Composition comprising isomer mixture of itaconimide norbornene and citraconimide norbornene

Abstract

Compositions are provided that include a mixture of isomers of itaconamide norbornene and citraconamide norbornene. These compositions and optionally at least one additional norbornene monomer may be used to form copolymers. In addition, membranes can be prepared that include the cross-linking reaction product of any of these copolymers. These compositions, copolymers, and films may have useful dielectric properties.

Description

BACKGROUND OF THE INVENTION

[0001] The current state of the low dielectric material field is represented by fluoropolymers such as poly(tetrafluoroethylene) (PTFE) and poly(hexafluoropropylene-tetrafluoroethylene) (fluorinated ethylene / propylene or FEP). These materials provide a dielectric constant (Dk) of <2.0 and a dissipation factor (Df) of <0.001 in some cases, but are costly and have processing difficulties such as extremely high processing temperatures (above 250 °C for FEP and above 350 °C for PTFE) and high melt viscosities. Hydrocarbon polymers can provide low Dk / Df performance, but materials such as polyethylene, polypropylene, and styrenics suffer from low use temperatures. SUMMARY OF THE INVENTION

[0002] In a first aspect, a composition is provided. The composition comprises a mixture of isomers, the mixture of isomers comprising:

[0003] at least 10 wt% of isomer A having the formula:

[0004] and

[0005] at most 90 wt% of isomer B having the formula:

[0006]

[0007] In a second aspect, a copolymer is provided. The copolymer is the reaction product of a polymerizable composition comprising:

[0008]

[0009] and

[0010]

[0011] wherein each of R 1 、R 2 、R 3 and R 4 is independently selected from H, straight or branched C1 to C20 hydrocarbon groups; straight or branched C1 to C20 hetero-hydrocarbon groups, C1 to C20 carbosilanes, and C5 to C20 heterocycles, or R 1 and R 2 together or R 3 and R 4 together form a C1 to C20 alkylene group; n is an integer from 0 to 5; and wherein each Y is independently selected from -CH 2 -, -CH 2 CH 2 -, and O.

[0012] In a third aspect, another copolymer is provided. The copolymer comprises the following divalent monomer units:

[0013] as well as

[0014]

[0015] wherein each Y is independently selected from -CH 2 -、-CH 2 CH 2 - and O.

[0016] In a fourth aspect, another copolymer is provided. The copolymer comprises the following divalent monomer units:

[0017]

[0018] as well as

[0019]

[0020] Where R 1 , R 2 , R 3 and R 4 Each of R is independently selected from H, a linear or branched C1 to C20 hydrocarbon group, a linear or branched C1 to C20 heterohydrocarbon group, a C1 to C20 carbosilane and a C5 to C20 heterocycle, or 1 and R 2 Together or R 3 and R 4 together to form a C1 to C20 alkylene group; n is an integer from 0 to 5; and wherein each Y is independently selected from -CH 2 -、-CH 2 CH 2 - and O.

[0021] In a fifth aspect, a composition is provided, comprising a solvent and the copolymer of any one of the second to fourth aspects.

[0022] In a sixth aspect, a film is provided, comprising a cross-linked reaction product of the copolymer of any one of the second to fourth aspects.

[0023] The polymerizable compositions containing isomer A and isomer B are suitable for applications requiring polymers exhibiting low dielectric constants (Dk) and dissipation factors (Df). For example, structures incorporating copolymers prepared using isomer A and isomer B provide a means of improving thermal performance without the use of aromatic groups that tend to be detrimental to the dielectric properties of the resulting polymer.

[0024] The foregoing summary of the disclosure is not intended to describe every disclosed embodiment or every implementation of the disclosure. The following description more particularly exemplifies illustrative embodiments. Throughout this application, guidance is provided through lists of examples, which may be used in various combinations. In each case, the cited lists are only to be used as representative groups and should not be construed as exclusive lists. Detailed Description

[0025] Glossary

[0026] The term "aliphatic" refers to a C1-C40 (suitably C1-C30) straight-chain or branched alkenyl, alkyl, or alkynyl group, which may or may not be interrupted or substituted by one or more heteroatoms such as O, N, or S. The term "alicyclic" refers to a cyclized aliphatic C3-C30 (suitably C3-C20) group and includes those interrupted by one or more heteroatoms such as O, N, or S. Additionally, the term "heterocyclic" refers to a cyclized aliphatic C5-C20 (suitably C5-C10) or C5 containing one or more heteroatoms such as O, N, or S.

[0027] The term "alkyl" refers to a monovalent group that is a radical of an alkane and includes straight-chain, branched, cyclic, and bicyclic alkyl groups and combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise specified, alkyl groups generally contain 1 to 30 carbon atoms. In some embodiments, the alkyl group contains 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 7 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples of "alkyl" groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, tert-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like.

[0028] The term "alkoxy" refers to a monovalent group of the formula -OR a wherein R a is an alkyl as defined above.

[0029] Each of "alkenyl" and "ene" refers to a monovalent straight-chain or branched unsaturated aliphatic group having one or more carbon-carbon double bonds, such as vinyl.

[0030] The term "chain atom" refers to an atom that is in the chain (as opposed to an atom of a chain substituent). The term "chain heteroatom" refers to a heteroatom that replaces one or more carbon atoms in a carbon chain. Heteroatoms are typically oxygen, sulfur, or nitrogen.

[0031] The term "hydrocarbyl" refers to a monovalent group of a hydrocarbon. The hydrocarbyl group can be saturated, partially unsaturated or unsaturated, and can have up to 20 carbon atoms, up to 10 carbon atoms, up to 6 carbon atoms or up to 4 carbon atoms. The hydrocarbyl group usually has at least 1 carbon atom or at least 2 carbon atoms. The hydrocarbyl group is usually an alkyl group, an aryl group, an aralkyl group or an alkaryl group. The term "heterohydrocarbyl" refers to a hydrocarbyl group in which at least one but not all of the carbon atoms in the chain are replaced by a heteroatom selected from O, N or S.

[0032] The term "hydrocarbylene" is a divalent analogue of "hydrocarbyl" in which two hydrogen atoms have been removed from the same carbon atom (e.g., such that the group is bonded by a double bond). The hydrocarbylene group can be saturated, partially unsaturated or unsaturated, and can have up to 20 carbon atoms, up to 10 carbon atoms, up to 7 atoms, up to 6 carbon atoms or up to 4 carbon atoms. The hydrocarbylene group usually has at least 1 carbon atom or at least 2 carbon atoms. The hydrocarbylene group is usually a methylene group (=CHR).

[0033] The term "carbosilane" refers to a compound consisting only of Si, C and H and having no Si-Si bonds, suitably C1-C20, C1-C10 or C1-6.

[0034] As used herein, the term "cyclic monomer" refers to a monomer having at least one cyclic group, and can include bicyclic and tricyclic.

[0035] The term "aromatic" refers to an aromatic group of C3-C40, suitably C3-C30, including an aromatic group of a carbocyclic ring, and a heterocyclic aromatic group containing one or more of the heteroatoms O, N or S and a fused ring system containing one or more of these aromatic groups fused together. The term "aryl" refers to a monovalent group that is aromatic and optionally a carbocyclic ring. The aryl group has at least one aromatic ring. Any additional ring can be unsaturated, partially saturated, saturated or aromatic. Optionally, the aromatic ring can have one or more additional carbocyclic rings fused to the aromatic ring. Unless otherwise specified, the aryl group usually contains 6 to 30 carbon atoms. In some embodiments, the aryl group contains 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms or 6 to 10 carbon atoms. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthryl and anthracenyl.

[0036] The term "aralkyl" refers to an alkyl group substituted with at least one aryl group. That is, the aralkyl group has the formula —R d —Ar, where R d is an alkylene group, and Ar is an aryl group. The aralkyl group contains 6 to 40 carbon atoms. The aralkyl group often contains an alkylene group having 1 to 20 carbon atoms or 1 to 10 carbon atoms, and an aryl group having 5 to 20 carbon atoms or 6 to 10 carbon atoms.

[0037] As used herein, "C1", "1C", and "one carbon" are interchangeable ways of describing a single carbon atom and are used interchangeably when indicating any number of carbon atoms.

[0038] As used herein, the term "actinic radiation" means electromagnetic radiation of a wavelength that can be absorbed by a composition exposed to it and that thereby causes at least one chemical reaction or transformation to occur.

[0039] The terms "preferred" and "preferably" refer to embodiments of the present disclosure that may provide certain benefits in certain circumstances. However, in the same or other circumstances, other embodiments may also be preferred. Moreover, the recitation of one or more preferred embodiments does not imply that other embodiments are not available and is not intended to exclude other embodiments from the scope of the present disclosure.

[0040] In this application, terms such as "a", "an", and "the" are not intended to refer only to a single entity but include general categories for which specific examples may be used for illustration. The terms "a", "an", and "the" may be used interchangeably with the term "at least one". The phrases "at least one of... " and "comprising at least one of... " followed by a list refer to any one of the items in the list and any combination of two or more items in the list.

[0041] As used herein, the term "or" is generally used in its ordinary sense, including "and / or", unless the context clearly indicates otherwise. The term "and / or" means one or all of the listed elements, or any combination of two or more of the listed elements.

[0042] Likewise, all numerical values herein are assumed to be modified by the term "about" and preferably by the term "exactly". As used herein, with respect to measured quantities, the term "about" refers to a deviation in the measured quantity that is commensurate with the precision of the measurement objective and the measuring equipment used, of the kind that a person of ordinary skill in the art making the measurement with due care would expect. Also herein, a numerical range expressed by endpoints includes all numbers and end values within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0043] As used herein, as a modifier of a property or attribute, unless specifically defined otherwise, the term "substantially" means that the property or attribute will be readily recognizable by one of ordinary skill in the art without absolute precision or perfect match (e.g., within + / - 20% for a quantifiable property). Unless specifically defined otherwise, the term "essentially" means a high degree of approximation (e.g., within + / - 10% for a quantifiable property), but also does not require absolute precision or perfect match. Terms such as same, equal, uniform, constant, exact, etc. should be understood to be within ordinary tolerances, or within the measurement error applicable to a particular case, rather than requiring absolute precision or perfect match.

[0044] In a first aspect, a composition is provided. The composition comprises a mixture of isomers, the mixture of isomers comprising:

[0045] at least 10% by weight of isomer A, which has the following formula:

[0046] and

[0047] at most 90% by weight of isomer B, which has the following formula:

[0048]

[0049] In a second aspect, a copolymer is provided. The copolymer is the reaction product of a polymerizable composition, the polymerizable composition comprising:

[0050]

[0051] and

[0052]

[0053] wherein each of R 1 , R 2 , R 3 and R 4 is independently selected from H, a straight-chain or branched C1 to C20 hydrocarbon group; a straight-chain or branched C1 to C20 hetero-hydrocarbon group, a C1 to C20 carbosilane, and a C5 to C20 heterocycle, or R 1 and R 2 together or R 3 and R 4 together form a C1 to C20 alkylene group; n is an integer from 0 to 5; and wherein each Y is independently selected from -CH 2 -, -CH 2 CH 2 -, and O.

[0054] The following disclosure relates to both the first aspect and the second aspect.

[0055] It has been found that a mixture of itaconimide norbornene (i.e., isomer A) and citraconimide norbornene (i.e., isomer B) can be synthesized by reacting norbornenemethylamine with itaconic anhydride or citraconic anhydride. Exemplary specific reaction and purification conditions are described in the following examples.

[0056] The resulting isomer mixture contains at least 10 weight percent (wt.%) of isomer A, such as 12 wt.% or greater, 15 wt.%, 17 wt.%, 20 wt.%, 22 wt.%, 25 wt.%, 27 wt.%, 30 wt.%, 32 wt.%, 35 wt.%, 37 wt.%, or 40 wt.% or greater; and 75 wt.% or less, 72 wt.%, 70 wt.%, 67 wt.%, 65 wt.%, 62 wt.%, 60 wt.%, 57 wt.%, 55 wt.%, 52 wt.%, 50 wt.%, 47 wt.%, 45 wt.%, 42 wt.%, 40 wt.%, 37 wt.%, 35 wt.%, 30 wt.%, 27 wt.%, or 25 wt.% or less.

[0057] The isomer mixture contains at most 90 wt.% of isomer B, such as 90 wt.% or less, 87 wt.%, 85 wt.%, 82 wt.%, 80 wt.%, 77 wt.%, 75 wt.%, 72 wt.%, 70 wt.%, 67 wt.%, 65 wt.%, 62 wt.%, or 60 wt.% or less; and 25 wt.% or greater, 27 wt.%, 30 wt.%, 32 wt.%, 35 wt.%, 37 wt.%, 40 wt.%, 42 wt.%, 45 wt.%, 47 wt.%, 50 wt.%, 52 wt.%, 55 wt.%, 57 wt.%, or 60 wt.% or greater.

[0058] In some cases, isomer A is present in an amount of 10 wt.% to 75 wt.% of the isomer mixture and isomer B is present in an amount of 25 wt.% to 90 wt.% of the isomer mixture. Generally, the total amount of isomer A and isomer B is equal to 100 wt.% of the isomer mixture. In some cases, isomer A and isomer B together account for 95 wt.% to 100 wt.% of the total composition. In such embodiments, the composition may contain up to about 5 weight percent of other components, such as additives, impurities, etc.

[0059] It should be understood that the chemical structures of the substituted norbornene compounds herein are intended to cover all exo / endo isomers and all enantiomers / diastereomers that will be consistent with the indicated atomic connectivity.

[0060] Compositions according to at least some embodiments of the present disclosure can be used to prepare copolymers suitable for low dielectric applications. It has been found that curable polynorbornene resins containing higher amounts of pendant itaconimide functional groups can be used to form copolymers, which can provide enhanced thermal curing and crosslinking kinetics compared to systems containing lower amounts of pendant itaconimide functional groups, as shown, for example, by the storage modulus data in the following examples.

[0061] The copolymers described herein can be prepared by (e.g., via) addition polymerization. As used herein, the term "addition polymerization" (which is sometimes also referred to in the art as vinyl addition polymerization) refers to a polymerization method involving an olefin coordination insertion pathway mediated by an organometallic catalyst. A schematic is shown in Scheme I below.

[0062]

[0063] Wherein M-H represents an addition polymerization catalyst substance having a metal hydride bond, and p represents an integer greater than 10. This method is distinct from common alternative polymerization methods, namely ring-opening metathesis polymerization (ROMP), in terms of mechanism and final product. ROMP polymers contain double bonds in the polymer backbone, while the addition polymers according to the present disclosure do not contain double bonds.

[0064] Exemplary cyclic monomers suitable for addition polymerization with a mixture of isomer A and isomer B include 7-oxabicyclo[2.2.1]hept-2-ene, alkyl norbornene, cis-cyclooctene, cyclopentadiene, cyclopentene, dicyclopentadiene, hexyl norbornene, norbornadiene, norbornene (2-norbornene), tetracyclo[6.2.13.6.0]dodeca-4,9-diene, tetracyclopentadiene, tricyclopentadiene, and their derivatives having substituents including aliphatic groups, aromatic groups, esters, amides, ethers, and silanes.

[0065] Examples of suitable addition polymerizable cycloolefins containing a ring with a single carbon-carbon double bond include norbornene, 1-methylnorbornene, 5-methylnorbornene, 7-methylnorbornene, 5-(2-ethylhexyl)methylnorbornene, 1-pentadecylnorbornene, 5,5-dimethylnorbornene, 5,5-dibutylnorbornene, 5,7-dibutylnorbornene, 5-methyl-5-ethylnorbornene, 5,6-docosylnorbornene, 5-ethyl-6-propylnorbornene, 5,5,6,6-tetramethylnorbornene, 1-phenylnorbornene, 5-naphthylnorbornene, 5,5-diphenylnorbornene, 5-vinylnorbornene, 7-vinylnorbornene, 5-propenyl-6-methylnorbornene, 5-tolylmethylnorbornene, 5-benzyl-norbornene, 5-cyclopentyl-norbornene, 1,5,5-trimethylnorbornene, 5-isopropenylnorbornene, 1-isopropyl-norbornene, 1-ethylnorbornene, 1,5-dimethyl-norbornene, 1,5-diethylnorbornene, 1,6-dimethyl-norbornene, 5,5,6-trimethylnorbornene, 5-cyclopropenylnorbornene, 5-cyclohexyl-norbornene, 5-cyclopentenylnorbornene, 5-(2'-norbornenyl)norbornene, 5-phenylnorbornene, 5-benzylnorborn-2-ene, 5-(2'-phenylethyl)-norbornene, 5-(3'-phenylpropyl)norbornene, 5-(4'-phenylbutyl)norbornene, 2,5-norbornadiene, cyclopentene, dicyclopentadiene, 2,5-norbornadiene, bicyclo[2.2.2]-2-octene, indene, 5-methylene norbornene, 5-ethylene norbornene, 5-propylene-norbornene, 5-hexylene-norbornene, 5-decylene norbornene, 5-methylene-6-methylnorbornene, 5-methylene-6-hexylnorbornene, 5-cyclohexylidenenorbornene, 5-cyclooctylidenenorbornene, 7-isopropylidenenorbornene, 5-methyl-7-isopropylidenenorbornene, 5-hydroxymethyl-6-methylenenorbornene, 7-ethylene norbornene and 5-methyl-7-propylene norbornene.

[0066] The composition according to the present disclosure contains one or more addition polymerization catalysts. Many addition polymerization catalysts are known in the art and are generally based on organometallic complexes containing Ti, Zr, Cr, Co, Fe, Cu, Ni, or Pd. Among them, the most commonly used are addition polymerization catalysts containing Ni or Pd. There is a large amount of literature on organometallic addition polymerization catalysts, especially for norbornene-type monomers. Generally, the active catalyst substance is a cationic transition metal complex having an alkyl or allyl ligand and a weakly coordinating anion. The addition polymerization catalyst can be included in the polymerizable composition according to the present disclosure as a single active substance (or a combination thereof), or the addition polymerization catalyst can be provided as a combination of a precatalyst and a precursor of an activator; for example, as is common in the art. Generally, the precatalyst provides an active site for the olefin insertion mechanism to form the addition polymer. The combination with the activator converts the precatalyst into its active form.

[0067] In some embodiments, suitable catalyst and precatalyst / activator combinations for the addition polymerization of cycloolefins containing a ring with a single carbon-carbon bond may include Group 10 (i.e., in the Periodic Table of the Elements) catalysts or precatalyst / activator combinations; for example, Ni-based, Pd-based, or Pt-based addition polymerization catalysts. In some preferred embodiments, late metal (e.g., Ni- or Pd-based) precatalysts have allyl / alkyl ligands and chloro ligands. These precatalysts are activated by adding a monovalent metal (Li, Na, Ag) salt of a weakly coordinating anion (e.g., BF 4 4, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (BARF), or perfluorotetraphenylborate).

[0068] Exemplary suitable precatalysts include: (1,1-dimethylallyl)palladium(triisopropylphosphine)trifluoroacetate, (2-chloroallyl)palladium(triisopropylphosphine)trifluoroacetate, (allyl)palladium(tricyclohexylphosphine)chloride, (allyl)palladium(tricyclohexylphosphine)p-toluenesulfonate, (allyl)palladium(tricyclohexylphosphine)trifluoromethanesulfonate, (allyl)palladium(tricyclohexylphosphine)trifluoroimine, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate, (allyl)palladium(triisopropylphosphine)trifluoromethanesulfonate, (allyl)palladium(triisopropylphosphine)trifluoroimine, (allyl)palladium(triisopropylphosphine)trifluoroacetate, (allyl)palladium(trinaphthylphosphine)trifluoromethanesulfonate, (allyl)palladium(tri-o-tolylphosphine)acetate, (allyl)palladium(tri-o-tolylphosphine)nitrate, (allyl)palladium(tri-o-tolylphosphine)trifluoromethanesulfonate, (allyl)palladium(triphenylphosphine)trifluoromethanesulfonate, (allyl)palladium(triphenylphosphine)trifluoroimine, (allyl)palladium(tricyclopentylphosphine)trifluoromethanesulfonate, (allyl)palladium(tri-o-tolylphosphine)chloride, (allyl)Pd(AsPh 3)Cl, (allyl)Pd(PPh 3 )Cl, (allyl)Pd(PCy 3 )C 6 F 5 , (allyl)Pd(P-i-Pr 3 )C 6 F 5 , (allyl)Pd(PMe 3 )OC(O)CH 2 CH=CH 2 , (allyl)Pd(SbPh 3 )Cl, (C 2 H 5 )Pd(PMe 3 ) 2 Br, (C 2 H 5 )Pd(PMe 3 ) 2 Br, (C 2 H 5 )Pd(PMe 3 ) 2 Cl(Ph), (CH 3 )Pd(P(i-Pr) 3 ) 2 O 3 SCF 3 , (CH 3 )Pd(PMe 2 Ph) 2 Cl, (CH 3 )Pd(PMe 3 ) 2 Cl, (CH 3 )Pd(PMe 3 )NO 3 , (crotyl)palladium(tricyclohexylphosphine) trifluoromethanesulfonate, (crotyl)palladium(tricyclopentylphosphine) trifluoromethanesulfonate, (crotyl)palladium(triisopropylphosphine) trifluoromethanesulfonate, (cyclooctadiene)palladium(II) dichloride, (hydrido)palladium bis(tricyclohexylphosphine) chloride, (hydrido)palladium bis(tricyclohexylphosphine) formate, (hydrido)palladium bis(tricyclohexylphosphine) nitrate, (hydrido)palladium bis(tricyclohexylphosphine) trifluoromethanesulfonate, (hydrido)palladium bis(tricyclohexylphosphine) trifluoroacetate, (hydrido)palladium bis(triisopropylphosphine) chloride, (hydrido)palladium bis(triisopropylphosphine) trifluoromethanesulfonate, (Me 2 NCH 2 C 6 H 4 )Pd(O 3 SCF 3 )P(cyclohexyl) 3, (methallyl)palladium(tricyclohexylphosphine)acetate, (methallyl)palladium(tricyclohexylphosphine)chloride, (methallyl)palladium(tricyclohexylphosphine)trifluoromethanesulfonate, (methallyl)palladium(tricyclohexyl - phosphine)trifluoroimine, (methallyl)palladium(tricyclohexylphosphine)trifluoroacetate, (methallyl)-palladium(tricyclopentylphosphine)acetate, (methallyl)palladium(tricyclopentylphosphine)chloride, (methallyl)palladium(tricyclopentylphosphine)trifluoromethanesulfonate, (methallyl)palladium(tricyclopentylphosphine)trifluoroimine, (methallyl)palladium(tricyclopentylphosphine)trifluoroacetate, (methallyl)palladium(triisopropylphosphine)acetate, (methallyl)palladium(triisopropylphosphine)chloride, (methallyl)-palladium(triisopropylphosphine)trifluoromethanesulfonate, (methallyl)palladium(triisopropylphosphine)trifluoroimine, (methallyl)palladium(triisopropylphosphine)trifluoroacetate, (methallyl)Pd(AsPh 3 )Cl, (methallyl)-Pd(P[(OCH 2 ) 3 CH)Cl, (methallyl)Pd(PBu 3 )Cl, (methallyl)Pd(PPh 3 )Cl, (methallyl)Pd(SbPh 3 )Cl, (Ph)Pd(PMe 3 ) 2 Br, (PMe 3 ) 2 Br, (η 1 -benzyl)Pd(PEt 3 ) 2 Cl, [(allyl)Pd(HOCH 3 )(P - i - Pr 3 )][B(O 2 -3,4,5,6 - Br 4 C 6 ) 2 , [(allyl)Pd(HOCH 3 )(P - i - Pr 3 )][B(O 2 -3,4,5,6 - Cl 4 C 6 ) 2 , [(allyl)Pd(HOCH 3 )(P - i - Pr 3 )]-[B(O 2 C6H4)z], [(allyl)Pd(OEt 2 )(PCy 3 )][BF 4, [(allyl)Pd(OEt 2 )(PCy 3 )][PF 6 , [(allyl)Pd(OEt 2 )(P-iPr 3 )], [(allyl)Pd(OEt 2 )(P-i-Pr 3 )][BPh 4 , [(allyl)Pd(OEt 2 )(P-i-Pr 3 )][ClO 4 , [(allyl)Pd(OEt 2 )(PPh 3 )][SbF 6 , [(allyl)Pd(OEt 2 )(P-i-Pr 3 )][PF 6 , [(allyl)Pd(OEt 2 )(PPh 3 )][BF 4 , [(allyl)Pd(OEt 2 )(PPh 3 )][PF 6 , [(dimethylamino)methyl]phenyl-C,N-}-palladium(tricyclohexylphosphine) trifluoromethanesulfonate, [(allyl)Pd(OEt 2 )(P-i-Pr 3 )][BF 4, {2-[(dimethylamino)methyl]phenyl-C,N-}-palladium(tricyclohexylphosphine) chloride, bis(benzonitrile)palladium(II) dibromide, bis(acetone)palladium(II) dichloride, bis(acetonitrile)palladium(II) dichloride, bis(benzonitrile)palladium(II) dichloride, palladium(II) bis(tricyclohexylphosphine) bis(trifluoroacetate), palladium(II) bis(tricyclohexylphosphine) diacetate, palladium(II) bis(tricyclohexylphosphine) dibromide, palladium(II) bis(tricyclohexylphosphine) dichloride, palladium(II) bis(triisopropylphosphine) bis(trifluoroacetate), palladium(II) bis(triisopropylphosphine) diacetate, palladium(II) bis(triisopropylphosphine) dibromide, palladium(II) bis(triisopropylphosphine) dichloride, palladium(II) bis(triphenylphosphine) bis(trifluoroacetate), palladium(II) bis(triphenylphosphine) diacetate, palladium(II) bis(triphenylphosphine) dibromide, palladium(II) bis(triphenylphosphine) dichloride, palladium(II) bis(tritolylphosphine) bis(trifluoroacetate), palladium(II) bis(tritolylphosphine) diacetate, palladium(II) bis(tritolylphosphine) dibromide, palladium(II) bis(tritolylphosphine) dichloride, palladium(II) 2-ethylhexanoate, palladium(II) acetylacetonate, palladium(II) bis(trifluoroacetate), palladium(II) 2-ethylhexanoate, Pd(acetate) 2 (PPh 3 ) 2 、Pd(PMe 3 ) 2 Cl、(CH 3 )Pd、PdBr 2 (P(p-tolyl) 3 ) 2 、PdBr 2 (PPh 3 ) 2 、PdCl 2 (P(cyclohexyl) 3 ) 2 、PdCl 2 (P(o-tolyl) 3 ) 2 、PdCl 2 (PPh 3 ) 2 ;platinum(II) chloride; platinum(II) bromide, platinum bis(triphenylphosphine) dichloride, trans-PdCl 2 (PPh 3 ) 2 、(methallyl)nickel-(tricyclohexylphosphine) trifluoromethanesulfonate, nickel acetylacetonate, nickel carboxylate, nickel(II) chloride, nickel(II) bromide, nickel 2-ethylhexanoate, nickel(II) trifluoroacetate, nickel(II) hexafluoroacetylacetonate, NiCl 2 (PPh 3 )2 , NiBr 2 P(p - tolyl) 3 ) 2 , (allyl)platinum(tricyclohexylphosphine) chloride, (allyl)platinum(tricyclohexylphosphine) trifluoromethanesulfonate, allyl chloride[1,3 - bis(2,6 - di - i - propylphenyl)-4,5 - dihydroimidazol - 2 - yliden]palladium(II), allyl chloride[1,3 - bis(2,6 - di - i - propylphenyl)imidazol - 2 - yliden]palladium(II), chloro[(1,2,3 - η)-3 - phenyl - 2 - propenyl][1,3 - bis(2,6 - di - i - propylphenyl)-4,5 - dihydroimidazol - 2 - yliden]palladium(II), chloro[(1,2,3 - η)-3 - phenyl - 2 - propenyl][1,3 - bis(2,6 - di - i - propylphenyl)imidazol - 2 - yliden]palladium(II), allyl chloride[1,3 - bis(2,6 - di - i - propylphenyl)-4,5 - dihydroimidazol - 2 - yliden]nickel(II), allyl chloride[1,3 - bis(2,6 - di - i - propylphenyl)imidazol - 2 - yliden]nickel(II), chloro[(1,2,3 - η)-3 - phenyl - 2 - propenyl][1,3 - bis(2,6 - di - i - propylphenyl)-4,5 - dihydroimidazol - 2 - yliden]nickel(II) and chloro[(1,2,3 - η)-3 - phenyl - 2 - propenyl][1,3 - bis(2,6 - di - i - propylphenyl)imidazol - 2 - yliden]nickel(II).

[0069] The addition of a Lewis base that coordinates to the metal atom can improve the activity of the addition polymerization catalyst and / or precatalyst. That is, the Lewis base bonds to the metal atom by sharing two electrons of the lone pair of electrons of the metal atom. Any Lewis base known in the art can be used for this purpose. Preferably, the Lewis base can be easily dissociated under polymerization conditions.

[0070] Exemplary suitable Lewis bases include substituted and unsubstituted nitriles, including alkyl nitriles, aryl nitriles or aralkyl nitriles; phosphine oxides, including substituted and unsubstituted trialkylphosphine oxides, triarylphosphine oxides, triaralkylphosphine oxides and various combinations of alkyl, aryl and aralkyl phosphine oxides; substituted and unsubstituted pyrazines; substituted and unsubstituted pyridines; phosphites, including substituted and unsubstituted trialkyl phosphites, triaryl phosphites, triaralkyl phosphites and various combinations of alkyl, aryl and aralkyl phosphites; phosphines, including substituted and unsubstituted trialkyl phosphines, triaryl phosphines, triaralkyl phosphines and various combinations of alkyl, aryl and aralkyl phosphines. Various other Lewis bases that can be used include various ethers, alcohols, ketones, amines and anilines, arsenic, and stibine. In some embodiments, the Lewis base can be selected from acetonitrile, propionitrile, n - butyronitrile, tert - butyronitrile, benzonitrile (C 6 H 5CN), 2,4,6 - trimethylbenzonitrile, phenylacetonitrile (C 6 H 5 CH 2 CN), pyridine, 2 - methylpyridine, 3 - methylpyridine, 4 - methylpyridine, 2,3 - dimethylpyridine, 2,4 - dimethylpyridine, 2,5 - dimethylpyridine, 2,6 - dimethylpyridine, 3,4 - dimethylpyridine, 3,5 - dimethylpyridine, 2,6 - di - 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, benzophenone, triphenylphosphine oxide, triphenyl phosphate, and PR 1 3 , where each R 1 is independently selected from methyl, ethyl, (C 3 -C 6 ) alkyl, substituted or unsubstituted (C 3 -C 7 ) cycloalkyl, (C 6 -C 10 ) aryl, (C 6 -C 10 ) aralkyl, methoxy, ethoxy, (C 3 -C 6 ) alkoxy, substituted or unsubstituted (C 3 -C 7 ) cycloalkoxy, (C 6 -C 10 ) aryloxy, and (C 6 -C 10 ) aralkoxy.

[0071] PR 1 3 Representative examples of PR

[0072] Other examples of organophosphorus compounds suitable as Lewis bases include phosphites and phosphite ligands. Representative examples of phosphite ligands include methyldiphenylphosphite, ethyldiphenylphosphite, isopropyldiphenylphosphite, and phenyldiphenylphosphite. Representative examples of phosphite ligands include diphenyl phenylphosphite, dimethyl phenylphosphite, diethyl methylphosphite, diisopropyl phenylphosphite, and diethyl phenylphosphite.

[0073] If added, the Lewis base can generally be added in stoichiometric excess, but this is not necessary.

[0074] Exemplary activators include: lithium tetrakis(2-fluorophenyl)borate, sodium tetrakis(2-fluorophenyl)borate, silver tetrakis(2-fluorophenyl)borate, thallium tetrakis(2-fluorophenyl)borate, lithium tetrakis(3-fluorophenyl)borate, sodium tetrakis(3-fluorophenyl)borate, silver tetrakis(3-fluorophenyl)borate, thallium tetrakis(3-fluorophenyl)borate, ferrocene tetrakis(3-fluorophenyl)borate, ferrocene tetrakis(pentafluorophenyl)borate, lithium tetrakis(4-fluorophenyl)borate, sodium tetrakis(4-fluorophenyl)borate, silver tetrakis(4-fluorophenyl)borate, thallium tetrakis(4-fluorophenyl)borate, lithium tetrakis(3,5-difluorophenyl)borate, sodium tetrakis(3,5-difluorophenyl)borate, thallium tetrakis(3,5-difluorophenyl)borate, triphenylmethyl tetrakis(3,5-difluorophenyl)borate, 2,6-dimethylaniline tetrakis(3,5-difluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium(diethyl ether)tetrakis(pentafluorophenyl)borate, lithium(diethyl ether)tetrakis(pentafluorophenyl)borate, lithium tetrakis(2,3,4,5-tetrafluorophenyl)borate, lithium tetrakis(3,4,5,6-tetrafluorophenyl)borate, lithium tetrakis(1,2,2-trifluorovinyl)borate, lithium tetrakis(3,4,5-trifluorophenyl)borate, lithium methyl tris(pentafluorophenyl)borate, lithium phenyl tris(pentafluorophenyl)borate, lithium tris(isopropanol)tetrakis(pentafluorophenyl)borate, lithium tetrakis(methanol)tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, silver tris(toluene)tetrakis(pentafluorophenyl)borate, silver tris(xylene)tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(4-triisopropylsilyltetrafluorophenyl)borate, triphenylmethyl tetrakis(4-dimethyl-tert-butylsilyl-tetrafluorophenyl)borate, thallium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, 2,6-dimethylaniline tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, lithium(triphenylsilyloxy)-tris(pentafluorophenyl)borate, sodium(triphenylsilyloxy)tris(pentafluorophenyl)borate, sodium tetrakis(2,3,4,5-tetrafluorophenyl)borate, sodium tetrakis(3,4,5,6-tetrafluorophenyl)borate, sodium tetrakis(1,2,2-trifluorovinyl)borate, sodium tetrakis(3,4,5-trifluorophenyl)borate, sodium methyl tris(pentafluorophenyl)borate, sodium phenyl tris(pentafluorophenyl)borate, thallium tetrakis(2,3,4,5-tetrafluorophenyl)borate, thallium tetrakis(3,4,5,6-tetrafluorophenyl)borate, thallium tetrakis(1,2,2-trifluorovinyl)borate, thallium tetrakis(3,4,5-trifluorophenyl)borate, sodium methyl tris-(pentafluorophenyl)borate, thallium phenyl tris(pentafluorophenyl)borate, triphenylmethyl tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyl tetrakis(3,4,5,6-tetrafluorophenyl)borate, triphenylmethyl tetrakis(1,2,(2-trifluorovinyl)borate, trityl tetrakis(3,4,5-trifluorophenyl)borate, trityl methyl tris(pentafluorophenyl)borate, trityl phenyl tris(pentafluorophenyl)borate, silver tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, silver(toluene) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, thallium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, lithium hexyl tris(pentafluorophenyl)borate, lithium triphenylsilyloxy tris(pentafluorophenyl)borate, lithium(octyloxy) tris(pentafluorophenyl)borate, sodium lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(pentafluorophenyl)borate, trityl tetrakis(pentafluorophenyl)borate, sodium(octyloxy)-tris(pentafluorophenyl)borate, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, potassium tetrakis(pentafluorophenyl)borate, trityl tetra-(pentafluorophenyl)borate, potassium(octyloxy) tris(pentafluorophenyl)borate, potassium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, magnesium tetrakis(pentafluorophenyl)borate, magnesium(octyloxy) tris(pentafluorophenyl)-borate, magnesium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, calcium tetrakis(pentafluorophenyl)borate, calcium(octyloxy) tris(pentafluorophenyl)borate, calcium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, lithium tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, sodium tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, silver tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, thallium tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, lithium tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, sodium tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, silver tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, thallium tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, lithium tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, sodium tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, silver tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, thallium tetrakis[3-[2,2,2-trifluoro-1-(2,2,(2-Trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, trimethylsilylium tetrakis(pentafluorophenyl)-borate, trimethylsilylium etherate tetrakis-(pentafluorophenyl)borate, triethylsilylium tetrakis(pentafluorophenyl)borate, triphenylsilylium tetrakis(pentafluorophenyl)borate, tris(mesityl)silylium tetrakis(pentafluorophenyl)borate, tribenzyl-silylium tetrakis(pentafluorophenyl)-borate, trimethylsilylium methyltris(pentafluorophenyl)borate, triethylsilylium methyltris-(pentafluorophenyl)borate, triphenylsilylium methyltris(pentafluorophenyl)-borate, tribenzylsilylium methyltris(pentafluorophenyl)borate, trimethylsilylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triethylsilylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylsilylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, tribenzylsilylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, trimethylsilylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylsilylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, trimethylsilylium tetrakis(3,4,5-trifluorophenyl)borate, tribenzylsilylium tetrakis(3,4,5-trifluorophenyl)-aluminate, triphenylsilylium tetrakis(3,4,5-trifluorophenyl)aluminate, triethylsilylium tetrakis(1,2,2-trifluorovinyl)borate, tricyclohexylsilylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, dimethyloctadecylsilylium tetrakis(pentafluorophenyl)borate, tris(trimethylsilyl)-silylium methyltris(2,3,4,5-tetrafluorophenyl)borate, 2,2'-dimethyl-1,1'-binaphthyl-methylsilylium tetrakis(pentafluorophenyl)borate, 2,2'-dimethyl-1,1'-binaphthylmethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, lithium tetrakis(pentafluorophenyl)aluminate, trityl tetrakis(pentafluorophenyl)aluminate, trityl(pentafluorophenyl)fluoroaluminate, lithium(octyloxy)-tris(pentafluorophenyl)aluminate, lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, sodium tetrakis(pentafluorophenyl)aluminate, trityl tetrakis(pentafluorophenyl)aluminate, sodium(octyloxy)-tris(pentafluorophenyl)aluminate, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)-aluminate, potassium tetrakis(pentafluorophenyl)aluminate, trityl tetrakis(pentafluorophenyl)aluminate, potassium(octyloxy)-tris(pentafluorophenyl)aluminate, potassium tetrakis(3,5-bis(trifluoromethyl)-phenyl)aluminate, magnesium tetrakis(pentafluorophenyl)aluminate, magnesium(octyloxy)tris-(pentafluorophenyl)aluminate, magnesium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, calcium tetrakis(pentafluorophenyl)aluminate, calcium(octyloxy)tris(pentafluorophenyl)aluminate, calcium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, LiB(OC(CF, 3 ) 3 ) 4 、LiB(OC(CF 3 ) 2 (CH 3 )) 4 、LiB(OC(CF 3 ) 2 H) 4 、LiB(OC(CF 3 )(CH 3 )H) 4 、Tl(OC(CF 3 ) 3 ) 4 、TlB(OC(CF 3 ) 2 H) 4 、TlB(OC(CF 3 )(CH 3 )H) 4 、TlB(OC(CF 3 ) 2 (CH 3 )) 4 、(Ph 3 C)B(OC(CF 3 ) 3 ) 4 、(Ph 3 C)B(OC(CF 3 ) 2 (CH 3 )) 4 、(Ph 3 C)B(OC(CF 3 ) 2 H) 4 、(Ph 3 C)B(OC(CF 3 )(CH 3 )H) 4 、AgB(OC(CF 3 )) 4 、AgB(OC(CF 3 ) 2 H) 4 、AgB(OC(CF 3 )(CH 3 )H) 4 、LiB(O 2 C 6 F 4 ) 2 、TlB(O 2 C 6 F4 ) 2 、Ag(toluene) 2 B(O 2 C 6 F 4 ) 2 、Ph 3 CB(O 2 C 6 F 4 ) 2 LiB(OCH(CF 3 ) 2 ) 4 、[Li(HOCH 3 ) 4 B(O 2 C 6 Cl 4 ) 2 、[Li(HOCH 3 )4]B(O 2 C 6 F 4 ) 2 、[Ag(toluene) 2 B(O 2 C 6 Cl 4 ) 2 、LiB(O 2 C 6 Cl 4 ) 2 、(LiAl(OC(CF 3 ) 2 Ph) 4 )、(TlAl(OC(CF 3 ) 2 Ph) 4 )、(AgAl(OC(CF 3 ) 2 Ph) 4 )、(Ph 3 CAl(OC(CF 3 ) 2 Ph) 4 、(LiAl(OC(CF 3 ) 2 C 6 H 4 CH 3 ) 4 )、(TlAl(OC(CF 3 ) 2 C 6 H 4 CH 3 ) 4 )、(AgAl(OC(CF3 ) 2 C 6 H 4 CH 3 ) 4 )、(Ph 3 CAl(OC(CF 3 ) 2 C 6 H 4 CH 3 ) 4 )、LiAl(OC(CF 3 )) 4 、TlAl(OC(CF 3 ) 3 ) 4 、AgAl(OC(CF 3 ) 3 ) 4 、Ph 3 CAl(OC(CF 3 ) 3 ) 4 、LiAl(OC(CF 3 )(CH 3 )H) 4 、TlAl(OC(CF 3 )(CH 3 )H) 4 、AgAl(OC(CF 3 )(CH 3 )H) 4 、Ph 3 CAl(OC(CF 3 )(CH 3 )H) 4 、LiAl(OC(CF 3 ) 2 H) 4 、TlAl(OC(CF 3 ) 2 H) 4 、AgAl(OC(CF 3 ) 2 H) 4 、Ph 3 CAl(OC(CF 3 ) 2 H) 4 、LiAl(OC(CF 3 ) 2 C6H 4 -4-i-Pr) 4 、TlAl(OC(CF 3 ) 2 C6H 4-4-isopropyl 4 、AgAl(OC(CF 3 ) 2 C 6 H 4 -isopropyl 4 、Ph 3 CAl(OC(CF 3 ) 2 C 6 H 4 -4-isopropyl 4 、LiAl(OC(CF 3 ) 2 C 6 H 4 -tert-butyl 4 、TlAl(OC(CF 3 ) 2 C 6 H 4 -tert-butyl 4 、AgAl(OC(CF 3 ) 2 C 6 H 4 -4-tert-butyl 4 、LiAl(OC(CF 3 ) 2 C 6 H 4 -4-SiMe 3 ) 4 、TlAl(OC(CF 3 ) 2 C 6 H 4 -4-SiMe 3 ) 4 、AgAl(OC(CF 3 ) 2 C 6 H 4 -4-SiMe 3 ) 4 、Ph 3 CAl(OC(CF 3 ) 2 C 6 H 4 -4-SiMe 3 ) 4 、LiAl(OC(CF 3 ) 2 C 6 H 4 -4-Si-isopropyl 3 ) 4 、TlAl(OC(CF 3) 2 C 6 H 4 -4-Si-i-Pr 3 ) 4 、AgAl(OC(CF 3 ) 2 C 6 H 4 -4-Si-i-Pr 3 ) 4 、Ph 3 CAl(OC(CF 3 ) 2 C 6 H 4 -4-Si-i-Pr 3 ) 4 、LiAl(OC(CF 3 ) 2 C 6 H 2 -2,6-(CF 3 ) 2 -4-Si-i-Pr 3 ) 4 、TlAl(OC(CF 3 ) 2 C 6 H 2 -2,6-(CF 3 ) 2 -4-Si-i-Pr 3 ) 4 、AgAl(OC(CF 3 ) 2 C 6 H 2 -2,6-(CF 3 ) 2 -4-Si-i-Pr 3 ) 4 、Ph 3 CAl(OC(CF 3 ) 2 C 6 H 2 -2,6-(CF 3 ) 2 -4-Si-i-Pr 3 ) 4 、LiAl(OC(CF 3 ) 2 C 6 H 3 -3,5-(CF 3 ) 2 ) 4 、TlAl(OC(CF3 ) 2 C 6 H 3 -3,5-(CF 3 ) 2 ) 4 、AgAl(OC(CF 3 ) 2 C 6 H 3 -3,5-(CF 3 ) 2 ) 4 、Ph 3 CAl(OC(CF 3 ) 2 C 6 H 3 -3,5-(CF 3 ) 2 ) 4 、LiAl(OC(CF 3 ) 2 C 6 H 2 -2,4,6-(CF 3 )) 4 、TlAl(OC(CF 3 ) 2 C 6 H 2 -2,4,6-(CF 3 ) 3 ) 4 、AgAl(OC(CF 3 ) 2 C 6 H 2 -2,4,6-(CF 3 ) 3 ) 4 、Ph 3 CAl(OC(CF 3 ) 2 C 6 H 2 -2,4,6-(CF 3 L) 4 、LiAl(OC(CF 3 ) 2 C 6 F 5 ) 4 、TlAl(OC(CF 3 ) 2 C 6 F 5 ) 4 、AgAl(OC(CF 3 ) 2C 6 F 5 ) 4 Ph 3 CAl(OC(CF 3 ) 2 C 6 F 5 ) 4 , [1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-boryl lithium, [1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-boryl triphenylmethylium, 4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-boryl lithium, 4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-boryl triphenylmethylium, 1 -1,2-dihydro-4-(pentafluorophenyl)-2-boryl lithium, 1-fluoro-1,2-dihydro-4-pentafluorophenyl)-2-boryl triphenylmethylium, 1-[3,5-bis(trifluoromethyl)phenyl]-dihydro-4-(pentafluorophenyl)-2-boryl lithium, 1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-boryl triphenylmethylium, LiBF 4 , NaBF 4 KBF 4 , AgBF 4 、[Ph 3 C]BF 4 , TlBF 4 Mg(BF 4 ) 2 , Ca(BF 4 ) 2 、LiPF 6 、NaPF 6 、KPF 6 、[Ph 3 C]PF 6 、TlPF 6 、Mg(PF 6 ) 2 、Ca(PF 6 ) 2 、LiSbF 6 、NaSbF 6 , KSb 6 、[Ph 3 C]SbF 6 ,TlSbF 6 Mg(SbF 6 ) 2 and Ca(SbF 6 ) 2 .

[0075] Typically, the molar ratio of activator to precatalyst ranges from 10:1 to 1:10 (preferably 10:1 to 1:1), but other ratios can also be used.

[0076] Many useful addition polymerization catalysts and precatalyst / activator combinations are known and are disclosed in the following documents: for example, columns 8, line 28 to column 9, line 56 of U.S. Patent No. 3,330,815 (McKeon et al.); columns 3, line 9 to column 17, line 16 of U.S. Patent No. 6,455,650 B1 (Lipian et al.); columns 3, line 18 to column 31, line 53 of U.S. Patent No. 6,825,307 (Goodall); columns 3, line 31 to column 17, line 16 of U.S. Patent No. 6,903,171 B2 (Rhodes et al.); and columns 16, line 32 to column 28, line 31 of U.S. Patent No. 7,759,439 B2 (Rhodes et al.); columns 20, line 28 to column 21, line 30 of U.S. Patent No. 10,266,720 (Burgoon et al.); and paragraphs

[0015] to

[0075] of U.S. Patent Application Publication 2005 / 0187398 A1 (Bell et al.), the disclosures of which are incorporated herein by reference. Another class of catalysts relates to precatalyst complexes of early or late metals that initially do not have alkyl / allyl ligands but are alkylated by cocatalysts such as, for example, methylaluminoxane.

[0077] Details regarding certain addition polymerization catalysts are also reported by M.V. Bermeshev and P.P. Chapala in “Addition polymerization of functionalized norbornenes as a powerful tool for assembling molecular moieties of new polymers with versatile properties”, Progress in Polymer Science (2018), 84, pp. 1–46.

[0078] It may contain any effective amount of an addition polymerization catalyst to cause at least partial polymerization of the polymerizable composition, optionally by heating. Generally, based on 100 parts by weight of the addition polymerizable compound present in the polymerizable composition, the amount of the addition polymerization catalyst can range from about 0.0001 part by weight to about 20 parts by weight, preferably, about 0.01 part by weight to about 5 parts by weight per 100 parts by weight of the addition polymerizable compound present in the polymerizable composition; however, this is not necessary.

[0079] In some cases, the copolymer is the reaction product of a polymerizable composition comprising isomer A and isomer B or consisting essentially of isomer A and isomer B. "Consisting essentially of" means that the copolymer is formed from 95 wt.% to 100 wt.% of isomer A and isomer B. The polymerizable composition consisting essentially of isomer A and isomer B may contain up to 5 wt.% of other components such as additives, impurities, etc.

[0080] In some cases, the copolymer is the reaction product of a polymerizable composition comprising isomer A and isomer B and at least one additional monomer (such as a norbornene-type monomer).

[0081] Based on the total number of moles of the combination of isomer A, isomer B, and one or more additional monomers of the polymerizable composition, the at least one additional monomer (e.g., the combination of all additional monomers) can be present in the polymerizable composition in an amount of 5 mole percent (mol%) or greater: 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 12 mol%, 15 mol%, 17 mol%, 20 mol%, 22 mol%, 25 mol%, 27 mol%, 30 mol%, 32 mol%, 35 mol%, 37 mol%, 40 mol%, 42 mol%, 45 mol%, 47 mol%, 50 mol%, 52 mol%, 55 mol%, 57 mol%, 60 mol%, 62 mol%, 65 mol%, 67 mol%, or 70 mol% or greater; and based on the total number of moles of the polymerizable components of the polymerizable composition, 95 mol% or less, 92 mol%, 90 mol%, 87 mol%, 85 mol%, 82 mol%, 80 mol%, 77 mol%, 75 mol%, 72 mol%, 70 mol%, 67 mol%, 65 mol%, 62 mol%, 60 mol%, 57 mol%, 55 mol%, 52 mol%, 50 mol%, 47 mol%, 45 mol%, 42 mol%, 40 mol%, 37 mol%, 35 mol%, 32 mol%, 30 mol%, 27 mol%, 25 mol%, 22 mol%, or 20 mol% or less. In some cases, the additional monomer can be present in the polymerizable composition in an amount of 40 mol% to 60 mol%.

[0082] Based on the total moles of the combination of isomer A, isomer B, and one or more additional monomers in the polymerizable composition, isomer A can be present in the polymerizable composition in an amount of 0.5 mol% or greater: 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol%, 13 mol%, 14 mol%, 15 mol%, 17 mol%, 20 mol%, 22 mol%, 25 mol%, 27 mol%, 30 mol%, 32 mol%, 35 mol%, 37 mol%, 40 mol%, 42 mol%, 45 mol%, 47 mol%, or 50 mol%; and based on the total moles of the polymerizable components of the polymerizable composition, 75 mol% or less, 72 mol%, 70 mol%, 67 mol%, 65 mol%, 62 mol%, 60 mol%, 57 mol%, 55 mol%, 52 mol%, 50 mol%, 47 mol%, 45 mol%, 42 mol%, 40 mol%, 37 mol%, 35 mol%, 32 mol%, 30 mol%, 27 mol%, 25 mol%, 22 mol%, or 20 mol% or less.

[0083] Based on the total number of moles of the combination of isomer A, isomer B, and one or more additional monomers in the polymerizable composition, isomer B can be present in the polymerizable composition in an amount of 1 mol% or greater: 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol%, 13 mol%, 14 mol%, 15 mol%, 17 mol%, 20 mol%, 22 mol%, 25 mol%, 27 mol%, 30 mol%, 32 mol%, 35 mol%, 37 mol%, 40 mol%, 42 mol%, 45 mol%, 47 mol%, 50 mol%; 52 mol%, 55 mol%, 57 mol%, 60 mol%, 62 mol%, 65 mol%, 67 mol%, or 70 mol% or greater; and based on the total number of moles of the polymerizable components of the polymerizable composition, 90 mol% or less, 87 mol%, 85 mol%, 82 mol%, 80 mol%, 77 mol%, 75 mol% or less, 72 mol%, 70 mol%, 67 mol%, 65 mol%, 62 mol%, 60 mol%, 57 mol%, 55 mol%, 52 mol%, 50 mol%, 47 mol%, 45 mol%, 42 mol%, 40 mol%, 37 mol%, 35 mol%, 32 mol%, 30 mol%, 27 mol%, 25 mol%, 22 mol%, or 20 mol% or less.

[0084] Exemplary suitable norbornene-type monomers include the above-mentioned addition-polymerizable cycloolefins. In some cases, suitable monomers include monomers of formula (C):

[0085]

[0086] wherein each of R 1 , R 2 , R 3 , and R 4 is independently selected from H, linear or branched C1 to C20 hydrocarbon groups; linear or branched C1 to C20 heterohydrocarbon groups, C1 to C20 carbosilanes, and C5 to C20 heterocycles, or R 1 and R 2 together or R 3 and R 4 together form a C1 to C20 alkylene group; n is an integer from 0 to 5; and wherein each Y is independently selected from -CH 2 -, -CH 2 CH 2 -, and O.

[0087] The C1 to C20 groups (such as those mentioned throughout the present disclosure) have 1 or more carbon atoms, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 or more carbon atoms, and 20 or fewer carbon atoms, 19, 18, 17, 16, 15, 14, 13, 12, 10, 9, 8, 7, 6, 5, or 4 or fewer carbon atoms.

[0088] In a selected embodiment, in the monomer of formula (C) depicted above, R 1 , R 2 , R 3 and R 4 each is H; n is 0; and Y is -CH 2 -. In a selected embodiment, in the monomer of formula (C) depicted above, R 1 , R 2 , R 3 and R 4 one of them is C6 alkyl; the remainder of R 1 , R 2 , R 3 and R 4 each is H; n is 0; and Y is -CH 2 -. In other words, the copolymer comprises the reaction product of a polymerizable composition containing isomer A, isomer B, and hexylnorbornene.

[0089] Optionally, the copolymer comprises at least two monomers of formula (C) that are different from each other. In one embodiment, the copolymer comprises at least two monomers of formula (C) that are different from each other, wherein in the first monomer of formula (C), R 1 , R 2 , R 3 and R 4 each is H; n is 0; and Y is -CH 2 (-), and in the second monomer of formula (C), R 1 , R 2 , R 3 and R 4 one of them is C6 alkyl; the remainder of R 1 , R 2 , R 3 and R 4 each is H; n is 0; and Y is -CH 2 (-). In other words, the copolymer comprises the reaction product of a polymerizable composition containing isomer A, isomer B, norbornene, and hexylnorbornene.

[0090] Suitable solvents for preparing the copolymers described herein include ethers such as diethyl ether, ethyl propyl ether, dipropyl ether, methyl tert-butyl ether, di-tert-butyl ether, glyme (dimethoxyethane), diglyme, diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; alkanes; cycloalkanes; aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene; halogenated hydrocarbon solvents; acetonitrile; lactones such as butyrolactone and valerolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; sulfones such as tetramethylene sulfone, 3-methyl sulfolane, 2,4-dimethyl sulfolane, butadiene sulfone, methyl sulfone, ethyl sulfone, propyl sulfone, butyl sulfone, methyl vinyl sulfone, 2-(methylsulfonyl)ethanol and 2,2'-sulfonyldiethanol; sulfoxides such as dimethyl sulfoxide; cyclic carbonates such as propylene carbonate, ethylene carbonate and vinylene carbonate; carboxylic acid esters such as ethyl acetate, Methyl Cellosolve TM and methyl formate; alcohols such as ethanol, methanol and propanol; and other solvents such as dichloromethane, nitromethane, acetonitrile, ethylene sulfite and 1,2-dimethoxyethane (glyme), and combinations of such solvents.

[0091] The molecular weight of the copolymer can be controlled by including one or more chain transfer agents or chain blockers in the polymerizable composition. For example, suitable chain transfer agents include monofunctional end chain transfer agents such as formic acid and primary olefins (such as 1-octene), alcohols, and other chain transfer agents known in the art.

[0092] The copolymers according to the present disclosure can be prepared, for example, by reacting the polymerizable composition at a sufficient temperature for a sufficient time to cause at least partial curing of the polymerizable components, preferably substantially complete polymerization. The heating temperature will depend on the specific polymerizable composition and can be, for example, room temperature (i.e., 20 °C to 25 °C), at least 30 °C, at least 40 °C, at least 50 °C, at least 75 °C, at least 100 °C or at least 150 °C. Generally, the reaction time for complete curing will be from a few minutes to 5 days, preferably 30 minutes to 3 days, and most preferably 1 hour to 24 hours. In some cases, the copolymers according to the present disclosure are provided in the form of a film.

[0093] In a third aspect, another copolymer is provided. The copolymer comprises the following divalent monomer units:

[0094] and

[0095]

[0096] where each Y is independently selected from -CH 2 -, -CH 2 CH2 - and O.

[0097] In a fourth aspect, additional copolymers are provided. The copolymer comprises the following divalent monomer units:

[0098]

[0099] and

[0100]

[0101] wherein each of R 1 , R 2 , R 3 and R 4 is independently selected from H, a linear or branched C1-C20 hydrocarbon group, a linear or branched C1-C20 hetero-hydrocarbon group, a C1-C20 carbosilane, and a C5-C20 heterocycle, or R 1 and R 2 together or R 3 and R 4 together form a C1-C20 alkylene group; n is an integer from 0 to 5; and wherein each Y is independently selected from -CH 2 -, -CH 2 CH 2 -, and O.

[0102] The following disclosure relates to both the third and fourth aspects.

[0103] In a selected embodiment, in the divalent unit of formula (III), at least one of R 1 , R 2 , R 3 and R 4 is a C1-C7 linear alkyl group, vinyl, or a C1-C20 carbosilane. In a selected embodiment, in the divalent unit of formula (III), each of R 1 , R 2 , R 3 and R 4 is H; n is 0; and Y is -CH 2 -. In a selected embodiment, R 1 and R 2 together or R 3 and R 4 together form a C1-C20 alkylene group, for example, the alkylene group can be ethylene or another alkylidene group. In a selected embodiment, in the divalent unit of formula (III), one of R 1 , R 2 , R 3 and R 4 is a C6 alkyl group; R1 , R 2 , R 3 and R 4 in each of the remaining portions is H; n is 0; and Y is -CH 2 -. In other words, the copolymer comprises the reaction product of a polymerizable composition containing isomer A, isomer B, and hexylnorbornene.

[0104] Optionally, the copolymer comprises at least two divalent units of formula (III) that are different from each other. For example, in one such copolymer, in the first divalent unit (III), R 1 , R 2 , R 3 and R 4 in each of them is H; n is 0; and Y is -CH 2 -; and in the second divalent unit (III), one of R 1 , R 2 , R 3 and R 4 is C6 alkyl, and R 1 , R 2 , R 3 and R 4 in each of the remaining portions is H; n is 0; and Y is -CH 2 -. In other words, the copolymer comprises the reaction product of a polymerizable composition containing isomer A, isomer B, norbornene, and hexylnorbornene.

[0105] The copolymers of the third and fourth aspects can be prepared as described in detail above with respect to the first and second aspects. In certain cases, the copolymer according to the third or fourth aspect is provided in the form of a film.

[0106] In a fifth aspect, a composition is provided. The composition comprises a solvent and a copolymer according to any one of the second to fourth aspects described in detail above.

[0107] In a sixth aspect, a film is provided. The film comprises the crosslinked reaction product of a copolymer according to any one of the second to fourth aspects described in detail above.

[0108] The following disclosure relates to both the fifth and sixth aspects.

[0109] The solvent in the composition can be used to dissolve the copolymer according to the present disclosure (i.e., any one of the copolymers of the second to fourth aspects). The use of the solvent can allow for the manipulation of the shape of the copolymer, for example, by enabling the formation of a film from the copolymer after removal of the solvent. Exemplary solvents include, for example, the solvents listed above with respect to the first and second aspects.

[0110] The composition may also include one or more additives. Examples of suitable additives include sensitizers, colorants (e.g., pigments and / or dyes), initiators, antioxidants, inhibitors, heat degradation stabilizers, light stabilizers (e.g., UV stabilizers), inert fillers, adhesion control agents, and other additives known to those skilled in the art. They may also be substantially non-reactive, such as inorganic and organic fillers, reinforcing agents, solid fillers, stabilizers, and combinations thereof. The additives may be added in an amount sufficient to obtain the desired properties of the prepared cured composition. The desired properties are largely determined by the intended application of the resulting copolymer or film. In selected embodiments, the composition further comprises at least one of a sensitizer, an initiator, a filler (e.g., silica), an antioxidant, an inhibitor, a stabilizer, a colorant, or an adhesion control agent (e.g., silanes, zirconates, and / or titanates).

[0111] When an initiator is present, optionally, the initiator comprises at least one of a thermal initiator or a photoinitiator.

[0112] Exemplary thermal curing initiators for use herein may be selected from the group consisting of fast-reacting thermal-initiator curing initiators, latent thermal-initiator curing initiators, and any combination or mixture thereof. Examples of suitable thermal initiators include, for example but not limited to, peroxides such as benzoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, cyclohexanone peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, hydroperoxides (e.g., tert-butyl hydroperoxide and cumene hydroperoxide), dicyclohexyl peroxydicarbonate, and tert-butyl perbenzoate, and diazo compounds such as 2,2'-azobis(isobutyronitrile). Examples of commercially available thermal initiators include: initiators available from Chemours Co. (Wilmington, DE) under the trade name VAZO, including VAZO 67 (2,2'-azobis(2-methylbutyronitrile)), VAZO 64 (2,2'-azobis(isobutyronitrile)), and VAZO 52 (2,2'-azobis(2,2-dimethylvaleronitrile)), and LUPEROX A98 from Arkema (King of Prussia, PA). As known to those skilled in the art, crosslinking of the copolymer of the film is achieved by exposing the film containing the thermal initiator to a temperature high enough to activate the thermal initiator.

[0113] In some embodiments, the initiator comprises a photoinitiator. Photoinitiators are used for actinic radiation, typically ultraviolet (UV) light, but other light sources may also be used depending on the appropriate selection of the initiator (such as visible light initiators, infrared light initiators, etc.). Generally, UV photoinitiators are used. As known to those skilled in the art, crosslinking of the copolymer of the film is achieved by exposing the film containing the photoinitiator to a light source to activate the photoinitiator.

[0114] Photoinitiators generally comprise photoinitiator groups selected from acylphosphine oxides, alkylamine acetophenones, benzil ketals, hydroxyacetophenones, organic or inorganic peroxides, persulfates, titanocene complexes or azo. When the initiator group includes persulfate, tetramethylethylenediamine may also be included as a curing accelerator.

[0115] Exemplary photoinitiators include benzoin and its derivatives such as α-methylbenzoin; α-phenylbenzoin; α-allylbenzoin; α-benzylbenzoin; benzoin ethers such as benzoyl dimethyl ketal (e.g., “OMNIRAD BDK” from IGM Resins USA Inc., Charlotte, NC), benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and its derivatives such as 2-hydroxy-2-methyl-1-phenyl-1-propanone (e.g., available under the trade name OMNIRAD 1173 from IGM Resins USA Inc., Charlotte, NC) and 1-hydroxycyclohexyl phenyl ketone (e.g., available under the trade name OMNIRAD 184 from IGM Resins USA Inc., Charlotte, NC); 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (e.g., available under the trade name OMNIRAD 907 from IGM Resins USA Inc., Charlotte, NC); 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (e.g., available under the trade name OMNIRAD 369 from IGM Resins USA Inc., Charlotte, NC); polyethylene glycol bis(β-4-[4-(2-dimethylamino-2-benzyl)butyryl)phenyl]piperazine) propionate (available under the trade name OMNIPOL 910 from IGM Resins USA Inc., Charlotte, NC); and phosphine oxide derivatives such as ethyl-2,4,6-trimethylbenzoyl phenylphosphinate (e.g., available under the trade name TPO-L from IGM Resins USA Inc., Charlotte, NC) and bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide (e.g., available under the trade name OMNIRAD 819 from IGM Resins USA Inc., Charlotte, NC).

[0116] Other available photoinitiators include, for example, pivaloin ethyl ether, anisoin ethyl ether, anthraquinones (e.g., anthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 1,4-dimethylanthraquinone, 1-methoxyanthraquinone or benzanthraquinone), halomethyltriazines, benzophenone and its derivatives, iodonium salts, titanium complexes such as bis(η-5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro 3-(1H-pyrrol-1-yl)phenyl]titanium (e.g., available under the trade name CGI 784DC from BASF, Florham Park, NJ); halomethyl-nitrobenzenes (e.g., 4-bromomethylnitrobenzene), and combinations of photoinitiators in which one component is a monoacylphosphine oxide or a bisacylphosphine oxide (e.g., available under the trade names IRGACURE1700, IRGACURE 1800 and IRGACURE 1850 from BASF, Florham Park, NJ, and under the trade name OMNIRAD 4265 from IGM Resins USA Inc., Charlotte, NC).

[0117] In some embodiments, the composition may comprise at least one filler. In some embodiments, the total amount of filler is at most 50 wt%, preferably at most 30 wt%, and more preferably at most 10 wt% of the filler. The filler may be selected from one or more materials known in the art and includes organic and inorganic fillers. Inorganic filler particles include silica, submicron silica, zirconia, submicron zirconia, and non-glassy microparticles of the type described in U.S. Patent 4,503,169 (Randklev).

[0118] Filler components include nanoscale silica particles, nanoscale metal oxide particles, and combinations thereof. Nanofillers are also described in U.S. Patents 7,090,721 (Craig et al.), 7,090,722 (Budd et al.), 7,156,911 (Kangas et al.) and 7,649,029 (Kolb et al.).

[0119] In some embodiments, the filler may be surface modified. A variety of conventional methods for surface modifying nanoparticles include, for example, adding a surface modifier (e.g., in the form of a powder or a colloidal dispersion) to the nanoparticles and allowing the surface modifier to react with the nanoparticles. Other useful surface modification methods are described, for example, in U.S. Patent Nos. 2,801,185 (Iler), 4,522,958 (Das et al.) and 6,586,483 (Kolb et al.), each incorporated herein by reference.

[0120] Exemplary Embodiment

[0121] In a first embodiment, the present disclosure provides a composition. The composition comprises a mixture of isomers, the mixture of isomers comprising at least 10% by weight of isomer A and at most 90% by weight of isomer B. Isomer A has the following formula:

[0122]

[0123] Isomer B has the following formula:

[0124]

[0125] In a second embodiment, the present disclosure provides the composition according to the first embodiment, wherein isomer A is present in an amount of 10% by weight (wt.%) to 75 wt.% of the mixture of isomers, and isomer B is present in an amount of 25% by weight to 90 wt.% of the mixture of isomers.

[0126] In a third embodiment, the present disclosure provides the composition according to the first embodiment or the second embodiment, wherein isomer A and isomer B together account for 95 wt.% to 100 wt.% of the total composition.

[0127] In a fourth embodiment, the present disclosure provides a copolymer. The copolymer comprises the following divalent units:

[0128] and

[0129]

[0130] wherein each Y is independently selected from -CH 2 -, -CH 2 CH 2 - and O.

[0131] In a fifth embodiment, the present disclosure provides a copolymer. The copolymer comprises the following divalent units:

[0132]

[0133] and

[0134]

[0135] wherein R 1 , R 2 , R 3 and R 4Each of them is independently selected from H, linear or branched C1-C20 hydrocarbon groups, linear or branched C1-C20 hetero-hydrocarbon groups, C1-C20 carbosilanes, and C5-C20 heterocycles, or R 1 and R 2 together or R 3 and R 4 together form a C1-C20 alkylene group; n is an integer from 0 to 5; and each Y is independently selected from -CH 2 -, -CH 2 CH 2 -, and O.

[0136] In a sixth embodiment, the present disclosure provides a copolymer according to the fifth embodiment, wherein in the divalent unit of formula (III), R 1 , R 2 , R 3 , and R 4 at least one of them is a C1-C7 linear alkyl group, vinyl group, or C1-C20 carbosilane.

[0137] In a seventh embodiment, the present disclosure provides a copolymer according to the fifth embodiment, wherein in the divalent unit of formula (III), R 1 , R 2 , R 3 , and R 4 each of them is H; n is 0; and Y is -CH 2 -.

[0138] In an eighth embodiment, the present disclosure provides a copolymer according to the fifth embodiment, wherein in the divalent unit of formula (III), R 1 , R 2 , R 3 , and R 4 one of them is a C6 alkyl group; the remainder of R 1 , R 2 , R 3 , and R 4 each of them is H; n is 0; and Y is -CH 2 -.

[0139] In a ninth embodiment, the present disclosure provides a copolymer according to the fifth embodiment, which comprises at least two divalent units of formula (III) that are different from each other.

[0140] In a tenth embodiment, the present disclosure provides a copolymer according to the ninth embodiment, wherein in the divalent unit of the first formula (III), R 1 , R 2 , R 3 , and R 4each of which is H; n is 0; and Y is -CH 2 -; and in the divalent unit of the second formula (III), R 1 , R 2 , R 3 and R 4 one of which is C6 alkyl, and each of the remaining parts of R 1 , R 2 , R 3 and R 4 is H; n is 0; and Y is -CH 2 -.

[0141] In the eleventh embodiment, the present disclosure provides a copolymer. The copolymer is a reaction product of a polymerizable composition comprising:

[0142]

[0143] and

[0144]

[0145] wherein each of R 1 , R 2 , R 3 and R 4 is independently selected from H, linear or branched C1 to C20 hydrocarbon groups; linear or branched C1 to C20 hetero-hydrocarbon groups, C1 to C20 carbosilanes and C5 to C20 heterocycles, or R 1 and R 2 together or R 3 and R 4 together form a C1 to C20 alkylene group; n is an integer from 0 to 5; and wherein each Y is independently selected from -CH 2 -, -CH 2 CH 2 - and O.

[0146] In the twelfth embodiment, the present disclosure provides the copolymer according to the eleventh embodiment, wherein the polymerizable composition further comprises a chain transfer agent.

[0147] In the thirteenth embodiment, the present disclosure provides the copolymer according to the eleventh or twelfth embodiment, which comprises at least two monomers of formula (C) that are different from each other, wherein in the first monomer of formula (C), R 1 , R 2 , R 3 and R 4 each of which is H; n is 0; and Y is -CH 2 -, and in the second monomer of formula (C), R1 , R 2 , R 3 and R 4 One of them is a C6 alkyl group; R 1 , R 2 , R 3 and R 4 Each of the remaining parts of and R is H; n is 0; and Y is -CH 2 -.

[0148] In the fourteenth embodiment, the present disclosure provides a copolymer according to any one of the fourth to thirteenth embodiments, wherein the copolymer is in the form of a film.

[0149] In the fifteenth embodiment, the present disclosure provides a composition. The composition comprises a solvent and a copolymer according to any one of the fourth to fourteenth embodiments.

[0150] In the sixteenth embodiment, the present disclosure provides the composition according to the fifteenth embodiment, and the composition further comprises at least one of a sensitizer, an initiator, a filler, an antioxidant, an inhibitor, a stabilizer, a colorant or a adhesion control agent.

[0151] In the seventeenth embodiment, the present disclosure provides the composition according to the sixteenth embodiment, wherein the initiator comprises at least one of a thermal initiator or a photoinitiator.

[0152] In the eighteenth embodiment, the present disclosure provides a film. The film comprises a cross-linked reaction product of a copolymer according to any one of the fourth to fourteenth embodiments.

[0153] The following examples further illustrate the advantages and embodiments of the present invention, but the specific materials, their amounts, and other conditions and details mentioned in these examples should not be construed as improper limitations of the present invention.

[0154] Example

[0155] Unless otherwise specified or readily apparent from the context, all parts, percentages, ratios, etc. in the examples and the remainder of the specification are by weight. Table 1 (below) lists the materials used in the examples and their sources.

[0156] Table 1. Table of Materials, Abbreviations, and Sources .

[0157]

[0158]

[0159] Synthesis of Norbornene Itaconimide (Mixture A)

[0160]

[0161] Into a 250 mL three-necked round-bottom flask equipped with a feed funnel, magnetic stirring, and an N 2 overlay, 16.8 g (0.15 mol) of itaconic anhydride and 100 mL of toluene were charged. 18.4 g (0.15 mol) of 5-norbornene-2-methylamine was charged into the feed funnel, and the liquid was added dropwise to the stirred mixture of toluene and itaconic anhydride while the flask was in an oil bath at 90 °C. The vial and the feed funnel were rinsed with an additional 10 mL of toluene, and this toluene was also added to the reaction mixture. After the addition was complete, the feed funnel was removed and replaced with a Dean-Stark water separator and a reflux condenser, and with the flask under a nitrogen overlay, the temperature of the oil bath was gradually increased to 145 °C to initiate toluene reflux. The apparatus was allowed to reflux overnight. Upon return, the reaction mixture was a clear reddish-brown solution, and a small amount of solid was visible on the walls of the flask. After refluxing for 20 hours, approximately 1.9 mL of water was collected in the water separator. The reaction mixture was washed twice with 100 mL portions of 1 N KOH and twice with 100 mL portions of 1 wt.% KCl solution. The toluene solution was dried over anhydrous MgSO 4 and gravity filtered through #4 filter paper to obtain a clear reddish-brown solution. The solvent was removed by rotary evaporation and then gently flushed with nitrogen to give a clear reddish-brown liquid.

[0162] The liquid was purified by Kugelrohr vacuum distillation at 140 °C to 185 °C and 500 mTorr to give a clear, colorless liquid distillate. In CDCl 3 solution by 1 1H NMR analysis of the distillate showed a clean mixture of 75% CMNB and 25% IMNB.

[0163] Synthesis of Norbornene Citraconimide (Mixture B)

[0164]

[0165] Into a 250 mL three-necked round-bottom flask equipped with a feed funnel, magnetic stirring, and an N 2Into a 250 mL three-necked round-bottom flask with an overlay, place 16.8 g (0.15 mol) of citraconic anhydride and 90 mL of toluene. Stir the mixture to dissolve the anhydride. Charge 18.4 g (0.15 mol) of 5-norbornene-2-methylamine into the addition funnel, and then add it dropwise to the mixture. Then rinse the funnel with 20 mL of toluene. When the mixture becomes cloudy and solidifies due to the precipitation of the amido acid adduct, maintain magnetic stirring. After the addition is complete, fit the flask with a Dean-Stark water separator and a condenser and transfer it to an oil bath at 90 °C, then gradually increase the temperature to 145 °C to initiate toluene reflux. After several hours, the reaction mixture melts. The reflux continues for a total of 21 hours. This gives a clear dark brown liquid reaction mixture with no trace of precipitate. 2.1 mL is collected in the water separator. Cool the reaction mixture to room temperature, then place it in a separatory funnel and wash it twice with 100 mL portions of 5 wt.% KHCO 3 solution and once with 100 mL of 2 wt.% KCl solution. Dry the toluene phase over anhydrous MgSO 4 and filter it through #4 filter paper into a 250 mL round-bottom flask. Remove the solvent by rotary evaporation to obtain a clear dark brown liquid.

[0166] Purify the liquid by Kugelrohr vacuum distillation at 145 °C to 185 °C and 1 Torr to obtain a light yellow liquid distillate. Analyze the distillate by 3 H NMR in CDCl 1 solution, which shows a clean mixture of 90% CMNB and 10% IMNB.

[0167] Synthesis of Polymer

[0168] In a 20 mL vial, prepare a catalyst solution by dissolving allyldichloride(1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene)palladium(II), tricyclohexylphosphine, and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate in 1,2-dichloroethane in the amounts listed in Table 2. This yields a clear light yellow solution.

[0169] Table 2. Composition of Catalyst Solution for Each Example

[0170]

[0171] In a 500 mL three-necked round-bottom flask equipped with a paddle stir bar and an N2 blanket, a mixture of norbornene (NB), hexylnorbornene (HNB), IMNB, and CMNB, along with an equimolar amount of 1-octene, was dissolved in toluene in the amounts listed in Table 3. The contents were then stirred using a Model 850 electric mixer from Arrow Engineering (Hillside, NJ, USA) with an analog dial at a setting of 2.

[0172]

[0173] Using a syringe with a 20-gauge needle tip, the catalyst solution was withdrawn from the vial and injected into the round-bottom flask along with the monomer mixture while stirring. The addition of the catalyst solution initiated the reaction of the monomers. The contents were polymerized at room temperature while mixing for several days.

[0174] The reaction was terminated by pipetting approximately 1 mL of pyridine into the polymerized mixture while stirring. Pyridine quenched the catalyst, rendering it inactive. The polymer was separated from the reaction mixture by very slowly pouring the polymer into a rapidly stirred large beaker containing 2 L of 2-butanone (using the same paddle stir bar). 2-Butanone served as a nonsolvent, and due to the rapid stirring, it immediately precipitated the polymer into fine threads. Once all of the reaction mixture had been added, 2-butanone was added to the round-bottom flask to precipitate any remaining reaction mixture still in the flask. The solid was then transferred to the stirred beaker. With all of the contents in the beaker, stirring was stopped and the paddle stir bar was removed. The polymer wrapped itself around the stirring blades, so a razor blade and scissors were used to help break the polymer into smaller pieces and to aid in its removal. Then the beaker was covered with aluminum foil and transferred to the refrigerator to cool overnight. The next day, the solid material was separated from the nonsolvent by vacuum filtration using a Buchner funnel. The solid material was then transferred to a large aluminum tray, which was then covered and placed in an oven to dry at 90 °C for 4 h. Table 4 lists the reaction times and yields for each example.

[0175] Table 4. Reaction Time and % Yield for Each Example

[0176] Example Reaction Time, hours Yield, % 1 166 24.6 2 144 34.5 3 96 86.6 4 94 86.9

[0177] Film Formation

[0178] In a separate 4 oz wide-mouth bottle, add approximately 2 g to 5 g of each polymer example (Examples 1 - 4) to enough toluene to prepare a 10% - 20% solid solution. Then seal the bottle and place it on a bottle roller and roll it overnight until the polymer is completely dissolved. Then pour the solution into a small glass Petri dish. Place the Petri dish uncovered in a cabinet and allow the toluene to evaporate for about 3 days to obtain a free-standing film.

[0179] For some samples, add 2 parts per hundred resin (PHR) of diisopropylbenzene peroxide thermal initiator or 1 PHR of Irgacure 819 photoinitiator to the bottle to dissolve with the polymer sample.

[0180] Crosslinking of Film

[0181] Stack the thermally crosslinked films between sheets of PTFE film and sandwich them between 2 heavy metal plates to keep the films flat. Then place this stack of films in a N 2 purged oven at room temperature. Using a temperature controller, ramp the temperature of the oven up to 200 °C at a rate of 5 °C / min. Once the temperature reaches 200 °C, hold it at that temperature for 2 hours and then cool it back down to room temperature.

[0182] Cure the photo-crosslinked films using a Fusion UV Light Hammer LHC10 Mark II (Heraeus Noblelight America, Gaithersburg, MD, USA) equipped with a D-bulb. Pass the films through the processor twice at 21 ft / min with the bulb at 100% power, which delivers a total energy of 4.1 J / cm 2 UVA, 1.3 J / cm 2 UVB, 0.6 J / cm 2 UVC, and 5.0 J / cm 2 UVV, as measured by an EITPowerPuck II (EIT, Leesburg, VA, USA). Details of the conditions and composition used for crosslinking the films can be found in Table 5.

[0183] Table 5. Conditions and Composition of Crosslinked Films

[0184] Example Starting Polymer Initiator Initiator Loading (PHR) Curing Conditions 5 Example 1 Di - tert - butyl peroxide 2 Thermal Curing 6 Example 2 Di - tert - butyl peroxide 2 Thermal Curing 7 Example 3 Di - tert - butyl peroxide 2 Thermal Curing 8 Example 4 Di - tert - butyl peroxide 2 Thermal Curing 9 Example 1 Irgacure 819 1 Photo - Curing 10 Example 2 Irgacure 819 1 Photo - Curing 11 Example 3 Irgacure 819 1 Photo - Curing 12 Example 4 Irgacure 819 1 Photo - Curing

[0185] Mechanical Property Evaluation Using DMA

[0186] Dynamic mechanical analysis was performed using a temperature ramp with oscillatory strain on a TA Instruments RSA-G2 DMA (New Castle, DE, USA) using the following parameters: equilibrated at -30 °C; isothermal for 3 minutes; ramped to 300 °C at 3 °C / min; strain = 0.1%; frequency = 1 Hz. Data are reported in Figures 13 to 16 and summarized in Table 6.

[0187] Table 6. Comparison of High - Temperature and Low - Temperature Storage Modulus E' Indicating Crosslinking Performance (Calculated Based on Starting Monomer Composition IMNB and CMNB Contents (Mole Fraction))

[0188]

[0189] DMA data revealed differences in membrane crosslinking caused by different IMNB / CMNB ratios. By examining the ratio of storage modulus E' at low temperature (30 °C) and high temperature (280 °C) (quantified as E' 30℃ / E' 280℃ ), the amount of crosslinking can be inferred. Example 2 / Example 1 and Example 4 / Example 3 are two good comparisons showing the effect of increasing IMNB; these pairs have similar NB, HNB, and amide monomer compositions but different IMNB / CMNB ratios. In both cases, the increased amount of IMNB resulted in a lower E' 30℃ / E' 280℃ , from 133 to 81.2 for Example 2 / Example 1 and from 379 to 351 for Example 4 / Example 3. This observation holds true for the photo-cured examples but not for the thermally cured examples. However, the E' 30℃ / E' 280℃ ratios for the thermally cured samples are very similar.

[0190] Another useful comparison is between samples with the same IMNB / CMNB ratio but an increased amount of these crosslinkable monomers, such as in Example 3 / Example 1 and Example 4 / Example 2. In both cases, a higher degree of crosslinking was shown in the samples with more IMNB / CMNB monomers, with an E' 30℃ / E' 280℃ of 351 to 81.2 for Example 3 / Example 1 and 379 to 133 for Example 4 / Example 2. This observation holds true for all examples. These data clearly show the benefit of a higher content of IMNB monomers for improving crosslinking in these thermosetting systems.

[0191] Dielectric Property Evaluation

[0192] Separation Column Dielectric Resonator Measurement

[0193] All split-post dielectric resonator measurements were performed at 10.1 GHz, 15.22 GHz, 24.7 GHz, and 25 °C according to standard IEC 61189-2-721. Each material was inserted between two fixed dielectric resonators. The resonant frequency and quality factor of the post are affected by the presence of the sample, and this enables the direct calculation of the complex permittivity (permittivity (ε') and dielectric loss (ε")). The geometry of the split dielectric resonator fixture used in our measurements was designed by Company QWED, Warsaw Poland. These resonators operate in the TE01d mode with only azimuthal electric field components, such that the electric field remains continuous across the dielectric interface. The split-post dielectric resonator measures the permittivity component in the plane of the sample. Ring coupling (critical coupling) was used in each of these dielectric resonator measurements. The split-post resonator measurement system was combined with a Keysight VNA (PNA N5222B type vector network analyzer and N5292A type millimeter wave test set, 900 Hz - 110 GHz). Calculations were performed with commercially available split-post resonator software from QWED to provide a powerful measurement tool for determining the complex permittivity of each sample at a specific frequency. Tan delta (tanδ) is also known as the dissipation factor in the art.

[0194] Table 7. Dielectric Properties

[0195]

[0196] Predictable modifications and changes of the present invention will be apparent to those skilled in the art without departing from the scope and essence of the present invention. The present invention should not be limited to the embodiments shown in this application for illustrative purposes.

Claims

1. A composition, the composition comprising a mixture of isomers, the mixture of isomers comprising: At least 10% by weight of isomer A, which has the following formula: and At most 90% by weight of isomer B, which has the following formula:

2. The composition according to claim 1, wherein isomer A is present in an amount of 10% by weight (wt.%) to 75 wt.% of the mixture of isomers, and isomer B is present in an amount of 25% by weight to 90% by weight of the mixture of isomers.

3. The composition according to claim 1 or claim 2, wherein isomer A and isomer B together account for 95 wt.% to 100 wt.% of the total composition.

4. A copolymer, the copolymer comprising the following divalent monomer units: where each Y is independently selected from -CH 2 -, -CH 2 CH 2 -, and O.

5. A copolymer, the copolymer comprising the following divalent monomer units: wherein R 1 , R 2 , R 3 and R 4 each independently selected from H, a linear or branched C1 to C20 hydrocarbyl group, a linear or branched C1 to C20 heterohydrocarbyl group, a C1 to C20 carbosilane, and a C5 to C20 heterocycle, or R 1 and R 2 together or R 3 and R 4 together form a C1 to C20 alkylene group; n is an integer from 0 to 5; and wherein each Y is independently selected from -CH 2 -, -CH 2 CH 2 - and O.

6. The copolymer according to claim 5, wherein in the divalent unit of formula (III), R 1 , R 2 , R 3 and R 4 at least one of which is a C1 to C7 straight-chain alkyl group, vinyl group or a C1 to C20 carbosilane.

7. The copolymer according to claim 5, wherein in the divalent unit of formula (III), R 1 , R 2 , R 3 and R 4 are each H; n is 0; and Y is -CH 2 -.

8. The copolymer according to claim 5, wherein in the divalent unit of formula (III), one of R 1 , R 2 , R 3 and R 4 is a C6 alkyl group; each of the remaining portions of R 1 , R 2 , R 3 and R 4 is H; n is 0; and Y is -CH 2 -.

9. The copolymer according to claim 5, the copolymer comprising at least two divalent units of formula (III) that are different from each other.

10. The copolymer according to claim 9, wherein in the divalent unit of the first formula (III), each of R 1 , R 2 , R 3 and R 4 is H; n is 0; and Y is -CH 2 -; and in the divalent unit of the second formula (III), one of R 1 , R 2 , R 3 and R 4 is C6 alkyl, and each of the remaining parts of R 1 , R 2 , R 3 and R 4 is H; n is 0; and Y is -CH 2 -.

11. A copolymer, the copolymer being a reaction product of a polymerizable composition, the polymerizable composition comprising: wherein R 1 , R 2 , R 3 and R 4 each independently selected from H, a linear or branched C1 to C20 hydrocarbyl group; a linear or branched C1 to C20 heterohydrocarbyl group, a C1 to C20 carbosilane, and a C5 to C20 heterocycle, or R 1 and R 2 together or R 3 and R 4 together form a C1 to C20 alkylene group; n is an integer from 0 to 5; and wherein each Y is independently selected from -CH 2 -, -CH 2 CH 2 -, and O.

12. The copolymer according to claim 11, wherein the polymerizable composition further comprises a chain transfer agent.

13. The copolymer according to claim 11 or claim 12, said copolymer comprising at least two monomers of formula (C) that are different from each other, wherein in the first monomer of formula (C), R 1 , R 2 , R 3 and R 4 are each H; n is 0; and Y is -CH 2 -, and in the second monomer of formula (C), one of R 1 , R 2 , R 3 and R 4 is C6 alkyl; the remainder of R 1 , R 2 , R 3 and R 4 are each H; n is 0; and Y is -CH 2 -.

14. The copolymer according to any one of claims 4 to 13, wherein the copolymer is in the form of a film.

15. A composition, the composition comprising a solvent and the copolymer according to any one of claims 4 to 14.

16. The composition according to claim 15, the composition further comprising at least one of a sensitizer, an initiator, a filler, an antioxidant, an inhibitor, a stabilizer, a colorant, or a tack control agent.

17. The composition according to claim 16, wherein the initiator comprises at least one of a thermal initiator or a photoinitiator.

18. A film, the film comprising a crosslinked reaction product of the copolymer according to any one of claims 4 to 14.

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