and

[0177] The extruded film is dried at a suitable temperature to remove the solvent.

[0178] The temperature of drying the film to remove any residual solvent and / or other volatile impurities depends on the type of solvent used when extruding the film. Typically, such drying temperatures can range from about 50°C to 280°C in an inert environment or under vacuum. In some embodiments, the film is dried under vacuum at a temperature range of about 100°C to 250°C for about 30 minutes to 4 hours; under vacuum at 150°C to 220°C for about 1 hour to 3 hours; and under vacuum at 170°C to 200°C for about 1 hour to 2 hours.

[0179] As disclosed in this specification, in the case where the polymer has been isolated as a solid, any solvent disclosed in this specification for dissolving the polymer can also be used to dissolve the polymer to form a polymer solution. The polymer concentration in the solution can be in the range of more than 5% by weight or less than 30%. In some embodiments, the polymer content in the solution is about 10%, 15%, 18%, 20% or 25%. In some embodiments, the polymer content in the solution can be higher than 30% by weight, higher than 40% by weight, higher than 50% by weight.

[0180] The extruder used can be any extruder known in the art for such film extrusion processes. Typically, a single screw extruder or a twin screw extruder is used. The screw can be composed of a plurality of elements well known in the art including mixing elements, kneading elements, etc.

[0181] As is well known in the art of film extrusion, the film thickness is controlled by a suitable die connected to the extruder. The extruded film is wound on a roll and dried at a temperature in the range of 50°C to 250°C to remove any residual solvent in the film. The film so formed is substantially transparent to visible light. That is, most visible light will pass through the film. In some embodiments, such films formed from the polymerizable composition of the present invention exhibit a visible light transmittance of more than 90%. In other embodiments, such films formed from the polymerizable composition of the present invention exhibit a visible light transmittance of more than 95%.

[0182] Then, the optical properties of the film so formed are evaluated using any method known in the art. For example, the refractive index of the film in the visible spectrum can be measured by ellipsometry. The optical properties of the film can be determined by visual observation. The quantitative transparency % can be measured by visible spectrum. Generally, the film formed according to the present invention shows excellent optical transparency characteristics and can be adjusted to the desired transparency as described in this specification.

[0183] Finally, the film can be stretched uniaxially or biaxially to obtain improved thermal and mechanical properties. For example, it has been found that biaxial stretching reduces the coefficient of thermal expansion (CTE) of the film formed therefrom by 10%. Similar reductions in CTE are also observed in uniaxially stretched films. Typically, such biaxial and / or uniaxial stretching also increases tensile and flexural moduli.

[0184] In yet another aspect of the present invention, there is further provided an article comprising an optical layer, the optical layer comprising an optical polymer obtained by polymerizing at least one polycyclic cycloolefin monomer of formula (IV) in the presence of a palladium compound of formula (I) or (II).

[0185] In another aspect of the present invention, there is provided a film formed from a polymer solution obtained using a polymerizable composition, the polymerizable composition comprising:

[0186] a) a palladium compound selected from the group consisting of compounds of the general formula (I) described in the present specification and compounds of the general formula (II) described in the present specification;

[0187] b) compounds of the general formula (III) described in this specification; and

[0188] c) at least one monomer of the general formula (IV) described in the present specification.

[0189] Advantageously, it has been found that films formed by the extrusion process of the present invention exhibit excellent optical, thermal and mechanical properties. For example, films formed by the extrusion process of the present invention exhibit a glass transition temperature (T g) is at least 200°C, and the storage modulus is at least 1x10 at 100°C 4 Pascal.

[0190] In another aspect of this embodiment, the vinyl addition polymer formed from the palladium compound of formula (I) or (II) and the suitable olefin monomer of formula (IV) can be easily prepared into various solid forms such as films. In one aspect of the invention, the composition comprising the vinyl addition polymer of the invention in a suitable solvent can be used for solvent-assisted extrusion of films.

[0191] The present invention is further described by the following examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention.

[0192] Embodiment (general)

[0193] The following abbreviations used in this specification are used to describe some compounds, instruments and / or methods used in specific embodiments of the present invention:

[0194] Pd601: Diadamantyl (n-butyl) phosphine diacetate palladium (H 2 O);

[0195] Pd445:Pd(OAc) 2 (P(tert-butyl) 2 (n-butyl))(H 2 O);

[0196] Pd1602: [Pd(OAc)(MeCN)(PAd 2 -n-Bu) 2 ]B(C 6 F 5 ) 4 ;

[0197] Pd942:Pd(OAc) 2 (PAd 2 -n-Bu) 2 ;

[0198] Pd785:Pd(OAc) 2 (PCy 3 ) 2 ;

[0199] Pd613: N,N-bis((2,6-diisopropylphenyl)-imidazol-2-ylidene)Pd(OAc) 2

[0200] LiFABA: Lithium (diethyl ether) tetrakis(pentafluorophenyl)borate ([Li(OEt 2 ) 2.5 ][B(C6 F 5 ) 4 ]);

[0201] NB: norbornene;

[0202] HexNB: 5-hexylbicyclo-[2.2.1]hept-2-ene;

[0203] 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;

[0204] M n : number average molecular weight; PDI: polydispersity;

[0205] GC-MS: gas chromatography-mass spectrometry;

[0206] NMR: nuclear magnetic resonance spectroscopy; FT-IR: Fourier transform infrared spectroscopy.

[0207] Unless otherwise stated, all palladium compounds described in this specification were prepared using standard Schlenk or dry box techniques. Anhydrous toluene and pentane were purchased from Aldrich and used directly without further purification after N2 sparging. Palladium acetate (Pd(OAc) 2 ) was purchased from Johnson Matthey Co., Ltd. Di-tert-butyl (n-butyl) phosphine was purchased from Solvay Co., Ltd., and di-adamantyl (n-butyl) phosphine was purchased from Strem Co., Ltd.

[0208] Example 1

[0209] Diadamantyl-(n-butyl)phosphine palladium diacetate (H 2 O)(Pd601)

[0210] A solution of palladium acetate (0.7 g, 3.12 mmol) and deionized water (0.112 mL, 6.14 mmol) in anhydrous toluene (20 mL) was placed in a Schlenk flask and flushed with nitrogen. The mixture was stirred while cooling to -78°C (dry ice / IPA bath). 2In the environment, n-butyl-di-1-adamantylphosphine (1.12g, 3.12mmol) was dissolved in anhydrous toluene (8mL) and added dropwise to the stirred palladium acetate solution. The mixture was further stirred at -78°C for 15 minutes. Then, the mixture was warmed to ambient temperature and stirred all night. The yellow solution became a yellow suspension overnight. The yellow precipitate was collected by filtration. The obtained solid was washed with toluene (15mLx3) and pentane (15mLx3) to obtain a yellow solid, which was vacuum dried. The yield was 1.54g (82%).

[0211] 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 obtained using a dual Mo ImuS microfocus optical system (Mo Kα radiation, The crystals were placed in a cryoloop under nitrogen vapor at 171 K (Oxford Cryosystems) using Paratone oil. The detector was placed 5.00 cm from the crystal. The data were corrected for absorption using the SADABS program. The structure was calculated using the Bruker SHELXTL software package (version 6.1) and solved by direct methods until F 2 The final anisotropic full-matrix least squares refinement is converged. Figure 1 The crystal structure is shown. 1 H and 31 The compound was further characterized by P NMR. Figure 2 express 1 H NMR spectroscopy. 1 H NMR: (CDCl 3 ,500MHz): δ0.93(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 PNMR (CDCl 3 ,202MHz):δ52.46.

[0212] Example 2

[0213] Pd(OAc) 2 (P(tert-butyl) 2 (n-butyl))(H 2 O)(Pd445)

[0214] Palladium acetate (1 g, 4.4 mmol) was added to a Schlenk flask equipped with a stirring bar and then flushed with nitrogen. It was then dissolved in anhydrous toluene (20 mL) and deionized water (0.16 mL, 8.9 mmol) was added. The reaction mixture was cooled to -15°C (dry ice and 85 / 15 water / IPA). Di-tert-butyl (n-butyl) phosphine (0.9 g, 4.4 mmol) was dissolved in anhydrous toluene (8 mL). The phosphine solution was slowly added dropwise to the stirring palladium acetate solution over 10 minutes. The reaction mixture was further stirred at -15°C for 15 minutes, then warmed to room temperature and stirred overnight. The obtained suspension was filtered and the collected solid was washed with pentane (15 mLx3). The orange-yellow solid was vacuum dried to obtain 1.8 g (90%) of the target material (Pd445). By 1 H. 31 The title compound was further characterized by P NMR and FT-IR. Figure 3 express 1 H NMR spectroscopy. 1 H NMR: (CDCl 3 ,500MHz): δ0.93(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 (CDCl 3 ,202MHz): δ60.08. FT-IR(neat):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).

[0215] Example 3

[0216] [Pd(OAc)(MeCN)(PAd 2 -n-Bu) 2 ]B(C 6 F 5 ) 4 (Pd1602)

[0217] PAd in DCM (5 mL) 2 A solution of -n-Bu (0.48 g, 1.34 mmol) was added dropwise to palladium acetate (Pd(OAc)) in DCM (15 mL) at -78 °C with stirring. 2) (0.12 g, 0.53 mmol) of reddish brown suspension. After further stirring for 10 minutes, the reaction mixture was warmed to room temperature and further stirred for 2 hours. The suspension turned into an orange solution. The solvent was removed under vacuum to obtain a yellow oily residue. The residue was dissolved in pentane and stirred to deposit a yellow precipitate. The precipitate was collected by filtration and washed with pentane (5 mL x 3 times). The obtained yellow powder was vacuum dried. The yield was 0.37 g (73%).

[0218] A suspension (0.3 g, 0.32 mmol) of the yellow solid obtained above in acetonitrile (20 mL) was added dropwise while stirring a solution of LiFABA (0.28 g, 0.32 mmol) in acetonitrile (15 mL) at room temperature. The mixture was stirred at room temperature for 5 hours. The obtained yellow suspension was diluted with DCM (15 mL) and stirred for 1 hour. The suspension was filtered through a syringe filter (0.2 μm, PTFE) to remove the precipitated LiCl. The filtrate was concentrated in vacuo to obtain a golden syrup. The residue was washed with 1:5 diethyl ether:pentane (v:v, 5 mLx3 times) and pentane (5 mLx3 times). The residue was dried in a vacuum to obtain the title compound as a yellow solid. The yield was 0.35 g (68%).

[0219] Example 4

[0220] Homopolymer of HexNB using Pd601

[0221] HexNB (4.5 g, 25 mmol) and BCO (0.022 g, 0.187 mmol) were dissolved in toluene (17 mL). The mixture was flushed with nitrogen for 1 hour and then heated to 80°C. 2 Under the environment, a mixture of the palladium compound Pd601 (0.001 mmol) of Example 1 and LiFABA (0.026 g, 0.003 mmol) in anhydrous THF (0.77 mL) was added to the stirred solution. The reaction mixture was sampled at 30, 60, 120 and 240 minutes, and the molecular weight and conversion rate were evaluated by GPC and GC-MS, respectively. The results are shown in Table 1. The obtained polymer solution was transparent.

[0222] Table 1

[0223] Time (h) <![CDATA[M w ]]> <![CDATA[M n ]]> PDI Conversion rate (%) 0.5 169,634 63,827 2.7 94.3 1 170,153 51,877 3.3 97.5 2 149,952 36,427 4.1 98.7 4 128,857 25,917 5 99.3

[0224] Example 5

[0225] Homopolymer of HexNB using Pd1602

[0226] In Example 5, the procedure of Example 4 was substantially repeated except that the palladium compound Pd1602 of Example 3 was used. The reaction mixture was sampled at 60, 120 and 240 minutes, and the molecular weight and conversion rate were evaluated by GPC and GC-MS, respectively. The results are shown in Table 2. The obtained polymer solution was transparent.

[0227] Table 2

[0228] Time (h) <![CDATA[M w ]]> <![CDATA[M n ]]> PDI Conversion rate (%) 1 170,811 50,026 3.4 93.8 2 165,327 43,639 3.8 97.4 3 165,144 45,418 3.6 98.5

[0229] Example 6

[0230] NB / HexNB (80 / 20 molar ratio) copolymer using Pd601 and BCO as CTA

[0231] NB (1.9 g, 20 mmol), HexNB (0.9 g, 5 mmol), and BCO (0.022 g, 0.19 mmol) were dissolved in toluene (10 mL). 2 After rinsing for 1 hour, the temperature was raised to 80°C. 2 Under the environment, a mixture of Pd601 (0.001 mmol) and LiFABA (0.0261 g, 0.003 mmol) in anhydrous THF (0.8 mL) was added to the stirred solution. The reaction mixture was sampled at 30, 60 and 120 minutes, and the molecular weight and conversion rate were evaluated by GPC and GC-MS, respectively. The results are shown in Table 3. The polymer formed is a transparent solution. The results further confirm that the use of the palladium compound Pd601 prepared according to the present invention not only provides a high conversion rate, but also provides a polymer with a higher molecular weight and excellent optical properties.

[0232] Table 3

[0233] Time (h) <![CDATA[M w ]]> <![CDATA[M n ]]> PDI Conversion rate (%) 0.5 144,108 40,944 3.5 98.8 1 145,234 41,456 3.5 99.2 2 142,190 39,771 3.66 99.4

[0234] Example 7

[0235] Homopolymer of HexNB using Pd601 and TES as CTA

[0236] 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). 2 After rinsing for 1 hour, the temperature was raised to 80°C. 2Under the environment, a mixture of Pd601 (0.001mmol) and LiFABA (0.026g, 0.003mmol) in anhydrous THF (0.77mL) was added to the stirred solution. The reaction mixture was sampled at 30, 120 and 240 minutes, and the molecular weight and conversion rate were evaluated by GPC and GC-MS, respectively. The results are shown in Table 4. The polymer formed is a transparent solution. The results further confirmed that by using the palladium compound Pd601 prepared according to the present invention, not only a high conversion rate is provided, but also a polymer with a higher molecular weight and excellent optical properties is provided.

[0237] Table 4

[0238] Time (h) <![CDATA[M w ]]> <![CDATA[M n ]]> PDI Conversion rate (%) 0.5 221,265 94,368 2.4 95.4 2 155,612 33,360 4.7 98.3 4 184,761 30,592 6 98.8

[0239] Example 8

[0240] NB / HexNB (80 / 20 molar ratio) copolymer using Pd601 and TES as CTA

[0241] 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). 2 After rinsing for 1 hour, heat to 80°C. 2 Under the environment, a mixture of Pd601 (0.001 mmol) and LiFABA (0.026 g, 0.003 mmol) in anhydrous THF (0.8 mL) was added to the stirred solution. The reaction mixture was sampled at 30, 60, 120 and 240 minutes, and the molecular weight and conversion rate were evaluated by GPC and GC-MS, respectively. The results are shown in Table 5. The polymer formed was a transparent solution. The results once again confirmed that by using the palladium compound Pd601 prepared according to the present invention, not only a high conversion rate of 100% is provided, but also a polymer with a higher molecular weight and excellent optical properties is provided.

[0242] Table 5

[0243] Time (h) <![CDATA[M w ]]> <![CDATA[M n ]]> PDI Conversion rate (%) 0.5 104,446 27,110 3.853 98.8 1 103,798 23,384 4.439 99.9 2 103,373 24,298 4.254 99.9 4 102,161 21,577 4.735 100

[0244] Example 9

[0245] NB / HexNB (80 / 20 molar ratio) copolymer using Pd601

[0246] In a glove box filled with nitrogen, a catalyst solution was prepared by mixing Pd601 (0.0044 g, 0.007 mmol) and LiFABA (0.019 g, 0.022 mmol) in a septum bottle at a molar ratio of 1:3. Anhydrous THF (0.87 g) was transferred to the septum bottle without air and mixed. NB was dissolved in toluene in advance to form a 75 wt% NB solution in toluene. Monomer NB solution (13.7 g or 0.144 mol), HexNB (6.5 g or 0.036 mol) and BCO (0.167 g, 1.54 mol) as CTA were added to a stirred glass container. Toluene (80.2 g) was added to a stirred glass container to form a 20 wt% monomer solution. The glass container was flushed with nitrogen while stirring at room temperature. The contents were heated to 80°C. Once the temperature was reached, the catalyst and co-catalyst solutions were transferred to a stirred glass container without air. The mixture was stirred for a total of 2 hours. The M of the obtained polymer measured by GPC was w The conversion rate was 99.1% as determined by GC-MS using residual monomers.

[0247] Example 10

[0248] NB / HexNB (80 / 20 molar ratio) copolymer using Pd445

[0249] In a glove box filled with nitrogen, Pd445 (0.0032 g, 0.007 mmol) and LiFABA (0.019 g, 0.022 mmol) were mixed in a septum bottle at a molar ratio of 1:3 to prepare a catalyst solution. Anhydrous THF (0.87 g) was transferred to a septum bottle without air and mixed. NB was dissolved in toluene in advance to form a 75 wt% NB solution in toluene. Monomer NB solution (13.65 g, 0.144 mol), HexNB (6.46 g, 0.036 mol) and BCO (0.167 g or 0.00154 mol) as CTA were added to a stirring glass container. Toluene (80.2 g) was added to a stirring glass container to form a 20 wt% monomer solution. The glass container was flushed with nitrogen while stirring at room temperature. The contents were heated to 80°C. Once the temperature was reached, the catalyst and co-catalyst solutions were transferred to a stirring glass container without air. The mixture was stirred for a total of 2 hours. The M of the obtained polymer measured by GPC was w The conversion was 122,980 and the conversion was 99.5% as determined by GC-MS using residual monomers.

[0250] Embodiment 11

[0251] NB / HexNB (80 / 20 molar ratio) copolymer using Pd1602

[0252] In a glove box filled with nitrogen, Pd1602 (0.0116 g, 0.007 mmol) and LiFABA (0.019 g, 0.022 mmol) were mixed in a septum bottle at a molar ratio of 1:3 to prepare a catalyst solution. Anhydrous THF (0.87 g) was transferred to a septum bottle without air and mixed. NB was dissolved in toluene in advance to form a 75 wt% NB solution in toluene. Monomer NB solution (13.65 g, 0.144 mol), HexNB (6.46 g, 0.036 mol) and BCO (0.147 g or 1.36 mol) as CTA were added to a stirring glass container. Toluene (91.4 g) was added to a stirring glass container to form an 18 wt% monomer solution. The glass container was flushed with nitrogen while stirring at room temperature. The contents were heated to 80°C. Once the temperature was reached, the catalyst and co-catalyst solutions were transferred to a stirring glass container without air. The mixture was stirred for a total of 4 hours. The M of the obtained polymer measured by GPC was w The conversion was 155,782 and the conversion was 99.6% as determined by GC-MS using residual monomers.

[0253] Example 12

[0254] NB / HexNB (90 / 10 molar ratio) copolymer using Pd601

[0255] In Example 12, the procedure of Example 4 was essentially repeated except that a mixture of NB and HexNB was used in a molar ratio of 90 / 10. The M of the polymer obtained was determined by HPLC (cyclohexane / decalin mixture as solvent and polybutadiene standard). w The mass fraction was 69,920 and the PDI was 2.8, with a conversion of 99% as determined by GC-MS using residual monomer.

[0256] Examples 13 and 14

[0257] NB / HexNB (95 / 5 molar ratio) copolymer

[0258] In Example 13, the steps of Example 7 were substantially repeated except that a mixture of NB and HexNB was used in a molar ratio of 95 / 5. In Example 14, the palladium compound Pd1602 of Example 3 was used instead of Pd601 of Example 1 to form a copolymer of NB / HexNB in ​​a molar ratio of 95 / 5. wThe PDI and conversion are shown in Table 6. M was determined by HPLC using a cyclohexane / decalin mixture as solvent and polybutadiene standards. w and PDI, and the conversion was determined by GC-MS and using residual monomers.

[0259] Table 6

[0260] Example No. <![CDATA[M w ]]> PDI Conversion rate (%) Embodiment 13 88,645 4.1 99.5 Embodiment 14 86,493 3 99.7

[0261] Embodiment 15

[0262] Films were made from a copolymer of NB / HexNB (90 / 10 molar ratio) using Pd601

[0263] The copolymer previously precipitated in Example 12 was dissolved in toluene to form a 20 wt% polymer solution. A wet film of 50 mm thickness was produced using a rod coater. The solvent was evaporated using a two-step drying process. The wet film was first heated to 80°C for 5 minutes and then heated to 110°C for 10 minutes. After drying, the tensile modulus, elongation at break (ETB) and CTE were measured, with a tensile modulus of 2192 MPa, an ETB of -4.6% and a CTE of 80 ppm.

[0264] Example 16

[0265] Film formation from NB / HexNB copolymer

[0266] Each polymer obtained from Examples 9, 11, 13 and 14 was dissolved in toluene to form a solution having about 18% by weight of the polymer. Each of these polymer solutions was then formed into a film using a solvent casting process. The film thus formed was vacuum dried at 250° C. for 3 hours. Thermomechanical properties were measured and are shown in Table 7. Glass transition temperature (T g ) was measured using a DMA Q800 (TA Instruments Inc., TX, USA) under the following conditions: multi-frequency strain temperature ramp mode, rate of 5°C / min in the range of 30-320°C, frequency of 1 Hz, strain of 0.1%, preload of 0.001N, nitrogen atmosphere. The length and width of the sample 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 as follows: using an Olympus OLS4000 laser microscope equipped with a Linkam Hotstage, the temperature was gradually increased from 50°C to 150°C in 5°C increments at a temperature gradient of 10°C / min. Strain ε xx and ε yyCalculations were performed using the digital image correlation method (DICM). The dielectric constant (Dk) and dielectric loss (Df) were determined using a copolymer (NB / HexNB) film cut into approximately 3.5 mm in width and 80 mm in length by a cutter. The cut film was vacuum dried at 100°C for 3 hours. The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the film were measured at 10 GHz using a resonant cavity microwave dielectric constant meter (ADMS010c, JIS C2565). Using a Shimadzu AG-500kNIS with a chuck spacing of 30 mm and a tensile rate of 1 mm / min, the stress-strain curve generated using a film stack of 30 mm in width × 60 mm in length × 0.1 mm in thickness was used to calculate the elongation at break (ETB). The tensile test was performed using an Instron in accordance with the guidelines specified in ASTM D638. From the data shown in Table 7, it can be seen that the two palladium compounds of the present invention, specifically the compounds of Example 1 and Example 3, have the same degree of activity in forming films that exhibit excellent properties. It should be further noted that any palladium catalyst known in the art cannot achieve the observed thermomechanical properties shown in Table 7.

[0267] Table 7

[0268]

[0269] Comparative Example 1

[0270] Pd(OAc) 2 (PAd 2 -n-Bu) 2 (Pd942)

[0271] Palladium acetate (0.1 g, 0.445 mmol) was placed in a Schlenk flask and flushed with nitrogen. It was then dissolved in anhydrous toluene (3 mL) and the mixture was cooled to -78 °C (dry ice / IPA bath). 2 Under the condition of -78°C and N 2 Under the environment, the phosphine solution was added dropwise to the stirring palladium acetate solution. The mixture was further stirred at -78 ° C for 15 minutes. Then, the mixture was warmed to ambient temperature and stirred all night. The yellow solution was converted into a yellow suspension. The suspension was diluted with anhydrous pentane (5mL), and the precipitate was collected by filtration. The obtained solid was washed with pentane (5mLx3), and the obtained yellow solid was vacuum dried. The yield was 0.25g (60%). 1 H NMR (CDCl 3,500MHz): 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 (CDCl 3 ,202MHz):d 26.8.

[0272] Comparative Example 2

[0273] Pd(OAc) 2 (PCy 3 ) 2 (Pd785)

[0274] In Comparative Example 2, the title compound was obtained by substantially following the procedure set forth in Comparative Example 1, except that tricyclohexylphosphine was used in place of n-butyldi-1-adamantylphosphine.

[0275] The following Comparative Examples 3 and 4 show that palladium compounds known in the art, namely Comparative Examples 1 and 2, do not provide high-quality polymers as described in Examples 4 and 5. That is, the palladium compounds according to the present invention provide polymers with excellent properties. Specifically, as shown in Table 8, Comparative Example 3 shows that the polymer prepared using Pd942 of Comparative Example 1 has a lower conversion rate and different polydispersities. The polymer prepared using Pd785 of Comparative Example 2 still provides an opaque polymer solution even after 30 minutes, and its molecular weight is low as shown in Table 9.

[0276] Comparative Example 3

[0277] Homopolymer of HexNB using Pd942

[0278] In Comparative Example 3, the procedure of Example 4 was substantially repeated except that the palladium compound Pd942 of Comparative Example 1 was used. The reaction mixture was sampled at 30, 60, 120 and 240 minutes, and the molecular weight and conversion rate were evaluated by GPC and GC-MS, respectively. The results are shown in Table 8. Although the obtained polymer solution was transparent, as shown in Table 8, the conversion rate was generally low after 4 hours.

[0279] Table 8

[0280] Time (h) <![CDATA[M w ]]> <![CDATA[M n ]]> PDI Conversion rate (%) 0.5 166,704 63,259 2.6 84.5 1 128,584 40,632 3.2 92.5 2 117,959 23,912 4.9 96.8 4 135,640 24,295 5.6 98.4

[0281] Comparative Example 4

[0282] Homopolymer of HexNB using Pd785

[0283] In Comparative Example 4, the procedure of Example 4 was substantially repeated except that the palladium compound Pd785 of Comparative Example 2 was used. The reaction mixture was sampled at 60, 120 and 240 minutes, and the molecular weight and conversion were evaluated by GPC and GC-MS, respectively. The results are shown in Table 9. As shown in Table 9, after 30 minutes of polymerization, although the conversion seemed to be about 99.8% or more, the obtained polymer solution was still opaque.

[0284] Table 9

[0285] Time (h) <![CDATA[M w ]]> <![CDATA[M n ]]> PDI Conversion rate (%) 1 144,514 39,607 3.7 99.8 2 nm nm nm 99.8 4 145,206 40,162 3.6 99.9

[0286] nm: Not determined

[0287] Comparative Example 5

[0288] Homopolymer of NB using Pd942 and TES / EtOH as CTA

[0289] In Comparative Example 5, the steps of Example 7 were substantially repeated except that the palladium compound Pd942 of Comparative Example 1 was used. The reaction mixture was sampled at 30, 60, 120 and 240 minutes, and the molecular weight and conversion were evaluated by GPC and GC-MS, respectively. After 4 hours, the reaction mixture remained liquid, and the viscosity of the reaction mixture did not change much. The conversion rate at 2 hours was determined to be only about 30%; the M of the obtained polymer determined by GPC was w 293,186, M n It is 142,545 and the PDI is 2.1.

[0290] Comparative Example 6

[0291] A copolymer of NB / HexNB (80 / 20 molar ratio) using Pd942 and TES / EtOH as CTA

[0292] In Comparative Example 6, the steps of Example 8 were substantially repeated except that the palladium compound Pd942 of Comparative Example 1 was used. The reaction mixture was sampled at 30, 60, 120 and 240 minutes, and the molecular weight and conversion were evaluated by GPC and GC-MS, respectively. After 4 hours, the reaction mixture remained liquid and the viscosity of the reaction mixture did not change much, indicating that Pd942 was ineffective as a vinyl addition polymerization catalyst under these conditions. Even after 4 hours, monomer polymerization did not proceed.

[0293] Comparative Example 7

[0294] NB / HexNB (80 / 20 molar ratio) copolymer using Pd613

[0295] In a glove box filled with nitrogen, Pd613 (0.0044 g, 0.007 mmol) and LiFABA (0.019 g, 0.022 mmol) were mixed in a diaphragm bottle at a molar ratio of 1:3 to prepare a catalyst solution. Anhydrous THF (0.87 g) was transferred to a diaphragm bottle without air and mixed. NB was dissolved in toluene in advance to form a 75 wt% NB solution in toluene. Monomer NB solution (13.65 g, 0.145 mol), HexNB (6.46 g, 0.036 mol) and BCO (0.167 g, 1.54 mmol) as CTA were added to a stirring glass container. Toluene (80.2 g) was added to a stirring glass container to form a 20 wt% monomer solution. The glass container was flushed with nitrogen while stirring at room temperature. The contents were heated to 80°C. Once the temperature was reached, the catalyst and co-catalyst solutions were transferred to a stirring glass container without air. The mixture was stirred for a total of 2 hours. The M of the obtained polymer measured by GPC was w The conversion was 70,647 and the conversion was 74% as determined by GC-MS using residual monomers.

[0296] This comparative example 7 clearly demonstrates that the use of palladium catalysts commonly used in the literature, such as N-heterocyclic carbene (NHC)-bonded palladium compounds, is not very effective in the vinyl addition polymerization of olefins of the general formula (IV) described in this specification. For example, under the same reaction conditions as those used in Examples 4 to 14 according to an embodiment of the present invention, the NHC-coordinated palladium catalyst Pd613 used in comparative example 7 not only resulted in a low conversion rate of only 74%, but also resulted in a polymer molecular weight as low as 70,647.

[0297]

[0298] Pd613: N,N-Bis(2,6-diisopropylphenyl)-imidazol-2-ylidenePd(OAc) 2

[0299] Although the present invention has been described by way of some embodiments, it should not be construed as being limited thereby, but rather as encompassing the general scope set forth above. Various modifications may be made without departing from the spirit and scope of the present invention.

Claims

1. A palladium compound selected from the group consisting of: Compounds of general formula (I): and Compounds of general formula (II): in, L is selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C6H5CN), 2,4,6-trimethylbenzonitrile, phenylacetonitrile (C6H5CH2CN), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2,6-di-tert-butylpyridine, 2,4-di-tert-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; Selected from including 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-trifluorovinyl)borate, tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate borate, tetrakis(3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, and Group; At least two of R1, R2 and R3 are the same and are selected from the group consisting of tertiary (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 group; the remaining R1, R2 or R3 is methyl, ethyl, straight or branched (C3-C 12 ) alkyl, (C6-C 10 )aryl and (C6-C 10 )aryl(C1-C3)alkyl; and R4, R5 and R6 are the same or different and are independently selected from the group consisting of methyl, ethyl and straight or branched (C3-C 20 ) alkyl, trifluoromethyl, pentafluoroethyl and straight or branched (C3-C 20 ) a perfluoroalkyl group.

2. The compound according to claim 1, wherein L is acetonitrile or propionitrile; 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; At least two of R1, R2 and R3 are the same and are 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 R1, R2 or R3 are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 3-methylbutyl (isopentyl) and 2,2-dimethylpropyl (neopentyl); 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.

3. The compound according to claim 1, wherein The compound of general formula (I) is selected from the group consisting of: n-Butyldi-1-adamantylphosphine palladium diacetate (H2O) (Pd601); n-Propyldi-1-adamantylphosphine palladium diacetate (H2O); n-Pentyldi-1-adamantylphosphine palladium diacetate (H2O); n-Butyldi-tert-butylphosphinediacetatepalladium(H2O) (Pd445); n-Propyldi-tert-butylphosphine palladium diacetate (H2O); n-Pentyldi-tert-butylphosphine palladium diacetate (H2O); n-Butyldi-1-norbornylphosphine palladium diacetate (H2O); and n-Butyldi-1-bicyclo[2,2,2]octylphosphine palladium diacetate (H2O).

4. The compound according to claim 1, wherein The compound of general formula (II) is selected from the group consisting of: Bis(n-butyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(pentafluorophenyl)borate; Bis(n-butyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; and Bis(n-propyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(pentafluorophenyl)borate.

5. A vinyl addition polymerization catalyst comprising the compound of general formula (I) according to claim 1. 6 . A vinyl addition polymerization catalyst comprising the compound of general formula (II) according to claim 1 .

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

8. The polymer solution according to claim 7, which is extruded into a film.

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

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

11. A polymerizable composition comprising: a) a palladium compound selected from the group consisting of: Compounds of general formula (I): and Compounds of general formula (II): in, L is selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C6H5CN), 2,4,6-trimethylbenzonitrile, phenylacetonitrile (C6H5CH2CN), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2,6-di-tert-butylpyridine, 2,4-di-tert-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; Selected from including 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-trifluorovinyl)borate, tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate borate, tetrakis(3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, and Group; At least two of R1, R2 and R3 are the same and are selected from the group consisting of tertiary (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 group; the remaining R1, R2 or R3 is methyl, ethyl, straight or branched (C3-C 12 ) alkyl, (C6-C 10 )aryl and (C6-C 10 )aryl(C1-C3)alkyl; and R4, R5 and R6 are the same or different and are independently selected from the group consisting of methyl, ethyl and straight or branched (C3-C 20 ) alkyl, trifluoromethyl, pentafluoroethyl and straight or branched (C3-C 20 ) a perfluoroalkyl group; b) Compounds of the general formula (III): (III); in, is a cation selected from lithium, sodium, potassium, cesium, barium, ammonium and linear or branched tetra(C1-C4)alkylammonium; is a weakly coordinating anion selected from the group consisting of or groups; and c) at least one monomer of the general formula (IV): in, m is an integer of 0, 1 or 2; R7, R8, R9 and R 10 are the same or different and are each independently selected from hydrogen, a straight chain or a branched chain (C1-C 16 ) alkyl, hydroxyl (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) alkyl maleimide (C3-C6) alkyl, di (C1-C2) alkyl maleimide (C2-C6) alkoxy (C1-C2) alkyl, hydroxyl, (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, wherein the above substituents may be substituted by halogen or hydroxy. 12 . The polymerizable composition according to claim 11 , further comprising a solvent.

13. The polymerizable composition according to 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, ethyl chloride, 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 of any combination thereof.

14. The polymerizable composition according to claim 11, wherein The compound of general formula (I) is selected from the group consisting of: n-Butyldi-1-adamantylphosphine palladium diacetate (H2O) (Pd601); n-Propyldi-1-adamantylphosphine palladium diacetate (H2O); n-Pentyldi-1-adamantylphosphine palladium diacetate (H2O); n-Butyldi-tert-butylphosphinediacetatepalladium(H2O) (Pd445); n-Propyldi-tert-butylphosphine palladium diacetate (H2O); n-Pentyldi-tert-butylphosphine palladium diacetate (H2O); n-Butyldi-1-norbornylphosphine palladium diacetate (H2O); and n-Butyldi-1-bicyclo[2,2,2]octylphosphine palladium diacetate (H2O).

15. The polymerizable composition according to claim 11, wherein The compound of general formula (II) is selected from the group consisting of: Bis(n-butyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(pentafluorophenyl)borate; Bis(n-butyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; and Bis(n-propyldi-1-adamantylphosphine)acetatepalladium(acetonitrile)tetrakis(pentafluorophenyl)borate.

16. The polymerizable composition according to claim 11, wherein The compound of formula (III) is selected from the group consisting of: Lithium tetrafluoroborate; Lithium trifluoromethanesulfonate; 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 hexaphenylphosphate; Lithium hexa(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexa(pentafluorophenyl)arsenate; Lithium hexa(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexa(pentafluorophenyl)antimonate; Lithium hexa(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 methyl tris(pentafluorophenyl)aluminate; and N,N-Dimethylanilinium tetrakis(pentafluorophenyl)-borate (DANFABA).

17. The polymerizable composition according to claim 11, wherein The monomer of general formula (IV) is selected from the group consisting of: 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 (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-Ethylene norbornene or 2-ethylidenebicyclo[2.2.1]hept-2-ene (ENB).

18. A film formed from a polymer solution obtained using a polymerizable composition, the polymerizable composition comprising: a) a palladium compound selected from the group consisting of: Compounds of general formula (I): and Compounds of general formula (II): in, L is selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C6H5CN), 2,4,6-trimethylbenzonitrile, phenylacetonitrile (C6H5CH2CN), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2,6-di-tert-butylpyridine, 2,4-di-tert-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; Selected from including 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-trifluorovinyl)borate, tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate borate, tetrakis(3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate, and Group; At least two of R1, R2 and R3 are the same and are selected from the group consisting of tertiary (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 group; the remaining R1, R2 or R3 is methyl, ethyl, straight or branched (C3-C 12 ) alkyl, (C6-C 10 )aryl and (C6-C 10 )aryl(C1-C3)alkyl; and R4, R5 and R6 are the same or different and are independently selected from the group consisting of methyl, ethyl and straight or branched (C3-C 20 ) alkyl, trifluoromethyl, pentafluoroethyl and straight or branched (C3-C 20 ) a perfluoroalkyl group; b) Compounds of the general formula (III): (III); in, is a cation selected from lithium, sodium, potassium, cesium, barium, ammonium and linear or branched tetra(C1-C4)alkylammonium; is a weakly coordinating anion, selected from or and c) at least one monomer of the general formula (IV): in, m is an integer of 0, 1 or 2; R7, R8, R9 and R 10 are the same or different and are each independently selected from hydrogen, a straight chain or a branched chain (C1-C 16 ) alkyl, hydroxyl (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) alkyl maleimide (C3-C6) alkyl, di (C1-C2) alkyl maleimide (C2-C6) alkoxy (C1-C2) alkyl, hydroxyl, (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, wherein the above substituents may be substituted by halogen or hydroxy.

19. The membrane according to claim 18, obtained by extrusion of a polymer solution.

20. The film of claim 18, which exhibits a glass transition temperature (T g ) is at least 200°C, and the storage modulus is at least 1x10 at 100°C 4 Pascal.

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