Monomer, polymerizable composition, and polymers derived therefrom

Abstract

A monomer represented by the following formula: Wherein: each R1 independently represents an alkyl group having 1 to 4 carbon atoms; Z represents an alkyl group having 1 to 40 carbon atoms, or a group represented by the following formula. Wherein: each L independently represents a divalent alkyl group having 1 to 12 carbon atoms, each n independently represents 0, 1, or 2; and p represents 0 or 1. The polymerizable composition includes monomers and can be polymerized to form polymerizable compositions. Polymers prepared by polymerizing the monomers are also disclosed.

Description

[Technical Field]

[0001] This disclosure relates broadly to silicone monomers, including polymerizable components thereof and polymers derived therefrom. [Previous Technology]

[0002] Fifth-generation wireless (5G) is the latest iteration of cellular technology, designed to significantly increase the speed and responsiveness of wireless networks. With 5G, data can be transmitted at multigigabit speeds over wireless broadband connections, with estimated potential peak speeds of up to 20 gigabits per second (Gbps). This speed increase is achieved by using radio waves at higher frequencies than current cellular networks. However, higher-frequency radio waves have a narrower frequency range than those used by previous networks. Therefore, to ensure wider coverage, 5G networks operate in three frequency bands: low, medium, and high. 5G networks will consist of up to three different types of cellular networks, each requiring different antennas, and each network will have different trade-offs between download speed, distance, and service area. 5G handsets and wireless devices will connect to the network using the fastest antennas within their range.

[0003] Low-frequency 5G uses a frequency range similar to current 4G phones, 600 to 700 MHz, providing download speeds slightly higher than 4G: 30 to 250 megabits per second (Mbit / s). Low-frequency mobile base stations will have a range and coverage area similar to current 4G mobile base stations. Mid-frequency 5G uses microwaves from 2.5 to 3.7 GHz, currently achieving speeds of 100 to 900 Mbit / s, with each mobile base station providing a service radius of up to several miles. High-frequency 5G uses frequencies from 25 to 39 GHz, close to the lower end of the millimeter wave band, to achieve download speeds of 1 to 3 gigabits per second (Gbit / s), equivalent to wired networks.

[0004] The advancement of communication technology towards 5G places higher demands on the properties of materials used in electronic applications. Examples include: dielectric constant Dk < 3.0, loss factor Df < 0.003 at 30 GHz, low thermal expansion (CTE: < 50 μm / (mπ℃), and good thermal oxidation stability (loss < 5 wt%) at approximately > 50 °C above the glass transition temperature (Tg) and / or melt transition temperature (Tm).

[0005] Many materials used in the telecommunications industry today do not perform well at 5G frequencies. Therefore, the higher frequencies of 5G require the identification and development of materials that can function at these frequencies without interfering with the normal functioning of electronic devices when communicating at high-frequency wavelengths. [Summary of the Invention]

[0006] Polyolefin thermosets offer the desired combination of: minimized signal loss at 5G / 6G, toughness, hydrolysis resistance, high service temperature (Tg up to 350°C), low viscosity, and simpler manufacturing (e.g., good adhesion without surface pretreatment). The low dielectric constant (Dk) and low loss factor (Df) suitable for 5G are achieved through a chemical structure that responds to an oscillating electric field with minimal polarizability (where Dk is a homophase response and Df is a heterophase loss response). For polymers, this can be achieved using CC, CH, CF, and C-Si bonds, and by avoiding π-bonding, aromaticity, polarity, and heavier atoms. Larger size scaling factors (e.g., crystallinity and polymer architecture) also affect Dk and Df. Olefin (CC and CH) structures also exhibit excellent hydrolysis and alkali resistance. Incorporating norepinephrine-based cycloolefin structures provides a means to improve thermal properties without using aromatic groups that are detrimental to dielectric properties.

[0007] This disclosure provides monomers based on norcamphene containing silicon side groups. These norcamphene-based monomers can be polymerized by ring-opening metathesis polymerization (ROMP) or addition polymerization (AP) to produce polymers suitable for applications requiring low dielectric constant (Dk) and dissipation factor (Df) and / or hydrolysis / chemical resistance for 5G / 6G. These nocamphenyl monomers can have a combination of the following benefits: (1) higher molecular weight, lower volatility, and lower odor compared to nocamphene; (2) increased mass and absence of heteroatoms that are harmful to Dk and Dff; (3) easy formulation into low viscosity olefin thermosets; and (4) the ability to customize the glass transition temperature of derivative polymers by changing the length and type of silicon-containing side groups and by using them alone or in combination with commercially available nocamphene-based monomers (e.g., nocamphene, hexylnocamphene, decylnocamphene, ethylidene nocamphene).

[0008] In one state, this disclosure provides a monomer represented by the following formula:

[0008] Among them:

[0008] Each R1 independently represents an alkyl group having 1 to 4 carbon atoms;

[0008] Z represents an alkyl group having 1 to 40 carbon atoms, or a group represented by the following formula.

[0008]

[0008] Among them:

[0008] Each L independently represents a divalent alkyl group having 1 to 12 carbon atoms.

[0008] Each n independently represents 0, 1, or 2; and

[0008] p represents 0 or 1.

[0009] The monomers disclosed herein may be used, for example, as components of polymerizable compositions.

[0010] In another embodiment, this disclosure provides a polymerizable composition comprising a monomer according to this disclosure and a curing agent for the monomer.

[0011] In another embodiment, this disclosure provides a polymerizable composition which can be prepared by polymerization of the polymerizable composition according to this disclosure.

[0012] In another embodiment, this disclosure provides a polymer comprising tetravalent or octavalent monomer units represented by the following formula.

[0012] Among them:

[0012] Each R1 independently represents an alkyl group having 1 to 4 carbon atoms;

[0012] Each n independently represents 0 or 1; and

[0012] Z represents an alkyl group having 1 to 40 carbon atoms, or a group represented by the following formula.

[0012]

[0012] Among them:

[0012] Each L independently represents a divalent alkyl group having 1 to 12 carbon atoms.

[0012] p represents 0 or 1.

[0013] In another embodiment, this disclosure provides a polymer comprising a divalent or tetravalent monomer unit represented by the following formula.

[0013] Among them:

[0013] Each R1 independently represents an alkyl group having 1 to 4 carbon atoms;

[0013] Z represents an alkyl group having 1 to 40 carbon atoms, or a group represented by the following formula.

[0013]

[0013] Among them:

[0013] Each L independently represents a divalent alkyl group having 1 to 12 carbon atoms.

[0013] Each n independently represents 0, 1, or 2; and

[0013] p represents 0 or 1.

[0014] As used herein:

[0014] The term "carbosilane" refers to a compound composed of carbon atoms, silicon atoms and hydrogen atoms.

[0015] The features and advantages of the present invention will be further understood once the implementation methods and the appended claims are taken into consideration.

Implementation Method

[0016] The individual entity according to this disclosure can be represented by the following formula.

[0016] Each R1 independently represents an alkyl group having 1 to 4 carbon atoms, such as methyl ethyl, propyl or butyl.

[0017] Z may represent an alkyl group having 1 to 40 carbon atoms (preferably 1 to 30 carbon atoms, more preferably 1 to 18 carbon atoms). Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl (including cyclohexyl), heptyl (including methylcyclohexyl), octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, triacontyl, and tetradecyl.

[0018] Alternatively, Z can be expressed by the following formula.

[0018] Each L independently represents a divalent alkyl group having 1 to 12 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl).

[0019] Each p represents 0 or 1. In many embodiments, p=0.

[0020] Each n independently represents 0, 1, or 2. In many embodiments, n=0.

[0021] In some preferred embodiments, the monomer according to this disclosure is represented by the following formula:

[0021] or

[0021] The monomer (where n=1 or 2) can be produced from its corresponding norbornel precursor by conventional synthetic techniques (such as Diels-Alder condensation with cyclopentadiene).

[0022] The monomer according to this disclosure can be manufactured, for example, by hydrosilicification of carbosilanes and olefins in the presence of a hydrosilicification catalyst, as shown below.

[0022] or

[0022]

[0022] 5-Vinyl-2-norbornene is available from many commercially available sources. Alternatively, various synthetic methods are known in this art. Hydrosilanes represented by the following formula...

[0022] It can be obtained from commercially available suppliers (e.g., Gelest Inc., Morrisville, Pennsylvania, and Millipore-Sigma, Saint Louis, Missouri) or prepared by known methods (e.g., by hydrosilicification of the corresponding dialkyl dihydrosilane and the corresponding divinyl dialkyl silane or diene in the presence of a hydrosilicification catalyst).

[0023] Examples of hydrosiliconization catalysts include platinum-based catalysts such as chloroplatinic acid, solutions of chloroplatinic acid in alcohols, reaction products of chloroplatinic acid with alcohols, reaction products of chloroplatinic acid with olefin compounds, reaction products of chloroplatinic acid with vinyl-containing siloxanes, platinum-olefin complexes, platinum-vinyl-containing siloxane complexes; and platinum group-based catalysts such as rhodium complexes and ruthenium complexes. A particularly useful catalyst (Karstedt's catalyst) is a platinum-divinyltetramethyldisiloxane complex in vinyl-terminated polydimethylsiloxane (PDMS) containing 3 wt% platinum concentration (concentration of pure platinum metal), available under product code SIP6830.3 from Gelest, Morrisville, Pennsylvania. Hydrosiliconization catalysts can be used by dissolving or dispersing in solvents such as isopropanol or toluene, or polysiloxane oils.

[0024] As determined by weight of platinum group metals, the amount of hydrosilicification catalyst can generally be based on the solid content of 100 parts by weight of polysiloxane pressure-sensitive adhesive of about 5 ppm or more, or about 10 ppm or more, and about 2,000 ppm or less, or about 500 ppm or less.

[0024] Polymerizable composition

[0025] The monomers according to this disclosure are generally polymerizable and can be included in a polymerizable composition together with a curing agent for the monomer and optional comonomers. Optional comonomers and additives can be included in the polymerizable composition in any amount, depending on the desired physical properties of the resulting polymer.

[0026] As used herein, the term "curative" means any compound or combination of compounds that can cause polymerization or copolymerization of (a plurality of) monomers and (a plurality of) optional comonomers. The selection of curative, amount, and polymerization conditions will necessarily depend at least in part on the type of polymerization selected (e.g., radical polymerization initiator, addition polymerization catalyst, or ring-opening metathesis polymerization (ROMP) catalyst, and within the capabilities of one skilled in the art).

[0027] The curing agent is generally included in at least an effective amount. The term "effective amount" means an amount sufficient to cause the polymerizable composition to polymerize under the polymerization conditions. Generally, the total amount of curing agent is used in an amount ranging from 0.0001% to 20% by weight (preferably 0.001% to 5% by weight) based on the total weight of the polymerizable composition, but this is not required.

[0027] Free radical polymerization

[0028] Suitable free radical polymerization initiators may include, for example, thermal and / or photoinitiators. Exemplary thermal initiators include organic peroxides (e.g., diacylperoxide, peroxyketal, ketone peroxide, hydroperoxide, dialkyl peroxide, peroxy ester, and peroxydicarbonate) and azo compounds (e.g., azobis(isobutyronitrile)). Examples of free radical photoinitiators include: 2-benzyl-2-(dimethylamino)-4'-morpholinyl-butyric acid phenoxy ketone; 1-hydroxycyclohexyl-phenyl ketone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-prop-1-one; 4-methylbenzophenone; 4-phenylbenzophenone; 2-hydroxy-2-methyl-1-phenylpropanone; 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl Acetone; 2,2-Dimethoxy-2-phenylacetophenone; 4-(4-methylphenylthio)benzophenone; benzophenone; 2,4-diethylthioxanthraphenone; 4,4'-bis(diethylamino)-benzophenone; 2-isopropylthioxanthraphenone; acetylphosphine oxide derivatives, acetylphosphinate derivatives, and acetylphosphine derivatives (e.g., phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (which can be OMNIRAD) 819 (obtained from IGM Resins, St. Charles, Illinois), phenyl bis(2,4,6-trimethylbenzoyl)phosphine (e.g., OMNIRAD 2100, obtained from IGM Resins), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide (e.g., OMNIRAD 8953X, obtained from IGM Resins), isopropoxyphenyl-2,4,6-trimethylbenzoylphosphine oxide, dimethyl terpenoid phosphonate, ethyl (2,4,6-trimethylbenzoyl)phenyl phosphinate (e.g., OMNIRAD TPO-L, obtained from IGM Resins); bis(cyclopentadienyl)bis[2,6-difluoro-3-(1-pyrrolidinyl)phenyl]titanium (e.g., OMNIRAD 784, obtained from IGM Resins). Resins (obtained); and their combinations.

[0029] Exemplary free radical copolymerizable monomers may include olefins having one or more carbon-carbon double bonds and having 1 to 18 carbon atoms (e.g., ethylene, propylene, butene, butadiene, isoprene, hexene, cyclohexene, octene, decene, hexadecene, or octadecene). While other free radical polymerizable monomers may be included, they preferably do not contain heteroatoms other than silicon (e.g., O, N, P, S).

[0029] Addition Polymerization

[0030] As used herein, the term "addition polymerization" (sometimes also referred to in this art as vinyl-addition polymerization) refers to a polymerization process involving an olefin coordination-insertion pathway mediated by an organometallic catalyst. A schematic diagram is shown in Scheme I below.

[0030] Wherein MH indicates an addition polymerization catalytic species having a metal hydride bond, and p represents an integer greater than 10. The mechanism and final product of this process differ from commonly used alternative polymerization methods such as ring-opening metathesis polymerization (ROMP). ROMP polymers contain double bonds in their polymer backbone, while the addition polymers according to this disclosure do not contain double bonds in their polymer backbone.

[0031] Numerous addition polymerization catalysts are known in this art and are generally based on organometallic catalysts containing Ti, Zr, Cr, Co, Fe, Cu, Ni, or Pd. Among these catalysts, addition polymerization catalysts containing Ni or Pd are the most commonly used. A large body of literature exists regarding organometallic addition polymerization catalysts, particularly those for norcamphene-type monomers. Typically, the active catalyst species is a cationic transition metal complex having alkyl or allyl ligands and weakly coordinating anions. Addition polymerization catalysts can incorporate a single active species (or a combination thereof) into the curable composition disclosed herein, or can be provided as a combination of pre-catalyst and activator precursors; for example, as commonly used in this art. Typically, the pre-catalyst provides the active site for the olefin insertion mechanism that forms the addition polymer. Combining with an activator converts the pre-catalyst into its active form.

[0032] In some embodiments, suitable catalysts and pre-catalyst / activator combinations for the addition polymerization of cyclic olefins comprising a single carbon-carbon ring may include various Group 10 (i.e., Group 10 of the periodic table) catalysts or pre-catalyst / activator combinations; for example, Ni-based addition polymerization catalysts, Pd-based addition polymerization catalysts, or Pt-based addition polymerization catalysts. In some preferred embodiments, the late metal (e.g., Ni-based or Pd-based) pre-catalyst has an allyl / alkyl ligand and a chloride ligand. These pre-catalysts are activated by a monovalent metal (Li, Na, Ag) salt that adds a weakly coordinating anion (e.g., BF4, tetra(3,5-bis(trifluoromethyl)phenyl)borate (BARF), or perfluorotetraphenylborate).

[0033] Exemplary suitable precatalysts include: trifluoroacetic acid (1,1-dimethylallyl)palladium (triisopropylphosphine), trifluoroacetic acid (2-chloroallyl)palladium (triisopropylphosphine), (allyl)palladium-(tricyclohexylphosphine), p-toluylsulfonic acid (allyl)palladium (tricyclohexylphosphine), trifluoromethanesulfonic acid (allyl)palladium (tricyclohexylphosphine), (allyl)palladium (tricyclohexylphosphine)trifluoromethaneimide, trifluoroacetic acid (allyl)palladium (tricyclohexylphosphine), trifluoromethanesulfonic acid (allyl)palladium (triisopropylphosphine), (allyl)palladium (triisopropylphosphine)trifluoromethaneimide, trifluoroacetic acid (allyl)palladium (triisopropylphosphine), trifluoromethanesulfonic acid (allyl)palladium (trinaphthylphosphine), acetic acid (allyl)palladium (tri-ortho) Tolylphosphine), (allyl)palladium nitrate (tri-o-tolylphosphine), (allyl)palladium trifluoromethanesulfonic acid (tri-o-tolylphosphine), (allyl)palladium trifluoromethanesulfonic acid (triphenylphosphine), (allyl)palladium (triphenylphosphine)trifluoromethaneimine, (allyl)palladium trifluoromethanesulfonic acid (tricyclopentylphosphine), (allyl)palladium chloride (tri-o-tolylphosphine), (allyl)Pd(AsPh3)Cl, (allyl)Pd(PPh3)Cl, (allyl)Pd(PCy3)C6F5, (allyl)Pd(Pi-Pr3)C6F5, (allyl)Pd(PMe3)OC(O)CH2CH=CH2, (allyl)Pd(SbPh3)Cl, (C2H5)Pd(PM e3)2Br, (C2H5)Pd(PMe3)2Br, (C2H5)Pd(PMe3)2Cl(Ph), (CH3)Pd(P(i-Pr)3)2O3SCF3, (CH3)Pd(PMe2Ph)2Cl, (CH3)Pd(PMe3)2Cl, (CH3)Pd(PMe3)NO3, trifluoromethanesulfonic acid (crotyl)palladium (tricyclohexylphosphine), trifluoromethanesulfonic acid (crotyl)palladium (tricyclopentylphosphine), trifluoromethanesulfonic acid (crotyl)palladium (triisopropylphosphine), dichloride (cyclooctadiene)palladium(II), chloride (hydrogen ion)palladium bis(tricyclohexylphosphine), formic acid (hydrogen ion)palladium bis(tricyclohexylphosphine), nitrate (hydrogen ion)palladium bis(tricyclohexylphosphine) The following compounds are listed: trifluoromethanesulfonic acid (hydrogen ion)palladium bis(tricyclohexylphosphine), trifluoroacetic acid (hydrogen ion)palladium bis(tricyclohexylphosphine), (hydrogen ion)palladium bis(triisopropylphosphine), trifluoromethanesulfonic acid (hydrogen ion)palladium bis(triisopropylphosphine), (Me2NCH2C6H4)Pd(O3SCF3)P(cyclohexyl)3, acetate (methylallyl)palladium (tricyclohexylphosphine), chloride (methylallyl)palladium (tricyclohexylphosphine), trifluoromethanesulfonic acid (methylallyl)palladium (tricyclohexylphosphine), (methylallyl)palladium (tricyclohexylphosphine)trifluoromethaneimine, trifluoroacetic acid (methylallyl)palladium (tricyclohexylphosphine), acetate (methylallyl)-palladium (tricyclopentylphosphine), chloride (methylallyl)palladium (tricyclopentylphosphine).Trifluoromethanesulfonic acid (methylallyl)palladium (tricyclopentylphosphine), (methylallyl)palladium (tricyclopentylphosphine)trifluoromethaneimide, trifluoroacetic acid (methylallyl)palladium (tricyclopentylphosphine), acetic acid (methylallyl)palladium-(triisopropylphosphine), methylallyl)palladium chloride (triisopropylphosphine), trifluoromethanesulfonic acid (methylallyl)-palladium (triisopropylphosphine), (methylallyl)palladium (triisopropylphosphine)trifluoromethaneimide, trifluoroacetic acid (methylallyl)palladium (triisopropylphosphine), (methylallyl)Pd(AsPh3)Cl, (methylallyl)-Pd(P[(OCH2)3]CH)Cl, (methylallyl)Pd(PBu3)Cl, (methylallyl)Pd(PPh3)C l、(methylallyl)Pd(SbPh3)Cl、(Ph)Pd(PMe3)2Br、(PMe3)2Br、(η1-benzyl)Pd(PEt3)2Cl、[(allyl)Pd(HOCH3)(Pi-Pr3)][B(O2-3,4,5,6-Br4C6)2]、[(allyl)Pd(HOCH3)(Pi-Pr3)][B(O2-3,4,5,6-Cl4C6)2]、[(allyl)Pd(HOCH3)(Pi-Pr3)]-[B(O2C6H4)2]、[(allyl)Pd(OEt2)(PCy3)][BF4]、[(allyl)Pd(OEt2)(PCy3) [PF6], [(allyl)Pd(OEt2)(P-iPr3)], [(allyl)Pd(OEt2)(Pi-Pr3)][BPh4], [(allyl)Pd(OEt2)(Pi-Pr3)][ClO4], [(allyl)Pd(OEt2)(PPh3)][SbF6], [(allyl)Pd(OEt2)(Pi-Pr3)][PF6], [(allyl)Pd(OEt2)(PPh3)][BF4], [(allyl)Pd(OEt2)(PPh3)][PF6], trifluoromethanesulfonic acid [(dimethylamino)methyl]phenyl-C,N-}-palladium (tricyclohexylphosphine), [SbF6][(allyl)Pd(OEt2)(PPh3)][PF6], trifluoromethanesulfonic acid [(dimethylamino)methyl]phenyl-C,N-}-palladium (tricyclohexylphosphine), [SbF6][(allyl)Pd(OEt2)(PPh3)][PF6], trifluoromethanesulfonic acid [(dimethylamino)methyl]phenyl-C,N-}-palladium (tricyclohexylphosphine), [SbF6][(allyl)Pd(OEt2)(PPh3)][P-iPr3] [Propyl)-Pd(OEt2)(Pi-Pr3)][BF4], 2-[(dimethylamino)methyl]phenyl-C,N-}-palladium (tricyclohexylphosphine), dibromobis(benzonitrile)palladium(II), dichlorobis(acetone)palladium(II), dichlorobis-(acetonitrile)-palladium(II), dichlorobis(benzonitrile)palladium(II), bis(trifluoroacetic acid)palladium(II)bis(tricyclohexylphosphine), palladium(II)diacetate bis(tricyclohexylphosphine), palladium(II)dibromide bis(tricyclohexylphosphine), palladium(II)dichloride bis(tricyclohexylphosphine), bis(trifluoroacetic acid)palladium(II)di(triisopropylphosphine), palladium(II)diacetate bis(triisopropylphosphine), palladium(II)dibromide bis(triisopropylphosphine),Palladium(II) dichloride bis(triisopropylphosphine), bis(trifluoroacetic acid)palladium(II) bis(triphenylphosphine), palladium(II) diacetate bis(triphenylphosphine), palladium(II) dibromide bis(triphenylphosphine), palladium(II) dichloride bis(triphenylphosphine), bis(trifluoroacetic acid)palladium(II) bis(tri-p-tolylphosphine), palladium(II) diacetate bis(tri-p-tolylphosphine), palladium(II) dichloride bis(tri-p-tolylphosphine), palladium(II) dichloride bis(tri-p-tolylphosphine), palladium(II) ethylhexanoate, palladium(II) acetylacetonate, palladium(II) bis(trifluoroacetic acid)palladium(II), palladium(II) ethylhexanoate, Pd(acetate)2(PPh3)2, Pd (PMe3)2Cl, (CH3)Pd, PdBr2(P(p-tolyl)3)2, PdBr2(PPh3)2, PdCl2(P(cyclohexyl)3)2, PdCl2(P(o-tolyl)3)2, PdCl2(PPh3)2; Platinum chloride (II); Platinum bromide (II), Platinum dichloride bis(triphenylphosphine), trans-PdCl2(PPh3)2, Nickel trifluoromethanesulfonate (methylallyl)-(tricyclohexylphosphine), Nickel acetylacetonate, Nickel carboxylate, Nickel chloride (II), Nickel bromide (II), Nickel ethylhexanoate, Nickel trifluoroacetate (II), Nickel hexafluoroacetylacetonate (II), NiCl2(PPh3) 2. NiBr2P (p-Tolyl) 3) 2. Allyl chloride (tricyclohexylphosphine), trifluoromethanesulfonic acid (allyl) platinum (tricyclohexyl-phosphine), allyl chloride [1,3-bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazolium-2-ylidene]palladium(II), allyl chloride [1,3-bis(2,6-di-isopropylphenyl)imidazolium-2-ylidene]palladium(II), chloro[(1,2,3-η)-3-phenyl-2-propenyl][1,3-bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazolium-2-ylidene]palladium(II), chloro[(1,2,3-η)-3-phenyl-2-propenyl][1,3-bis( [2,6-Di-isopropylphenyl)imidazolium-2-ylidene]palladium(II), allyl chloride [1,3-bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazolium-2-ylidene]nickel(II), allyl chloride [1,3-bis(2,6-di-isopropylphenyl)imidazolium-2-ylidene]nickel(II), chloro[(1,2,3-η)-3-phenyl-2-propenyl][1,3-bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazolium-2-ylidene]nickel(II), and chloro[(1,2,3-η)-3-phenyl-2-propenyl][1,3-bis(2,6-di-isopropylphenyl)imidazolium-2-ylidene]nickel(II).

[0034] The addition of a Lewis base that coordinates with a metal atom can improve the activity of the addition polymerization catalyst and / or the pre-catalyst. That is, the Lewis base bonds with the metal atom by sharing its lone pair electrons. Any Lewis base known in this art can be used for this purpose. Preferably, the Lewis base can be readily dissociated under polymerization conditions.

[0035] Typical 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, triarylalkylphosphine oxides, and various combinations thereof; substituted and unsubstituted pyridines; substituted and unsubstituted pyridines; phosphites, including substituted and unsubstituted trialkyl phosphites, triaryl phosphites, triarylalkyl phosphites, and various combinations thereof; phosphines, including substituted and unsubstituted trialkylphosphites, triarylphosphites, triarylalkyl phosphites, and various combinations thereof; phosphines, including substituted and unsubstituted trialkylphosphites, triarylphosphites, triarylalkylphosphites, and various combinations thereof; alkylphosphites, arylphosphites, and aralkylphosphines. Various other Lewis bases that may be used include various ethers, alcohols, ketones, amines, and anilines, arsines, and phosphines. In some embodiments, the Lewis base may be selected from acetonitrile, propionitrile, n-butyronitrile, tri-butyronitrile, benzyl nitrile (C6H5CN), 2,4,6-trimethylbenzyl nitrile, phenylacetonitrile (C6H5CH2CN), 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-tri-butylpyridine, 2,4-di-tri-butylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine The following are compounds: pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran, benzophenone, triphenylphosphine oxide, triphenyl phosphate, and PR13, wherein each R1 is independently selected from methyl, ethyl, (C3-C6)alkyl, substituted or unsubstituted (C3-C7)cycloalkyl, (C6-C10)aryl, (C6-C10)aralkyl, methoxy, ethoxy, (C3-C6)alkoxy, substituted or unsubstituted (C3-C7)cycloalkoxy, (C6-C10)aryloxy, and (C6-C10)aralkyloxy. Representative examples of PR13 include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, triterpenoid phosphine, tricyclopentylphosphine, triallylphosphine, tricyclohexylphosphine, triphenylphosphine, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, triterpenoid phosphite, tricyclopentyl phosphite, triallyl phosphite, tricyclohexyl phosphite, and triphenyl phosphite.

[0037] Other examples of organophosphorus compounds suitable as Lewis bases include phosphonates and phosphonite ligands. Representative examples of phosphonate ligands include methyl diphenylphosphonate, ethyl diphenylphosphonate, isopropyl diphenylphosphonate, and phenyl diphenylphosphonate. Representative examples of phosphonite ligands include diphenylphenylphosphonite, dimethylphenylphosphonite, diethylmethylphosphonite, diisopropylphenylphosphonite, and diethylphenylphosphonite.

[0038] If added, Lewis bases can generally be added in excess at stoichiometric levels, but this is not necessary.

[0039] Exemplary activators include: lithium tetra(2-fluorophenyl)borate, sodium tetra(2-fluorophenyl)borate, silver tetra(2-fluorophenyl)borate, thallium tetra(2-fluorophenyl)borate, lithium tetra(3-fluorophenyl)borate, sodium tetra(3-fluorophenyl)borate, silver tetra(3-fluorophenyl)borate, thallium tetra(3-fluorophenyl)borate, ferrocene tetra(3-fluorophenyl)borate, ferrocene tetra(pentafluorophenyl)borate, lithium tetra(4-fluorophenyl)borate, sodium tetra(4-fluorophenyl)borate, silver tetra(4-fluorophenyl)borate, thallium tetra(4-fluorophenyl)borate, lithium tetra(3,5-difluorophenyl)borate, sodium tetra(3,5-difluorophenyl)borate, thallium tetra(3,5-difluorophenyl)borate, thallium tetra(3,5-difluorophenyl)borate, and tetra(3,5-difluorophenyl)boronic acid. Triphenylmethyl ester, 2,6-dimethylphenylammonium tetra(3,5-difluorophenyl)borate, lithium tetra(pentafluorophenyl)borate, lithium tetra(pentafluorophenyl)borate (ether), lithium tetra(pentafluorophenyl)borate (ether), lithium tetra(pentafluorophenyl)borate (ether), lithium tetra(2,3,4,5-tetrafluorophenyl)borate, lithium tetra(3,4,5,6-tetrafluorophenyl)borate, lithium tetra(1,2,2-trifluorovinyl)borate, lithium tetra(3,4,5-trifluorophenyl)borate, methyl-perfluorophenyl)borate, phenyl-perfluorophenyl)borate, lithium tetra(isopropanol)tetra(pentafluorophenyl)borate, lithium tetra(methanol)tetra(pentafluorophenyl)borate, silver tetra(pentafluorophenyl)borate, silver tetra(pentafluorophenyl)borate (toluene), silver tetra(pentafluorophenyl)borate (xylyl) Triphenylmethyl tetra(pentafluorophenyl)borate, Triphenylmethyl tetra(4-triisopropylsilyltetrafluorophenyl)borate, Triphenylmethyl tetra(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, Thallium tetra[3,5-bis(trifluoromethyl)phenyl]borate, 2,6-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra[3,5-bis(trifluoromethyl)phenyl]borate, Lithium triphenylsiloxytris(pentafluorophenyl)borate, Sodium triphenylsiloxytris(pentafluorophenyl)borate, Sodium tetra(2,3,4,5-tetrafluorophenyl)borate, Sodium tetra(3,4,5,6-tetrafluorophenyl)borate, Sodium tetra(1,2,2-trifluorovinyl)borate, Sodium (3,4,5-trifluorophenyl)borate, sodium methylpheno-(perfluorophenyl)borate, sodium phenylpheno-(perfluorophenyl)borate, thallium tetra(2,3,4,5-tetrafluorophenyl)borate, thallium tetra(3,4,5,6-tetrafluorophenyl)borate, thallium tetra(1,2,2-trifluorovinyl)borate, thallium tetra(3,4,5-trifluorophenyl)borate, sodium methylpheno-(perfluorophenyl)borate, thallium phenylpheno-(perfluorophenyl)borate, triphenylmethyl tetra(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyl tetra(3,4,5,6-tetrafluorophenyl)borate, triphenylmethyl tetra(1,2,2-trifluorovinyl)borate, triphenylmethyl tetra(3,4,5-trifluorophenyl)borate, triphenylmethyl methyl pentafluorophenyl)borate,Triphenylmethyl phenyltrifluorophenyl borate, silver tetra[3,5-bis(trifluoromethyl)phenyl]borate, silver tetra[3,5-bis(trifluoromethyl)phenyl]borate (toluene), thallium tetra[3,5-bis(trifluoromethyl)phenyl]borate, lithium hexyltrifluorophenyl borate, lithium triphenylsiloxytrifluorophenyl borate, lithium (octoxy)trifluorophenyl borate, lithium tetra(3,5-bis(trifluoromethyl)phenyl)borate, sodium tetra(pentafluorophenyl)borate, triphenylmethyl tetra(pentafluorophenyl)borate, sodium (octoxy)trifluorophenyl borate, sodium tetra(3,5-bis(trifluoromethyl)phenyl)borate, potassium tetra(pentafluorophenyl)borate, triphenylmethyl tetra(pentafluorophenyl)borate, (octoxy)trifluorophenyl borate Potassium, potassium tetra(3,5-bis(trifluoromethyl)phenyl)borate, magnesium tetra(pentafluorophenyl)borate, magnesium tetra(octoxy)tris(pentafluorophenyl)borate, magnesium tetra(3,5-bis(trifluoromethyl)phenyl)borate, calcium tetra(pentafluorophenyl)borate, calcium tetra(octoxy)tris(pentafluorophenyl)borate, calcium tetra(3,5-bis(trifluoromethyl)phenyl)borate, lithium tetra[3,5-bis[1-methoxy-2,2,2-trifluoro-1-trifluoromethyl)ethyl]phenyl]borate, sodium tetra[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, silver tetra[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, Thallium tetroxide-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]boron, lithium tetroxide-5-(trifluoromethyl)phenyl]boron, sodium tetroxide-5-(trifluoromethyl)phenyl]boron, silver tetroxide-5-(trifluoromethyl)phenyl]boron, thallium tetroxide-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]boron, thallium tetroxide-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]boron, thallium tetroxide-1-(2,2,2-trifluoroethoxy)-1- Lithium [(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, sodium [3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, silver [3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, thallium [3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, trimethylsilane-onium tetra(pentafluorophenyl)borate, trimethylsilane-onium tetra(pentafluorophenyl)borate ether, triethylsilane-onium tetra(pentafluorophenyl)borate,Triphenylsilane-1,4-dimethyl ... Tribenzylsilanetonium, trimethylsilanetonium tetra(2,3,4,5-tetrafluorophenyl)borate, triethylsilanetonium tetra(2,3,4,5-tetrafluorophenyl)borate, triphenylsilanetonium tetra(2,3,4,5-tetrafluorophenyl)borate, tribenzylsilanetonium tetra(2,3,4,5-tetrafluorophenyl)borate, triphenylsilanetonium tetra(2,3,4,5-tetrafluorophenyl)borate Trimethylsilanetonium borate, tetra(2,3,4,5-tetrafluorophenyl)boronium borate, tetra(3,4,5-trifluorophenyl)boronium borate, tetra(3,4,5-trifluorophenyl)aluminate tribenzylsilanetonium, methyltriphenyl(3,4,5-trifluorophenyl)aluminate tribenzylsilanetonium, tetra(1,2,2-trifluorovinyl)boronium Ethylsilane-onium, tricyclohexylsilane-onium tetra(2,3,4,5-tetrafluorophenyl)borate, dimethyloctadecylsilane-onium tetra(pentafluorophenyl)borate, trimethylsilane-onium methylphenoxy(2,3,4,5-tetrafluorophenyl)borate, 2,2'-dimethyl-1,1'-binaphthylmethylsilane-onium tetra(pentafluorophenyl)borate, ethylsilane-onium tetra(3,5-tetrafluorophenyl)borate, tricyclohexylsilane-onium tetra(pentafluorophenyl)borate, dimethyl-1,1'-naphthylmethylsilane-onium tetra(3,5-tetrafluorophenyl)borate, dimethylsilane-onium tetra(pentafluorophenyl)borate, di ... -Bis(trifluoromethyl)phenyl)boronic acid 2,2'-dimethyl-1,1'-binaphthylmethylsilaneonium, lithium tetra(pentafluorophenyl)aluminate, triphenylmethyl tetra(pentafluorophenyl)aluminate, triphenylmethyl (perfluorobiphenyl)fluoroaluminate, lithium (octoxy)tris(pentafluorophenyl)aluminate, lithium tetra(3,5-bis(trifluoromethyl)phenyl)aluminate, sodium tetra(pentafluorophenyl)aluminate, triphenylmethyl tetra(pentafluorophenyl)aluminate, biphenyl (octoxy)tris(pentafluorophenyl)aluminate, sodium tetra(3,5-bis(trifluoromethyl)phenyl)aluminate, potassium tetra(pentafluorophenyl)aluminate, triphenylmethyl tetra(pentafluorophenyl)aluminate, potassium (octoxy)tris(pentafluorophenyl)aluminate, potassium tetra(3,5-bis(trifluoromethyl)phenyl)aluminate, potassium tetra(pentafluorophenyl)aluminate Magnesium aluminate, (octoxy)tris(pentafluorophenyl)magnesium aluminate, tetra(3,5-bis(trifluoromethyl)phenyl)magnesium aluminate, tetra(pentafluorophenyl)calcium aluminate, (octoxy)tris(pentafluorophenyl)calcium aluminate, tetra(3,5-bis(trifluoromethyl)phenyl)calcium aluminate, LiB(OC(CF3)3)4, LiB(OC(CF3)2(CH3))4, LiB(OC(CF3)2H)4, LiB(OC(CF3)(CH3)H)4, Tl(OC(CF3)3)4, TlB(OC(CF3)2H)4, TlB(OC(CF3)(CH3)H)4, TlB(OC(CF3)2(CH3))4, (Ph3C)B(OC(CF3)3)4.(Ph3C)B(OC(CF3)2(CH3))4, (Ph3C)B(OC(CF3)2H)4, (Ph3C)B(OC(CF3)(CH3)H)4, AgB(OC(CF3))4, AgB(OC(CF3)2H)4, AgB(OC(CF3)(CH3)H)4, LiB(O2C6F4)2, TlB(O2C6F4)2, Ag( toluene )2B(O2C6F4)2, Ph3CB(O2C6F4)2LiB(OCH(CF3)2)4, [Li(HOCH3)4]B(O2C6Cl4)2, [Li(HOCH3)4]B(O2C6F4)2, [Ag( toluene )2]B(O2C6Cl4)2, LiB(O2C6Cl4)2, (LiAl(OC(CF3)2Ph)4), (TlAl(OC(CF3)2Ph)4), (AgAl(OC(CF3)2Ph)4), (Ph3CAl(OC(CF3)2Ph)4, (LiAl(OC(CF3)2C6H4CH3)4), (TlAl(OC(CF3)2C6H4CH3)4), (AgAl(OC(CF3)2C6H4CH3)4), (Ph3CAl(OC(CF3)2C6H4CH3)4), LiAl(OC(CF3))4, TlAl(OC(CF3)3)4, AgAl(OC(CF3)3)4, Ph3CAl(OC(CF3)3)4, LiAl(OC(CF3)(CH3)H)4, TlAl(OC(CF3)(CH3)H)4, AgAl(OC(CF3)(CH3)H)4, Ph3CAl(OC(CF3)(CH3)H)4, LiAl(OC(CF3)2H)4, TlAl(OC(CF3)2H)4, AgAl(OC(CF3)2H)4, Ph3CAl(OC(CF3)2H)4, LiAl(OC(CF3)2C6H4-4-i-Pr)4, TlAl(OC(CF3)2C6H4-4-i-Pr)4, AgAl(OC(CF3)2C6H4-i-Pr)4, Ph3CAl(OC(CF3)2C6H4-4-i-Pr)4, LiAl(OC(CF3)2C6H4- tert -butyl )4, TlAl(OC(CF3)2C6H4-t-butyl)4, AgAl(OC(CF3)2C6H4-4- tert -butyl )4, LiAl(OC(CF3)2C6H4-4-SiMe3)4, TlAl(OC(CF3)2C6H4-4-SiMe3)4, AgAl(OC(CF3)2C6H4-4-SiMe3)4, Ph3CAl(OC(CF3)2C6H4-4-SiMe3)4,LiAl(OC(CF3)2C6H4-4-Si-i-Pr3)4, TlAl(OC(CF3)2C6H4-4-Si-i-Pr3)4, AgAl(OC(CF3)2C6H4-4-Si-i-Pr3)4, Ph3CAl(OC(CF3)2C6H4-4- Si-i-Pr3)4, LiAl(OC(CF3)2C6H2-2,6-(CF3)2-4-Si-i-Pr3)4, TlAl(OC(CF3)2C6H2-2,6-(CF3)2-4-Si-i-Pr3)4, AgAl(OC(CF3)2C6H2-2, 6-(CF3)2-4-Si-i-Pr3)4, Ph3CAl(OC(CF3)2C6H2-2,6-(CF3)2-4-Si-i-Pr3)4, LiAl(OC(CF3)2C6H3-3,5-(CF3)2)4, TlAl(OC(CF3)2C6H3- 3,5-(CF3)2)4, AgAl(OC(CF3)2C6H3-3,5-(CF3)2)4, Ph3CAl(OC(CF3)2C6H3-3,5-(CF3)2)4, LiAl(OC(CF3)2C6H2-2,4,6-(CF3))4, TlAl(OC (CF3)2C6H2-2,4,6-(CF3)3)4, AgAl(OC(CF3)2C6H2-2,4,6-(CF3)3)4, Ph3CAl(OC(CF3)2C6H2-2,4,6-(CF3L)4, LiAl(OC(CF3)2C6F5)4, TlAl(OC(CF3)2C6F5)4, AgAl(OC(CF3)2C6F5)4, Ph3CAl(OC(CF3)2C6F5)4, [1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-boronyl lithium, [1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2- Boronyltriphenylmethylonium, 4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borylalkyl lithium, 4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borylalkyltriphenylmethylonium, 1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borylalkyl lithium, 1-fluoro-1,2-dihydro-4-pentafluorophenyl)-2-borylalkyltriphenylmethylonium, 1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borylalkyl lithium, and 1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borylalkyltriphenylmethylonium.

[0040] Generally, the molar ratio of activator to precatalyst is between 10:1 and 1:10, preferably between 10:1 and 1:1, but other ratios may also be used.

[0041] To control the molecular weight, the desired system may include alkenes, such as, for example, 1-octene, 1-hexene, 1-pentene, 1-decene, or 1-dodecene.

[0042] Many available addition polymerization catalysts and pre-catalyst / activator combinations are known and disclosed, for example, in: U.S. Patent No. 3,330,815 (McKeon et al.) col. 8, line 28 to col. 9, line 56; U.S. Patent No. 6,455,650 B1 (Lipian et al.) col. 3, line 9 to col. 17, line 16; U.S. Patent No. 6,825,307 (Goodall) col. 3, line 18 to col. 31, line 53; U.S. Patent No. 6,903,171 B2 (Rhodes et al.) col. 3, line 31 to col. 17, line 16; and U.S. Patent No. 7,759,439 B2 (Rhodes et al.) col. 16, line 32 to col. 28, line 31; U.S. Patent No. 10,266,720 (Burgoon et al.) col. 20, line 28 To col. 21, line 30; and U.S. Patent Application Publication 2005 / 0187398 A1 (Bell et al.) paragraphs

[0015] to

[0075] , the disclosures of which are incorporated herein by reference. Another class of catalysts relates to early metal or late metal pre-catalyst complexes that do not initially have alkyl / allyl ligands but are alkylated by a co-catalyst (such as methylaluminoxane). In some embodiments, the organometallic addition polymerization catalyst comprises palladium or nickel.

[0043] Details regarding certain addition polymerization catalysts are also reported below: MVBermeshev and PPChapala 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.

[0043] ROMP aggregation

[0044] ROMP is a well-known method for converting cyclic olefins into polymers using ROMP catalysts. Ring-opening metathesis polymerization of cyclic olefin monomers generally yields cross-linked polymers with unsaturated linear backbones. The degree of unsaturation of the repeating backbone units of the polymer is the same as the degree of unsaturation of the monomer. For example, in the presence of a suitable catalyst, using norcamphene reactants, the resulting polymer can be represented as follows:

[0044] The number of repeating monomer units in the α-polymer chain.

[0045] As another example, in the presence of a suitable catalyst, using polymers such as dicyclopentadiene, the resulting polymer can be represented as follows:

[0045] where b+c is the mole number of the polymerized monomer, and c / (b+c) is the mole fraction of the monomer units that open the ring at the two reactive sites, and * indicates the continued polymerization structure. As shown in the above reaction, metathesis polymerization of dienes, trienes, etc., can lead to crosslinked polymers. Representative cycloalkane monomers, catalysts, procedures, etc., that can be used for metathesis polymerization are described, for example, in the following: U.S. Patent No. 4,400,340 (Klosiewicz); No. 4,751,337 (Espy et al.); No. 5,849,851 (Grubbs et al.); and No. 6,800,170 B2 (Kendall et al.); and U.S. Patent Application Publication No. 2007 / 0037940 A1 (Lazzari et al.).

[0046] Exemplary ROMP catalysts include dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](benzylmethyl)bis(3-bromopyridine)ruthenium(II) (Grubbs catalyst C884); (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinyl)dichloro(o-isopropoxyphenylmethylene)ruthenium, dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](2-isopropoxyphenylmethylene)ruthenium(II) (Hoveyda-Grubbs catalyst C627); (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium (Grubbs catalyst C... 848), benzene-bis(tricyclohexylphosphine) ruthenium dichloro (Grubbs catalyst C823), ruthenium(II) dichloro(tricyclohexylphosphine)[(tricyclohexylphosphine)methylene]tetrafluoroborate (Grubbs catalyst C833); dichloro[1,3-bis(2-methylphenyl)-2-imidazolidine](benzene-bis(tricyclohexylphosphine)-ruthenium(II) (Grubbs catalyst C793), all of which are available from Millipore Sigma (Sigma-Aldrich, Saint Louis, Missouri), and ROMP catalyst product number 1250BP, from Materia Inc., Pasadena, California.

[0047] In some embodiments, the ROMP catalyst comprises at least one of ruthenium, tungsten, osmium, or molybdenum.

[0047] Optional comonomers and additives

[0048] The monomers disclosed herein are polymerizable and may optionally be polymerizable with other comonomers.

[0049] Examples of suitable copolymerizable monomers include norbornene, 1-methylnorbornene, 5-methylnorbornene, 7-methylnorbornene, 5-(2-ethylhexyl)norbornene, 1-pentadecanylnorbornene, 5,5-dimethylnorbornene, 5,5-dibutylnorbornene, 5,7-dibutylnorbornene, 5-methyl-5-ethylnorbornene, 5,6-docododecylnorbornene, 5-ethyl-6-propylnorbornene, 5,5,6,6-tetramethylnorbornene, 1-phenylnorbornene Camphene, 5-naphthylnorcamphene, 5,5-diphenylnorcamphene, 5-vinylnorcamphene, 7-vinylnorcamphene, 5-propenyl-6-methylnorcamphene, 5-tolylnorcamphene, 5-benzylnorcamphene, 5-cyclopentylnorcamphene, 1,5,5-trimethylnorcamphene, 5-isopropenylnorcamphene, 1-isopropylnorcamphene, 1-ethylnorcamphene, 1,5-dimethylnorcamphene, 1,5-diethylnorcamphene, 1,6-dimethylnorcamphene, 5,5,6- Trimethylnorcamphene, 5-cyclopropylnorcamphene, 5-cyclohexylnorcamphene, 5-cyclopentenylnorcamphene, 5-(2'-norcamphenyl)norcamphene, 5-phenylnorcamphene, 5-benzylnorcamphen-2-ene, 5-(2'-phenylethyl)norcamphene, 5-(3'-phenylpropyl)norcamphene, 5-(4'-phenylbutyl)norcamphene, 2,5-norcamphene, cyclohexene, cyclopentene, dicyclopentadiene, 2,5-norcamphene, bicyclo[2.2.2]-2- Octene, Indene, 5-Methylenenorcamphene, 5-Ethylenenorcamphene, 5-Propylenenorcamphene, 5-Hexylenenorcamphene, 5-Decylenenorcamphene, 5-Methylene-6-methylnorcamphene, 5-Methylene-6-hexylenenorcamphene, 5-Cyclohexylenenorcamphene, 5-Cyclooctylenenorcamphene, 7-Isopropylenenorcamphene, 5-Methyl-7-isopropylenenorcamphene, 5-Hydroxymethyl-6-methylenenorcamphene, 7-Ethylenenorcamphene, 5-Methyl-7-Propylenenorcamphene

[0049]

[0049]

[0049] where R2 represents an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl), and n represents an integer from 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 8, 10).

[0050] Especially in the case of catalytic addition polymerization and ring-opening metathesis polymerization, suitable alternative comonomers may include at least one cyclic olefin (e.g., norcamphene or its substituted derivatives). Examples include compounds represented by the following formula.

[0050] Includes its stereoisomers, wherein R represents H or an alkyl group having up to ten carbon atoms. Examples of R include hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and decyl.

[0051] For example, comonomers having multiple alicyclic rings containing double bonds can be used to form crosslinked polymeric compositions.

[0052] The polymerizable composition may optionally include other components such as fillers (e.g., thermal fillers and / or conductive fillers), thixotropic agents, plasticizers, colorants, fragrances, antioxidants, ultraviolet (UV) light stabilizers and / or tackifiers.

[0052] Polymer

[0053] In some preferred embodiments, when polymerized, the polymerizable composition according to this disclosure can form linear and crosslinked polymers (including homopolymers and copolymers).

[0054] An exemplary polymer comprises a tetravalent or octavalent monomer unit represented by the following formula.

[0054] Among them:

[0054] Each R1 independently represents an alkyl group having 1 to 4 carbon atoms;

[0054] Each n independently represents 0 or 1; and

[0054] Z represents an alkyl group having 1 to 40 carbon atoms, or a group represented by the following formula.

[0054] Among them:

[0054] Each L independently represents a divalent alkyl group having 1 to 12 carbon atoms, and

[0054] p represents 0 or 1.

[0055] Another exemplary polymer includes a divalent or tetravalent monomer unit represented by the following formula.

[0055] where R1, n, and p are as previously defined, and Z is a tetravalent segment.

[0055] Each R1 independently represents an alkyl group having 1 to 4 carbon atoms;

[0055] Z represents an alkyl group having 1 to 40 carbon atoms, or a group represented by the following formula.

[0055] Among them:

[0055] Each L independently represents a divalent alkyl group having 1 to 12 carbon atoms, and

[0055] p represents 0 or 1.

[0056] The purpose and advantages of this disclosure are further illustrated by the following non-limiting examples, but the invention should not be limited by over-interpreting the specific materials and their amounts, as well as other conditions and details detailed in these examples.

[0056] Example

[0057] Unless otherwise stated, all parts, percentages, ratios, etc. in the examples and other parts of this specification are by weight.

[0058] Table 1 (below) reports the materials used in the examples and their sources.

[0059]

[0059] Characteristics methods

[0059] Characterization by 1H NMR

[0060] NMR samples were analyzed in solutions in deuterated chloroform. ¹NMR spectra were performed using a Bruker AVANCE III 500 MHz NMR spectrometer equipped with a CPBBO gradient cryopreservation probe, a Bruker B-ACS 60 autosampler, and Bruker Topspin 3.04 software. Spectra were analyzed using Advanced Chemistry Development software (Toronto, Canada).

[0060] Characterized by GPC

[0061] A solution with an approximate concentration of 1.5 mg / mL was prepared in toluene. The sample was rotated on a fixed-track shaker for 12 hours. The sample solution was filtered through a 0.45 μm PTFE injection filter and then analyzed by GPC. The analysis was performed using an Agilent (Santa Clara, California) 1260 LC instrument set at 40 °C with a Jordi DVB + Jordi 500 Å (50 nm) column, 1.0 mL / min toluene eluent (+2% triethylamine), NIST polystyrene standard (SRM 705a), and an Agilent 1260 evaporative light scattering detector.

[0061] Characterization via GCMS

[0062] The sample was diluted in toluene and injected directly into an Agilent 7890A GC-MS instrument (Rxi-1ms, 30m×0.25mm, 0.25μm membrane column), where EI mass spectrometry was performed at 70eV for detection from 29 to 650Da.

[0062] Liquid circularity was measured using a dielectric resonator at 2.45 GHz.

[0063] The TE01δ cylindrical dielectric resonator was tuned to measure the complex dielectric constant of a dielectric at a frequency of 2.45 GHz using the method described in the conference journal "TE01Δ dielectric resonator technique for measuring the complex dielectric constant of lossy liquids at frequencies below 1 GHz" (Krupka, K. Derzakowski, MD Janezic, and J. Baker-Jarvis, pp. 469-470, London, June 27-July 2, 2004).

[0063] Example 1

[0063] Preparation of Monomer 1

[0064] Ethyl dimethyl silane (5.00 g, 56.7 mmol) was added dropwise to a solution of a complex of 5-vinylbicyclo[2.2.1]-hept-2-ene (6.81 g, 56.7 mmol) and platinum-divinyltetramethyldisiloxane (1 drop) in toluene (30 mL), which was cooled to 0 °C in an ice bath. The reaction mixture was allowed to warm to room temperature and stirred for 3 days, and toluene and excess reagent were removed under vacuum to give a product as a clear, colorless liquid. ¹H NMR (CDCl₃) showed a 94% yield (silicon position carrying the nobornene group); m / z (EI) 179 (M-Et), 121 (nobornene-CH₂CH₂), 87 (Si(CH₃)₂Et).

[0064] Example 2

[0064] Preparation of Monomer 2

[0065] A solution of a complex of 5-vinylbicyclo2,2,1-hept-2-ene (12.88 g, 10.7 mmol) and platinum-divinyltetramethyldisiloxane (1 drop) in toluene (100 mL) was added dropwise and cooled to 0 °C in an ice bath. The reaction mixture was allowed to warm to room temperature and stirred for 2 days, and toluene and excess reagent were removed under vacuum to give a product as a clear, colorless liquid. ¹H NMR (CDCl₃) showed a 98% yield (silicon position carrying the nobornene group); m / z (EI) 179 (M-Bu), 121 (nobornene-CH₂CH₂), 115 (Si(CH₃)₂Bu) 59 (Bu).

[0065] Example 3

[0065] Preparation of Monomer 3

[0066] Octyldimethylsilane (10.59 g, 33.9 mmol) was added dropwise to a solution of a complex of 5-vinylbicyclo2,2,1-hept-2-ene (4.07 g, 33.9 mmol) and platinum-divinyltetramethyldisiloxane (1 drop) in toluene (50 mL). The reaction mixture was stirred at room temperature for 4 days, and toluene and excess reagent were removed under vacuum to give a product as a clear, colorless oil. ¹H NMR (CDCl₃) showed a 95% yield (silicon position carrying the norcamphene group).

[0066] Example 4

[0066] Preparation of crosslinking agent 4

[0067] 1,1,4,4-Tetramethyl-1,4-disilylbutane (9.83 g, 67.0 mmol) was added dropwise to a solution of 5-vinylbicyclo2,2,1-hept-2-ene (16.15 g, 0.134 mol) and platinum-divinyltetramethyldisiloxane complex (1 drop) in toluene (100 mL). After initial exothermic reaction, the reaction mixture was stirred at room temperature for 2 days, and toluene and excess reagent were removed under vacuum to give a product as a clear, colorless oil. ¹H NMR (CDCl₃) showed a 70% yield (silicon position carrying the nobornene group); m / z (EI) 387 (M+), 179 (nobornene-CH₂CH₂Si(CH₃)₂).

[0067] Example 5

[0067] Preparation of crosslinking agent 5

[0068] 1,1,4,4-Tetramethyl-1,4-disilylbutane (10.12 g, 69.1 mmol) was added dropwise to a solution of 1,7-octadiene (3.81 g, 34.6 mmol) and platinum-divinyltetramethyldisiloxane complex (1 drop) in toluene (80 mL). After initial exothermic reaction, the reaction mixture was stirred at room temperature for 30 minutes. 5-Vinylbicyclo[2.2.1]hept-2-ene (8.31 g, 61.9 mmol) was added and the reaction mixture was stirred at 50 °C for 6 days. Toluene and excess reagents were removed under vacuum to give a product as a clear, pale yellow oil. 1H NMR (CDCl3) showed a 74% yield (silicon position carrying the norcamphene group). Molecular masses within the target range as shown by GPC (toluene, ELSD): Mn = 1300 g / mol, Mw = 1500 g / mol, polydispersity 1.1.

[0068] Example 6

[0068] Preparation of crosslinking agent 6

[0069] Tetra(dimethylsiloxy)silane (7.50 g, 22.8 mmol) was added dropwise to a solution of 5-vinylbicyclo2,2,1-hept-2-ene (10.97 g, 91.3 mmol) and a platinum-divinyltetramethyldisiloxane complex (1 drop) in toluene (100 mL). Initial exothermic reaction was managed by applying and removing a room temperature water bath over 30 minutes. The reaction mixture was stirred at 50 °C for 6 days, and toluene and excess reagent were removed under vacuum to give a product as a clear, pale yellow oil. ¹H NMR (CDCl₃) showed a 50% yield (silicon position carrying the norcamphene group). Molecular weights in the target range were shown by GPC (toluene, ELSD): Mn = 1100 g / mol, Mw = 1400 g / mol, polydispersity 1.3.

[0070] Table 2 below reports the dielectric constant and loss factor of unreacted liquid monomers and crosslinking agents at 2.45 GHz.

[0071]

[0071] Characterization membrane via DMA

[0072] Storage and loss moduli were measured using a multi-frequency strain module on an AresG2 dynamic mechanical analyzer (DMA, model Q800 V21.3 Build 96). Membrane samples were cut to specific dimensions and mounted in tension membrane clamps. The furnace was equilibrated at 30°C and then heated to 300°C at a rate of 5°C / min, while an oscillating strain of 0.1% was applied under a static force of 0.02 N.

[0072] Addition Polymerization (AP)

[0072] Palladium catalyst solution

[0073] A solution was prepared by dissolving allyl chloride [1,3-bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazol-2-yl]palladium(II) (12 mg, 21 mmol), tricyclohexylphosphine (11.8 mg, 42 mmol, 2.0 equivalent), and sodium tetra[3,5-bis(trifluoromethyl)phenyl]borate (91.3 mg, 103 mmol, 4.9 equivalent) in 1,2-dichloroethane (24.6 g) and stirring at room temperature for 30 minutes. Several batches of this palladium catalyst solution (with different total masses) were prepared for use according to the examples below, but they always contained the same weight ratio of materials as described in the above procedure.

[0073] Example 7

[0073] Addition polymerization of monomer 1

[0074] Monomer 1 (4.0 g) was mixed with catalyst solution (6.0 g) and toluene (30.0 g) and stirred at room temperature for 7 days, during which an increase in viscosity was observed. The product was separated by precipitation in methanol and drying at 90 °C for 4 hours. A white fibrous solid was obtained. ¹H NMR (CDCl₃) showed that 100% of the norcamphene groups were depleted. A 10 wt% product solution was prepared in toluene, the solution was poured, and dried at room temperature for 12 hours and at 70 °C for 2 hours to obtain a membrane. DMA showed a storage modulus of about 700 MPa at 30 °C and a plateau reaction at tan δ up to 300 °C, indicating Tg > 300 °C.

[0074] Example 8

[0074] Addition polymerization of monomer 2

[0075] Monomer 1 (4.0 g) was mixed with catalyst solution (5.3 g) and toluene (30.7 g) and stirred at room temperature for 3 days, during which an increase in viscosity was observed. The product was separated by precipitation in methanol and drying at 90 °C for 4 hours. A white fibrous solid was obtained. ¹H NMR (CDCl₃) showed that 98% of the norcamphene groups were depleted. A 10 wt% product solution was prepared in toluene, the solution was poured, and dried at room temperature for 12 hours and at 70 °C for 2 hours to obtain a membrane. DMA showed a storage modulus of about 150 MPa at 30 °C and a Tg of about 290 °C from the tan δ peak.

[0075] Example 9

[0075] Addition polymerization of crosslinking agent 5

[0076] Crosslinking agent 6 (4.0 g) was mixed with catalyst solution (3.9 g) and toluene (32.1 g) and stirred at room temperature for 7 days, during which no change in viscosity was observed. A viscous yellow oil was obtained after evaporation of toluene. Crosslinking was demonstrated by the formation of gel fragments in toluene. Characterization of the soluble components in CDCl3 by 1H NMR showed that 18% of the norcamphene groups had reacted.

[0076] Example 10

[0076] Addition polymerization of crosslinking agent 6

[0077] Crosslinking agent 6 (4.0 g) was mixed with catalyst solution (6.2 g) and toluene (29.8 g) and stirred at room temperature for 7 days, during which an increase in viscosity was observed. The product was separated by precipitation in methanol and drying at 90°C for 4 hours. A soft, adhesive solid was obtained. Crosslinking was demonstrated by the formation of a transparent gel with toluene. Characterization of the soluble components in CDCl3 by 1H showed that 16% of the norcamphene groups had reacted.

[0077] Example 11

[0077] Addition polymerization of crosslinking agent 4 (high temperature)

[0078] Crosslinking agent 4 (1.0 g) was mixed with catalyst solution (0.1 g) and toluene (0.4 g) and stirred at room temperature for 7 days, during which an increase in viscosity was observed. The mixture was cured at 90°C for 10 minutes, followed by curing at 130°C for 30 minutes to produce a transparent gel.

[0078] Comparative Example A

[0078] Addition polymerization of decyl-norbornene (comparative example)

[0079] A Pd catalyst solution (0.2 mL, 0.86 mM Pd in ​​dichloroethane) was added to a solution of decyl-norbornene (1.0 g) in toluene (6 mL), and the mixture was stirred at room temperature for 4 hours. The resulting viscous solution was precipitated in methanol (100 mL), and the white solid was separated by filtration and dried at 90 °C to a constant mass (0.94 g). The solid completely dissolved in toluene, indicating a lack of crosslinking.

[0079] Example 12

[0079] Addition polymerization of crosslinking agent 4 (room temperature)

[0080] A catalyst solution (0.10 mL, 0.86 mM Pd in ​​dichloroethane) was added to a solution of crosslinking agent 4 (0.33 g) in toluene (3.3 mL), and the mixture was stirred at room temperature for 4 hours. The resulting viscous solution was precipitated in methanol (20 mL), and the white solid was separated by filtration and dried at 90 °C to a constant mass (0.18 g). The product was insoluble in toluene, indicating crosslinking in the polymer.

[0080] Example 13

[0080] Addition copolymerization of decyl-norbornene and crosslinking agent 4

[0081] A Pd catalyst solution (0.2 mL, 0.86 mM Pd in ​​dichloroethane) was added to a solution of decyl-norbornene (1.0 g) and crosslinking agent 4 (0.33 g) in toluene (6 mL), and the mixture was stirred at room temperature for 4 hours. The resulting viscous solution was precipitated in methanol (100 mL), and the white solid was separated by filtration and dried at 90 °C to a constant mass (0.56 g). The solid was insoluble in toluene, indicating crosslinking in the polymer.

[0081] Ring-opening metathesis polymerization (ROMP)

[0081] General Procedure for Ring-Opening Metathesis Polymerization (ROMP)

[0082] For crosslinking agent 4 only, first dissolve 1g of crosslinking agent 4 in 0.4g of toluene. Add ROMP catalyst (20mg for crosslinking agents 4, 5, and 6; 200mg for monomers 1, 2, and 3) to 1g of monomer or crosslinking agent. Heat the solution at 120°C for 20 minutes.

[0083] The results are reported in Table 3 below, ROMP results, in which solid non-flowing products indicate successful polymerization.

[0084]

[0085] Any references, patents, and patent applications cited herein are incorporated in a consistent manner. In the event of any inconsistency or conflict between the incorporated references and this application, the information in this application shall prevail.

[0086] The foregoing is intended to enable those skilled in the art to implement the embodiments disclosed herein, and should not be construed as limiting the scope of the invention, which is defined by the scope of the claims and all their equivalents.

Claims

1. A monomer represented by the following formula, 1. Among them: Each R1 independently represents an alkyl group having 1 to 4 carbon atoms; Z represents a group represented by the following formula.

1. Wherein: each L independently represents a divalent alkyl group having 1 to 12 carbon atoms, each n independently represents 0, 1, or 2; and p represents 1.

2. A polymerizable composition comprising a monomer as claimed in claim 1 and a curing agent thereof.

3. The polymerizable composition of claim 2, wherein the curing agent of the monomer comprises an organometallic addition polymerization catalyst.

4. The polymerizable composition of claim 3, wherein the organometallic addition polymerization catalyst comprises palladium or nickel.

5. The polymerizable composition of claim 2, wherein the curing agent comprises a ring-opening metathesis polymerization catalyst.

6. The polymerizable composition of claim 5, wherein the ring-opening metathesis polymerization catalyst comprises at least one of ruthenium, tungsten, osmium, or molybdenum.

7. The polymerizable composition of claim 2, further comprising at least one cyclic olefin.

8. The polymerizable composition of claim 7, wherein the at least one cyclic olefin is composed of at least one of the following formulas.

8. or its stereoisomers, wherein R represents H or an alkyl group having up to 10 carbon atoms.

9. A polymerizable composition which can be prepared by polymerizing the polymerizable composition of claim 2.

10. A polymer comprising a divalent or tetravalent monomer unit represented by the following formula.

10. Wherein: each R1 independently represents an alkyl group having 1 to 4 carbon atoms; Z represents a group represented by the following formula.

10. Among them: Each L independently represents a divalent alkyl group having 1 to 12 carbon atoms, each n independently represents 0, 1, or 2; and p represents 1.

11. The polymer as requested in item 10, wherein each n-series is 0.