Curable polymer composition

Abstract

To provide a curable polymer composition which has high cure rates while minimizing premature cross-linking under standard processing conditions, and provides improved electrical properties, e.g., low Dk and Df values.SOLUTION: The disclosure relates to a curable polymer composition comprising (i) a copolymer of a diisoalkenylarene (DIAEA) and a divinylarene (DVA), and (ii) at least one anti-scorching agent. The solubility of the copolymer in a hydrocarbon solvent at 25°C in less than 4 hours is at least 10 wt. %, the glass transition temperature (Tg) of the copolymer is 50-300°C, and the gel content of the copolymer is less than 5 wt.%. The curable polymer composition is cured at a temperature higher than 140°C to obtain a cured polymer composition having a gel content greater than 90% in a hydrocarbon solvent and low Dk and Df values. The curable polymer composition does not cross-link or has minimal premature cross-linking in steps such as processing and storage, and can be used in copper clad lamination applications.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to curable polymer compositions, their methods of preparation and uses. [Background technology]

[0002] The electronics industry is interested in developing miniaturized electronic devices for various end applications. These miniaturized devices need to handle large amounts of information and have high-speed signal transmission at high frequencies. One of the very important components of the miniaturized devices is the circuit material, which has single or multiple dielectric layers / laminates. The preferred dielectric layers for use in the manufacture of substrates are characterized by low dielectric constant (Dk), low dissipation factor (Df), reduced coefficient of thermal expansion (CTE), etc.

[0003] A polymer with low Dk and Df must have a balance of other properties, such as mechanical properties, solubility in solvents, and flowability, to be suitable for use in dielectric layer applications. Compositions containing crosslinked polymers can contribute to improving the desired properties. Nevertheless, certain polymers in the composition are very reactive, and it is difficult to control their reactivity during transportation, storage, or processing of the composition. Scorch inhibitors or radical scavengers are known in the art to control the reactivity of the polymer in the composition, especially to avoid premature crosslinking. However, such additives may not be effective in reducing / stopping premature crosslinking of the polymer, or may negatively affect Dk and Df. Summary of the Invention [Problem to be solved by the invention]

[0004] Thus, there is a need for curable polymer compositions that have high cure rates and provide improved electrical properties, such as low Dk and Df, while minimizing premature crosslinking under standard processing conditions. [Means for solving the problem]

[0005] (Abstract) In one aspect, the disclosure relates to a curable composition comprising, consisting essentially of, or consisting of (i) a copolymer of a diisoalkenyl arene and a divinylarene and (ii) 0.001 to 10 wt % of a scorch inhibitor. The copolymer has a molar ratio of diisoalkenyl arene to divinylarene of 1:15 to 15:1; a solubility in hydrocarbon solvents of at least 10 wt % at 25° C. for less than 4 hours as measured by the Solubility Test described herein; a glass transition temperature (T) of 50° C. to 300° C. as measured by ASTM D3418. g and a gel content of less than 5 wt. %, based on the total weight of the copolymer, as measured by the Gel Content Test described herein. The scorch inhibitor is selected from the group consisting of styrene, α-methylstyrene monomer, α-methylstyrene dimer, α-methylstyrene oligomer, hindered phenolic compounds, non-hindered phenolic compounds, benzimidazole, and mixtures thereof. The curable polymer composition at a concentration of 72.5 wt. % in toluene has a solution viscosity, measured at 25° C. by Brookfield viscometer after storage at 40° C. for 1 day, that is at least 20% less than the solution viscosity of the polymer composition without the scorch inhibitor.

[0006] In a second embodiment, the curable polymer composition has a molar ratio of diisoalkenyl arene to divinylarene that is from 10:1 to 1:10.

[0007] In a third embodiment, the copolymer has a solubility of 10-75 wt % in a hydrocarbon solvent at 25° C. for less than 4 hours.

[0008] In a fourth embodiment, the copolymer has a gel content that is between 0.05 and 5 wt %. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The following terms are used throughout the specification:

[0010] "At least one of [a group such as A, B, and C]" or "any of [a group such as A, B, and C]" or "selected from [A, B, and C], and combinations thereof" means a single member from the group, more than one member from the group, or a combination of members from the group. For example, at least one of A, B, and C includes, for example, only A, only B, or only C, as well as A and B, A and C, B and C; or any other combination of A, B, and C, or A, B, and C.

[0011] "Scorch" refers to the phenomenon in which a polymer / composition prematurely crosslinks and loses its processability due to the influence of heat or light during storage, processing, transportation, etc. Premature crosslinking is crosslinking before the polymer / composition hardens under normal processing conditions.

[0012] "Scorch inhibitor" refers to an additive that inactivates / stops prematurely generated radicals in a polymer / composition by reaction with free radicals during processing, shipping, storage, or the like.

[0013] "Curing" or "crosslinking" are used interchangeably and refer to the formation of covalent bonds that link one polymer chain to another, or link one polymerized repeat unit to another within the same polymer chain, thereby modifying the properties of the material.

[0014] "Molecular Weight" or M w M refers to the polystyrene equivalent molecular weight in g / mole or kg / mol of a polymer block or block copolymer or copolymer. w can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, such as those performed by ASTM 5296-19. The GPC detector can be an ultraviolet detector or a refractive index detector, or a combination of these. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The M of a polymer measured using such a calibrated GPC is wis the polystyrene equivalent or apparent molecular weight. w is measured at the peak of the GPC trace and is commonly called the polystyrene equivalent "peak molecular weight", M p It is shown as:

[0015] "Substantially gel-free" refers to a polymer that contains <10, or <8, or <5, or <3, or <2, or <1 wt.% solids that are insoluble in hydrocarbon solvents, such as toluene, cyclohexane, methyl ethyl ketone (MEK), xylene, and the like.

[0016] "Gel content" refers to the insoluble content of the cured polymer composition in toluene as a percentage of the cured polymer composition (before immersion in a hydrocarbon solvent). In embodiments, the gel content is >90 wt% (<10 wt% toluene extractable), or >95 wt% (<5 wt% toluene extractable), or >98 wt% (<2 wt% toluene extractable).

[0017] "Gel content test" refers to the measurement of gel content by placing a sample of the cured polymer composition having weight G1 in 20 volumes of toluene at room temperature for 4 hours. The contents in toluene are then filtered, and the solid portion of the cured polymer composition is collected, then dried to completely remove the solvent, and weighed to give the insoluble content G2. The gel content is calculated as (G2 / G1). In an embodiment, the gel content can also be measured by soaking a sample of the cured polymer composition at 90°C for 9 hours, followed by filtering, drying, and recording the weight of the solid portion.

[0018] "Solubility test" refers to the measurement of solubility by placing a polymer / copolymer sample in about 10 volumes of a hydrocarbon solvent, such as toluene, shaking well, and leaving it at room temperature for up to 4 hours. Then, by visual observation, it is considered whether the polymer / copolymer has completely or partially dissolved in the solvent. The contents are decanted or filtered, and after drying, the weight of the remaining polymer / copolymer is measured, and the weight of the dissolved polymer / copolymer is calculated.

[0019] "Swelling content" refers to the weight difference (W%) between the weight of the cured polymer composition (W2) that no longer absorbs toluene after immersion in toluene until completely saturated, i.e., after a period of time while the sample weight remains the same, and the weight of the curable polymer composition before immersion (W1), calculated as W%=(W2-W1) / W1×100.

[0020] Df denotes the "dielectric tangent" or "loss tangent" (Df) and is a measure of the rate of loss of electrical energy in a dissipative system.

[0021] Dk denotes the dielectric constant or permittivity.

[0022] The present disclosure relates to a curable polymer composition comprising (i) a copolymer of diisoalkenyl arene (DIAEA) and divinylarene (DVA) (DIAEA-DVA copolymer) and (ii) at least one scorch inhibitor. The curable polymer composition has no or minimal crosslinking (premature crosslinking) prior to the intended curing step during steps such as processing, storage, shipping, etc. The curable polymer composition provides improved electrical properties, such as Dk and Df, when cured.

[0023] (DIAEA-DVA copolymer) This copolymer is disclosed and taught in US Patent Application Publication No. 2022 / 0195109. The DIAEA-DVA copolymer can be obtained from DIAEA and DVA monomers by cationic polymerization in the presence of a Lewis acid catalyst or a Bronsted acid catalyst. In an embodiment, the copolymerized DIAEA monomer comprises repeat units (A), (B), (C), and (D) as shown in the structure below, where R 1 is H or a C1-C8 alkyl group. The DIAEA-DVA copolymer can have the repeat units of copolymerized DIAEA and DVA monomers in any order.

[0024] [ka]

[0025] The DIAEA-DVA copolymer can have at least one end group selected from (E), (F), (G), and (H) having the structures shown below.

[0026] [ka]

[0027] Non-limiting examples of DIAEA monomers for producing copolymers include (I) 1,3-diisoalkenyl arenes, (II) 1,4-diisoalkenyl arenes, where R 1 is methyl, ethyl, isopropyl, or n-butyl, or a mixture thereof.

[0028] [ka]

[0029] In an embodiment, the DIAEA is selected from diisopropenylbenzene (DIPEB) and substituted variants thereof to produce copolymers. Examples of DIPEB include, but are not limited to, 1,3-diisopropenylbenzene; 1,2-diisopropenylbenzene; 1,4-diisopropenylbenzene; 3,4-dicyclohexyl-1,2-diisopropenyl-benzene; 5-(3-methyl-cyclopentyl)-1,3-diisopropenylbenzene; 3-cyclopentyl-methyl-6-n-propyl-1,4-diisopropenylbenzene; 4-(2-cyclobutyl-1-ethyl)-1,2-diisopropenylbenzene; 3-(2-n-propylcyclopropyl)-1,4-diisopropenylbenzene; 2-methyl-5-n-hexyl-1,3-diisopropenylbenzene; 4-methyl-1,2-diisopropenyl-benzene; 5-ethyl-1,3-diisopropenylbenzene; 3-methyl-1,4-diisopropenylbenzene; and mixtures thereof.

[0030] In embodiments, the DVA is selected from the group consisting of divinylbenzene (DVB), divinylnaphthalene, divinylbiphenyl, divinyldiphenylether, and mixtures thereof. DVB can include ortho-divinylbenzene, para-divinylbenzene, meta-divinylbenzene, trivinylbenzene, or mixtures thereof.

[0031] In embodiments, the copolymer further comprises a repeat unit derived from another polymerizable monomer, including (i) a cyclodiene or a dimer thereof, (ii) an adduct of a cyclodiene and an acyclic diene, (iii) an allylic compound having two or more allylic groups, (iv) a vinyl compound other than DVA having two or more vinyl groups, and any combination or subcombination thereof.

[0032] Examples of other polymerizable monomers include 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-cyclopentadiene, alkylcyclopentadienes, styrene, α-methylstyrene, paramethylstyrene, butadiene, isoprene, piperylene, divinyltoluene, divinylpyridine, divinylxylene, trivinylcyclohexane, ethylvinylbenzene, vinylnaphthalene, vinyltriisopropeneoxysilane, methoxytrivinylsilane, tetravinylsilane, diethoxydivinylsilane, 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane, and 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinylcyclopentasiloxane, or mixtures thereof.

[0033] In embodiments, the DIAEA-DVA copolymer is either a random copolymer or a block copolymer. Alternatively, the copolymer can contain a homopolymer of DIAEA end-capped with DVA to give a DVA end-capped polyDIAEA.

[0034] The copolymer can have at least one reactive end group selected from structures (E), (F), (G), and (H) and can be suitably functionalized with various functional groups, such as isocyanate, cyclic anhydride, carboxylic acid, carboxylic ester, or epoxy groups, using methods known in the art.

[0035] In embodiments, the DIAEA-DVA copolymer has a molar ratio of DIAEA to DVA that is from 15:1 to 1:15, or from 12:1 to 1:12, or from 10:1 to 1:10, or from 8:1 to 1:8, or from 5:1 to 1:5, or from 4:1 to 1:4, or from 3:1 to 1:3, or from 2:1 to 1:2, or from 1:1.

[0036] In embodiments, the DIAEA-DVA copolymer has a number average molecular weight (M) of 1 to 10, 1.5 to 8, or 2 to 10, or 1 to 5, or >1, or <10 kg / mol. n ); Weight average molecular weight (M) of 3 to 70, or 5 to 60, or 7 to 55, or 10 to 50 kg / mol w ); and a polydispersity index (PDI) of 2-20, 3-15, or 2-10, or 5-15.

[0037] In embodiments, the DIAEA-DVA copolymer is present in solid form or as a solution in a hydrocarbon solvent at a concentration of 20-75 wt%, or 30-75 wt%, or >20 wt%, or <75 wt%, based on the total weight of the solution.

[0038] In an embodiment, the curable polymer composition comprises the DIAEA-DVA copolymer in an amount of 90-99.999, or 90-99.995, or 90-99.99, or 99-99.95, or 95-99.999, or 95-99.995, or 95-99.99, or 95-99.95 wt%, based on the total weight of the curable polymer composition, excluding the amount of glass fibers.

[0039] (Method of preparing DIAEA-DVA copolymer) DIAEA-DVA copolymers can be prepared by methods known in the art and disclosed and taught in US Patent Application Publication No. 2022 / 0195109. In an embodiment, the copolymer is prepared by polymerization of DIAEA and DVA under cationic conditions in a suitable solvent in the presence of a catalyst, e.g., a Bronsted acid, or a Lewis acid. The addition of the monomer / comonomer can be carried out at a suitable temperature for a sufficient time, and the polymerization continued until essentially all the monomer / comonomer has disappeared, or alternatively, until analysis of the reaction mixture indicates that a copolymer of sufficient molecular weight has been formed. At the end of the reaction, the copolymer can be isolated by quenching the reaction mixture with water, followed by separation of the organic solvent layer and removal of the solvent. Traces of organic matter can be removed from the product under high vacuum.

[0040] (Scorch prevention agent) Scorch inhibitors prevent premature crosslinking of vinyl groups in the copolymer prior to the targeted curing step. Scorch inhibitors allow curing to occur at a higher temperature than desired. The effectiveness of the scorch inhibitor can be determined by its effect on the time of scorch delay, the temperature at which crosslinking begins, and the extent of cure of the copolymer.

[0041] In embodiments, the scorch inhibitor is selected from the group including styrene, α-methylstyrene monomer (AMSM), α-methylstyrene dimer (AMSD), α-methylstyrene oligomer (AMSO), hindered phenol compounds in which at least one phenolic OH group ortho-position is substituted with an alkyl group, a phenyl group, or the like, non-hindered phenol compounds, amine compounds, thiourea compounds, benzimidazoles, mixtures and derivatives thereof. The α-methylstyrene derivatives can have one or more functional groups located on each ring, which may all be the same or different.

[0042] In an embodiment, the α-methylstyrene dimer is selected from the group consisting of 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4-methyl-2-pentene, 1,2-trimethyl-3-phenylindane, cis-1,3-dimethyl-1,3-diphenylcyclobutene, trans-1,3-dimethyl-1,3-diphenylcyclobutene, and mixtures thereof.

[0043] In an embodiment, the α-methylstyrene derivative has the formula (J):

[0044] [ka] [In the formula, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is hydrogen, -CH(O), -CN, isocyanato, thioisocyanato, SO3H and their salts and esters, NR 8 R 9 , silane, halogen, C(O)OR 10 , -C(O)NR 11 R 12 , -CR 13 (O), -C(O)OC(O)R 14 , -C(O)NR 15 COR 16 , -OC(O)R 17 , -OR 18 R is independently selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, and substituted and unsubstituted aryl; 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are each independently selected from the group consisting of H, alkyl, aryl, substituted alkyl, or substituted aryl; R 18is selected from the group of alkyl, aryl, substituted alkyl, or substituted aryl; R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 cannot all be hydrogen at the same time. The alkyl and substituted alkyl can have chains of 1 to 12 carbons. It is further preferred that the substituents on the substituted alkyl or substituted aryl do not contain any functional groups that may substantially interfere with free radical polymerization.

[0045] In an embodiment, the scorch inhibitor is based on a hydrocarbon without heteroatoms or polar groups.

[0046] Examples of scorch inhibitors include 2,6-di-t-butyl-p-cresol, 2,2'-methylene-bis-(4-methyl-6-t-butylphenyl), 4,4'-thio-bis-(6-t-butyl-3-methylphenol), 1,3,5-trimethyl-2,4,6-tris-(2',6'-di-t-butyl-p-cresyl)benzene, 4,4'-butylidene-bis-(6-t-butyl-3-methylphenol), (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (bis-TEMPO), 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl (AOTEMPO), 1,1-diphenylethylene (DPE), 4-methacryloyloxy-2,2, 6,6-Tetramethylpiperidine-N-oxyl, 4-Cinnamoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-Crotonoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ol, 1-Methoxy-2,2,6,6-tetramethylpiperidin-4-ol, 1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl acrylate, 1-Methoxy-2,2,6,6-tetramethylpiperidin-4-yl acrylate, 2,5-Di-tert-amyl-hydroquinone, Isotridecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)proprionate, C-13 to C-15 alcohol esters, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, poly(oxyalkylene) chain-substituted 3-arylbenzofuranone, poly(caprolactone) chain-substituted 3-arylbenzofuranone, methoxyallylphenyl allyl ether (MAPAE), dibutyl maleate, allyl malonate, various monoallyl compounds, nonyl maleate, diethyl fumarate, 4-hydroxystyrene, 4-vinylaniline, butylated hydroxytoluene (BHT), stilbenequinone, a Alkylated diphenylamines, quinone imines, hindered phenols, bisphenols, thiobisphenols, substituted hydroquinones, tris(alkylphenyl)phosphites, dialkylthiodipropionates, phenylnaphthylamines, substituted diphenylamines, dialkyl, alkylaryl, and diaryl substituted p-phenylenediamines, monomeric and polymeric dihydroquinolines, 2-(4-hydroxy-3,5-t-butylaniline)-4,6-bis(octylthio)1,3,5-triamine ... , hexahydro-1,3,5-tris-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-s-triazine, 2,4,6-tris(n-1,4-dimethylpentylphenylene-diamino)-1,3,5-triazine, tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, nickel dibutyldithiocarbamate, 2-mercaptotolylimidazole and its zinc salt, petroleum wax, tetrakis[methylene(3,5-di-tert-butyl-4 -hydroxyhydro-cinnamate)]methane, bis[(β-(3,5-di-tert-butyl-4-hydroxybenzyl)-methylcarboxyethyl)]sulfide, 4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), thiodiethylenebis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate, tris(2,Thio compounds such as 4-di-tert-butylphenyl)phosphite, di-tert-butylphenyl-phosphonite, dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, siloxanes, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, n,n'-bis(1,4-dimethylpentyl-p-phenylenediamine), alkylated diphenylamines, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, diphenyl-p-phenylenediamine, mixed di-arylamines, Examples of suitable amines include phenyl-p-phenylenediamine, 2,2'-oxamide bis-(ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-oxamide bis-(ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-isopropylidene-diphenol, phenyl-β-naphthylamine, phenyl-α-naphthylamine, diphenyl-p-phenylenediamine, 1,3-bis-(dimethylaminopropyl)-2-thiourea, and mixtures thereof.

[0047] In an embodiment, the scorch inhibitor is a metal salt selected from the group consisting of bismuth dimethyldithiocarbamate, cadmium diamyldithiocarbamate, cadmium diethyldithiocarbamate, copper dimethyldithiocarbamate, lead diamyldithiocarbamate, lead dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, zinc diamyldithiocarbamate, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and mixtures thereof.

[0048] In an embodiment, the curable polymer composition contains a single scorch inhibitor or a mixture of two or more scorch inhibitors. The mixture of scorch inhibitors can have at least one scorch inhibitor based on α-methylstyrene dimer and / or based on hydrocarbons without heteroatoms or polar groups.

[0049] In embodiments, the scorch inhibitor is added to the curable polymer composition in an amount of 0.001 to 10, or 0.005 to 10, or 0.010 to 10, or 0.050 to 10, or 0.001 to 5, or 0.005 to 5, or 0.010 to 5, or 0.050 to 5 wt %, based on the total weight of the curable polymer composition, excluding the amount of glass fiber.

[0050] (optional ingredient) The curable polymer composition further comprises at least one additive selected from initiators, activators, curing agents, stabilizers, neutralizing agents, thickeners, coalescing agents, antioxidants, antiozonants, color changing pH indicators, plasticizers, tackifiers, film forming additives, dyes, pigments, crosslinkers, UV absorbers, UV stabilizers, catalysts, fillers, other polymers, fibers, flame retardants, viscosity modifiers, wetting agents, deaerators, toughening agents, adhesion promoters, colorants, heat stabilizers, lubricants, flow control agents, drip suppressants, antistatic agents, processing aids, accelerators, water resistance agents, waterproofing agents, thermal conductivity agents, electromagnetic wave shielding agents, fluorescent agents, radical scavengers, and mixtures thereof.

[0051] Non-limiting examples of accelerators include dibenzothiazole, N-cyclohexyl-2-benzothiazole, N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N,N-dicyclohexyl-2-benzothiazole sulfenamide (DCBS), thiocarbamyl sulfenamide, 2-(4-morpholinothio)-benzothiazole (MBS), N-oxydiethylenethiocarbamyl-N-oxydiethysulfonamide (OTOS), 2-mercaptobenzothiazole (MBT), 2-2′-dithiobis(benzothiazole) (M BTS), tetramethylthiuram disulfide (TMTD), N-tert-butyl-2-benzothiazole sulfonamide (TBBS), dipentamethylene thiuram tetrasulfide (DPTT), 4,4'-dithiodimorpholine (DTDM), zinc dimethyldithiocarbamate, thiourea, xanthates, thiophosphates, 2-mercaptobenzothiazole zinc salt (ZMBT), 2-(4-morpholinodithio)benzothiazole (MDB), diethylthiocarbamoyl-2-mercaptobenzothiazole, and mixtures thereof.

[0052] In an embodiment, the curable polymer composition may be selected from the group consisting of hydroperoxides, liquid peroxydicarbonates, dialkyl peroxides, diperoxyketals, monoperoxycarbonates, cyclic ketone peroxides, diacyl peroxides, dicumyl peroxide (DCP), t-butylcumyl peroxide, organosulfonyl peroxides, 1,3-bis-(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-(t-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(t-amylperoxy)hexane, 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne, di-t-butyl peroxide, α,α-di[(t-butylperoxy)-isopropyl]benzene, and mixtures thereof.

[0053] In embodiments, the additive is used in an amount from 0.1 to 10, or from 0.5 to 8, or from 0.1 to 5, based on the total weight of the curable polymer composition.

[0054] In an embodiment, the curable polymer composition further comprises a polymer other than the DIAEA-DVA copolymer. Examples of such other polymers include 1,2-polybutadiene, polyisoprene, polybutadiene-polyisoprene copolymer, polybutadiene-polystyrene-polydivinyl-benzene terpolymer, polyphenylene ether, curable cyclic olefins or copolymers thereof, polyacrylate, polydicyclopentadiene, styrene-isoprene-styrene copolymer, butadiene-acrylonitrile copolymer, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, polyester, styrene block copolymer, polyolefin, polytetrafluoroethylene (PTFE), polyetherimide (PEI), maleimide resin, cyanate ester resin, epoxy resin, phenolic resin, benzoxazine resin, polyamide resin, polyimide resin, polyphenylene ether, polyphenylene sulfide, polyacetal, polysulfone, polyesterimide, polyethersulfone, polyetherketone, fluororesin, and mixtures thereof.

[0055] In an embodiment, the curable polymer composition is selected from the group consisting of natural rubber (NR), butyl rubber, halogenated butyl rubber, and EPDM (ethylene propylene diene monomer rubber), styrene-butadiene rubber (SBR), butadiene rubber, synthetic polyisoprene rubber, epoxidized natural rubber, polybutadiene rubber, high cis polybutadiene rubber, ethylene propylene diene monomer rubber, ethylene propylene rubber, maleated ethylene propylene rubber, isobutylene-vinyl aromatic or diene monomer copolymer, brominated NR, chlorinated NR, brominated isobutylene p-methylstyrene copolymer, chloroprene rubber, epichlorohydrin homopolymer rubber, epichlorohydrin-ethylene oxide or The rubbery polymer may further comprise a rubbery polymer selected from allyl glycidyl ether copolymer rubber, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber, fluorinated silicone rubber, fluorinated phosphagen rubber, styrene elastomer, thermoplastic olefin elastomer, polyester elastomer, urethane elastomer, polyamide elastomer, and mixtures thereof.

[0056] Any suitable amount of other polymers and / or rubbery polymers can be incorporated into the curable polymer composition based on the desired end use, such polymers ranging from 10-99, or 15-95, or 20-70, or 25-60, or 30-55, or >25, or <50 wt %, based on the total weight of the curable polymer composition, excluding the amount of glass fiber, if used.

[0057] (Method of preparing a curable polymer composition) The curable polymer composition can be prepared by any process known in the art, such as compounding, blending, or in solution. In embodiments, the curable polymer composition is compounded by mixing all of the components of the composition. Compounding can be accomplished by any conventional mixing or compounding operation, such as single and twin screw extruders. The mixing temperature can be selected to obtain and maintain an intimate blend of the components after cooling, without premature crosslinking.

[0058] In embodiments, the curable polymer composition includes a mixture of the copolymer, the scorch inhibitor, and optional ingredients. A crosslinker can be added to the mixture to effect curing of the composition.

[0059] In embodiments, the scorch inhibitor is added to the copolymer along with any optional ingredients to form the curable polymer composition, followed by the addition of the crosslinker, and then the composition is subjected to curing.

[0060] In embodiments, the curable polymer composition is prepared by mixing all of the components in a hydrocarbon solvent, such as toluene, and stirring for a sufficient time to obtain the curable polymer composition in solution. The concentration of the curable polymer composition in the hydrocarbon solvent (total solids content) can be 10-80 wt%, or 20-75 wt%, or 25-80 wt%, or 30-75 wt%, or >20 wt%, or <75 wt%, based on the total weight of the solution.

[0061] The curable polymer composition can be used as is, for example in a solvent, or can be made into a film for downstream end use and cured and / or crosslinked for use, for example, in CCL applications.

[0062] In an embodiment, a polymer composition is prepared that includes a DIAEA-DVA copolymer and optional ingredients, but does not include a scorch inhibitor, and can be used to compare certain properties with curable polymer compositions.

[0063] (Curing of the curable polymer composition) The curable polymer composition can be cured by using an external source, such as heat, ultraviolet light (UV), visible light, electron beam, or a combination thereof, to obtain a cured polymer composition. Curing of the composition can be carried out with or without an initiator.

[0064] In embodiments, curing of the curable polymer composition is carried out at a temperature of 140-250°C, or 145-220°C, or 150-210°C, or 155-200°C, or >140°C, or >150°C, for a time of 0.5-60 minutes, or 1-50 minutes, or 5-40 minutes, or 10-30 minutes.

[0065] In embodiments, the curable polymer composition is cured at a temperature at least 30° C. higher than the curing temperature of the polymer composition without the scorch inhibitor. In embodiments, the curable polymer composition is cured at a temperature at least 35° C., or at least 40° C., or at least 45° C. higher than the curing temperature of the polymer composition without the scorch inhibitor.

[0066] In embodiments, after curing >60%, or >65%, or >70%, or >75%, or >80%, or >85%, or >90%, or >99% of the vinyl groups in the DIAEA-DVA copolymer are consumed due to the crosslinking step (relative to the total vinyl groups present in the DIAEA-DVA copolymer before curing).

[0067] Properties of DIAEA-DVA Copolymers and Curable Polymer Compositions In embodiments, DIAEA-DVA copolymers are resinous materials that have a good combination of molecular weight range and relatively broad molecular weight distribution (polydispersity index), which makes them partially more soluble in non-polar solvents, thereby enhancing their processability.

[0068] In embodiments, the DIAEA-DVA copolymer has a solubility in a hydrocarbon solvent that is at least 10, or >20, or >30, or >50, or >70, or <99, or 10-75, or 20-65, or 10-60 wt %, based on the total weight of the solvent, in less than 4 hours at 25° C. Exemplary solvents include hexane, heptane, octane, isooctane, cyclohexane, varnish paint naphtha (VM&P naphtha), petroleum ether, toluene, xylene, and mixtures thereof.

[0069] In embodiments, the DIAEA-DVA copolymer as a solid, when dissolved in a hydrocarbon solvent, forms a substantially gel-free solution, with <2, or <5, or <10, <15 wt % of the solid remaining insoluble in the solvent.

[0070] In embodiments, the DIAEA-DVA copolymer solution in the hydrocarbon solvent has a gel content, based on the total weight of the copolymer, of 0.05-5, or 0.1-4.5, or 1-4, or <5 wt%, or <2 wt%, or <1 wt%.

[0071] In embodiments, the DIAEA-DVA copolymer has an onset decomposition temperature of 200-450°C, or 220-420°C, or 240-400°C, or <600°C, or <500°C, or >300°C.

[0072] In embodiments, the DIAEA-DVA copolymer has a glass transition temperature (T) of 50-300° C., or 60-250° C., or 70-220° C., or 80-200° C., or 100-250° C., or 120-220° C., or >150° C., or <250° C., or <200° C., as measured using differential scanning calorimetry (DSC) or DMA (Dynamic Mechanical Analyzer) according to ASTM D3418. g ).

[0073] In embodiments, the DIAEA-DVA copolymer has a moisture absorption coefficient, as measured at 25° C. by ASTM D570, of <0.1, or <0.08, or <0.05.

[0074] In embodiments, the DIAEA-DVA copolymer has a density of >0.9, or >1.0, or from 1.0 to 2.0, or from 1.0 to 1.50 g / cc.

[0075] In embodiments, a curable polymer composition having a concentration of 72.5 wt % in toluene has a solution viscosity at 25° C. after storage at 40° C. for 1 day that is at least 20% less, or at least 30% less, or at least 40% less than the solution viscosity of the polymer composition without the scorch inhibitor.

[0076] In embodiments, the curable polymer composition having a concentration of 72.5 wt % in toluene and after aging at 40° C. for 50 days has an increase in solution viscosity of <30%, or <25%, or <20%, or <15% compared to the initial solution viscosity (before aging).

[0077] In embodiments, the curable polymer composition having a concentration of 72.5 wt % in toluene and after aging for 100 days at 40° C. has an increase in solution viscosity of <50%, or <45%, or <40%, or <35% compared to the initial solution viscosity (before aging).

[0078] In embodiments, the curable polymer composition having a concentration of 72.5 wt % in toluene and after aging for 181 days at 40° C. has an increase in solution viscosity of <50%, or <45%, or <40% compared to the initial solution viscosity (before aging).

[0079] In embodiments, the curable polymer composition has a gel point of >125°C, or >130°C, or >132°C, or >135°C, or >138°C, or >140°C, as measured on a film sample of the curable polymer composition dried at 120°C for 5 minutes using a Discovery Hybrid Rheometer (DHR).

[0080] In embodiments, the curable polymer composition has a gel point of >135°C, or >140°C, or >145°C, or >150°C, as measured on film samples dried at 35°C for 5 minutes using a Discovery Hybrid Rheometer (DHR).

[0081] In embodiments, the curable polymer composition has a gel point that is at least 10%, or at least 15%, or at least 20% higher than a polymer composition without the scorch inhibitor, as measured on film samples dried at 120° C. for 5 minutes using a Discovery Hybrid Rheometer (DHR).

[0082] Properties of the Cured Polymer Composition Due to the excellent crosslinking properties, the undesirable scorch phenomenon does not occur, and the cured polymer composition has high practical utility. The cured polymer composition has various degrees of toughness, flexibility, good chemical and oxidative stability, and high flame retardancy, which are useful for electronic applications.

[0083] In embodiments, the cured polymer composition has a Dk (dielectric constant) measured at 10 GHz by ASTM D2520 of <2.7, or <2.65, or <2.60, or <2.55.

[0084] In embodiments, the cured polymer composition has a Df (loss tangent) measured at 10 GHz by ASTM D2520 of <0.006, or <0.005, or <0.004, or from 0.003 to 0.0001, or from 0.002 to 0.0001.

[0085] In embodiments, the curable polymer composition during the curing process has an exotherm energy value of >80, or >100, or >120, or >140, or >160, or >180, or >200 J / g, or 60-220, or 80-210, or 100-200 J / g. The exotherm energy is an indication of the degree of crosslinking and can be measured by analysis of the exotherm peak obtained by increasing the temperature from room temperature to 300 or 400° C. at a rate of 10° C. / min using a differential scanning calorimeter (DSC).

[0086] The cured polymer composition has good adhesion to metals such as aluminum, copper, etc. In embodiments, the cured polymer composition has a 180° peel strength to metal of 0.1 to 1.0, or 0.2 to 0.9, or 0.3 to 0.7 N / m.

[0087] In embodiments, the cured polymer composition has a swell content at room temperature of <30%, or <25%, or <20%, or <15%, or <10%, or <5%, or from 0 to 30%, or from 0 to 20%, or from 0 to 10%, based on the total initial weight of the cured polymer composition.

[0088] In embodiments, the cured polymer composition has a swell content at 90° C. of <30%, or <25%, or <20%, or <15%, or <10%, or <7%, or from 0 to 30%, or from 0 to 20%, or from 0 to 10%, based on the total initial weight of the cured polymer composition.

[0089] In embodiments, the cured polymer composition has a gel content after 4 hours at room temperature that is >85%, or >88%, or >90%, or >95%, or >98%, or >99%, or less than or equal to 100%, based on the total weight of the cured polymer composition.

[0090] In embodiments, the cured polymer composition has a gel content after 9 hours at 90° C. that is >85%, or >88%, or >90%, or >95%, or >98%, or >99%, or less than or equal to 100%, based on the total weight of the cured polymer composition.

[0091] In embodiments, a cured polymer composition containing 40 wt. % glass fibers (based on the total weight of the cured polymer composition) has a coefficient of thermal expansion (CTE) of 5 to 40, or 10 to 25, or 15 to 20 ppm / °C in the XY plane and 30 to 120, or 40 to 95, or 45 to 85 ppm / °C in the Z direction, measured using DMA over the range of -50 to 300°C.

[0092] (Uses of the curable polymer composition) The curable polymer compositions can be used in automotive coating applications such as refinish, primers, basecoats, undercoats, overcoats, clearcoats, etc. Power cables, particularly cables useful in both alternating current (AC) and direct current (DC) applications in high voltage applications, can be obtained from the curable polymer compositions.

[0093] The curable polymer compositions may be useful for use as metal clad laminates, e.g., copper clad laminates (CCL), electrical appliance housings, electrical cables, electrical connectors, electronic switches, and electronic components such as printed circuit boards (PCBs), printed wiring boards, and flexible printed circuits (FPCs).

[0094] Prepregs for use in PCB fabrication can be made by processes known in the art using a curable polymer composition in combination with a rubber component and optional additives. In an embodiment, the curable polymer composition includes glass fibers for PCB preparation. The glass fibers can be pretreated with organosiloxanes, such as polyalkylsiloxanes, polyarylsiloxanes, etc., to increase adhesion between the glass fibers and the copolymer.

[0095] In an embodiment, the CCL comprises a metal foil disposed on one or both sides of an insulating layer made from the cured polymer composition. Additionally, the CCL may comprise a barrier layer disposed on the side of the surface in contact with the insulating layer. The barrier layer may contain a metal, such as cobalt, which may reduce transmission loss. The barrier layer may be formed by a plating process, for example, sputtering, electroplating, or electroless plating. A stacked laminate of a desired thickness may be produced by stacking individual laminates and subjecting them to heating, for example, at a temperature in the range of 110-220°C, or 120-210°C, or 125-180°C, and a pressure of, for example, 0.5-20, or 1-18, or 2-15, or 5-12 MPa, for a time in the range of 10 minutes to 5 hours, or 2 hours to 20 hours. EXAMPLES

[0096] The following examples are intended to be non-limiting.

[0097] The solution viscosity of the curable polymer composition is measured by a Brookfield viscometer. The concentration in the hydrocarbon solvent is the total solids content, e.g., copolymer with or without scorch inhibitor. The concentration can range from 10 to 80 wt %, based on the total weight of the solution.

[0098] Rheological properties, such as gel point, are measured using a Discovery Hybrid Rheometer (DHR) manufactured by TA Instruments.

[0099] The ingredients used in the examples include the following:

[0100] Scorch inhibitor-1 (ASA-1) is a sulfur-containing phenolic compound.

[0101] Scorch inhibitor-2 (ASA-2) is a nitrogen-containing cyclic compound.

[0102] Example 1 Preparation of copolymer of 1,3-DIPEB and 1,3-divinylbenzene. A 3-liter three-neck flask was charged with 921 g of cyclohexane and heated to 65°C, and 0.0125 g of triflic acid was added with continuous stirring. A mixture of 64.5 g of 1,3-DIPEB, 185.7 g of 1,3-divinylbenzene, and 250 g of cyclohexane was added over 30 minutes. After the addition of the mixture, the reaction contents were quenched with 750 mL of water and 2 g of NaHCO3, followed by heating the reaction contents at 65°C for an additional 15 minutes. The aqueous layer was removed from the bottom. The remaining organic layer was washed with water several times. The copolymer product was recovered by removing the solvent.

[0103] Example 2 Curable polymer compositions were prepared using the copolymer of Example 1 at a concentration of 50 wt% and various amounts of scorch inhibitor in toluene. The samples were aged in an oven at different temperatures and for various times. The evaluation of the viscosity change was done by visual observation of the samples and Comparative Example 2a without scorch inhibitor. Table 1 shows the data and results of various samples after visual observation.

[0104] [Table 1]

[0105] Example 3 Film samples of the curable polymer composition were prepared by combining the copolymer of Example 1 and different scorch inhibitors (various amounts) in toluene with a concentration of 70 wt%, and then solvent casting onto silicon substrates. Each film, 100 microns thick, was dried at room temperature for 1 hour, followed by drying at 120°C for 5 minutes. The film samples were then removed from the silicon substrates to measure the gel point using DHR. The results are shown in Table 2. Comparable is Example 3a.

[0106] [Table 2]

[0107] Example 4 Curable polymer compositions of the copolymer of Example 1 and various amounts of scorch inhibitor were prepared at a concentration of 72.5 wt% in toluene. The samples were kept in an oven at 40°C for aging up to 181 days. Visual observations were made on each sample and the viscosity was measured by using a DHR at 25°C. The results are shown in Table 3. Comparable is Example 4a.

[0108] [Table 3]

[0109] Example 5 Gel point measurements were performed on film samples prepared by repeating the procedure of Example 3, except for the combination of two scorch inhibitors. Each film was dried at room temperature for 1 hour, followed by 5 minutes at 35°C or 120°C. The film samples were then removed from the silicon substrate for gel point measurement using DHR as shown in Table 4. The thickness of each film was 100 microns. Comparable are Examples 5a and 5f.

[0110] [Table 4]

[0111] Example 6 Preparation of the cured polymer composition.

[0112] Samples 5f and 5i from Example 5 were mixed separately with 0.5 wt% dicumyl peroxide. Each sample was placed in a mold and pressed at 8,000 psi at 100°C for 5 minutes, followed by 20,000 psi at 180°C for 2 hours. The gel content (4 hours at room temperature), swell content (4 hours at room temperature), Dk, and Df of the samples were measured. The results are shown in Table 5.

[0113] [Table 5]

[0114] As used herein, the term "comprising" means including the elements or steps identified following the term, but any such elements or steps are not exhaustive and embodiments may include other elements or steps. Although the terms "comprising" and "including" have been used herein to describe various aspects, "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific aspects of the present disclosure, and are also disclosed.

Claims

1. A curable polymer composition, (i) A copolymer of diisoalkenylarene and divinylarene, The molar ratio of diisoalkenylarene to divinylarene is 1:15 to 15:

1. Solubility measured by the solubility test described in the specification, in a hydrocarbon solvent at 25°C for less than 4 hours at a concentration of at least 10 wt%, Glass transition temperature (T) between 50°C and 300°C as measured by ASTM D3418 ｇ ), The gel content, measured by the gel content test described in the specification, is less than 5 wt% of the total weight of the copolymer. A copolymer of diisoalkenylarene and divinylarene having, (ii) A scorch inhibitor in an amount of 0.001 to 10 wt% based on the total weight of the curable polymer composition, selected from the group comprising styrene, α-methylstyrene monomer, α-methylstyrene dimer, α-methylstyrene oligomer, hindered phenol compounds, non-hindered phenol compounds, benzimidazole, and mixtures thereof. Includes, The curable polymer composition, at a concentration of 72.5 wt% in toluene, is stored at 40°C for one day and then, when measured at 25°C using a Brookfield viscometer, has a solution viscosity at least 20% lower than that of the polymer composition without the scorch inhibitor. A curable polymer composition.

2. The curable polymer composition according to claim 1, having a molar ratio of diisoalkenylarene to divinylarene of 10:1 to 1:

10.

3. The curable polymer composition according to claim 1, wherein the copolymer has a solubility of 10 to 75 wt% in a hydrocarbon solvent at 25°C for less than 4 hours.

4. The curable polymer composition according to any one of claims 1 to 3, wherein the copolymer has a gel content of 0.05 to 5 wt%.

5. The curable polymer composition according to any one of claims 1 to 3, wherein the copolymer has a glass transition temperature of 100°C to 250°C.

6. A curable polymer composition according to any one of claims 1 to 3, having a solution viscosity at least 30% lower than the solution viscosity of the polymer composition that does not contain the scorch inhibitor.

7. The gelation point greater than 125°C was measured on a film of the curable polymer composition dried at 120°C for 5 minutes, and Gelation point greater than 140°C measured on a film of the curable polymer composition dried at 35°C for 5 minutes. A curable polymer composition according to any one of claims 1 to 3, having at least one of the above.

8. The curable polymer composition according to any one of claims 1 to 3, wherein, when measured on a film of the curable polymer composition dried at 120°C for 5 minutes, it has a gelation point at least 10% higher than that of the polymer composition without the scorch inhibitor.

9. The diisoalkenylarene is selected from the group consisting of 1,3-diisopropenylbenzene, 1,2-diisopropenylbenzene, 1,4-diisopropenylbenzene, 3,4-dicyclohexyl-1,2-diisopropenylbenzene, 5-(3-methyl-cyclopentyl)-1,3-diisopropenylbenzene, 3-cyclopentyl-methyl-6-n-propyl-1,4-diisopropenylbenzene, 4-(2-cyclo-butyl-1-ethyl)-1,2-diisopropenylbenzene, 3-(2-n-propylcyclopropyl)-1,4-diisopropenylbenzene, 2-methyl-5-n-hexyl-1,3-diisopropenylbenzene, 4-methyl-1,2-diisopropenylbenzene, 5-ethyl-1,3-diisopropenylbenzene, 3-methyl-1,4-diisopropenylbenzene, and mixtures thereof. The divinylarene is selected from the group consisting of divinylbenzene, divinylnaphthalene, divinylbiphenyl, divinyldiphenyl ether, and mixtures thereof. A curable polymer composition according to any one of claims 1 to 3.

10. The copolymer has a number average molecular weight (M) of 1 to 10 kg / mol. ｎ ), weight-average molecular weight (M) of 3-70 kg / mol ｗ A curable polymer composition according to any one of claims 1 to 3, having a polydispersity index of 2 to 20.

11. The curable polymer composition according to any one of claims 1 to 3, comprising 0.010 to 5 wt% of the scorch inhibitor based on the total weight of the curable polymer composition.

12. A cured polymer composition obtained by curing the curable polymer composition according to any one of claims 1 to 3 at a temperature higher than 140°C, A gel content greater than 90%, as measured by the gel content test described in the specification, Both values ​​are measured at 10 GHz using an ASTM D2520, with a dielectric constant (Dk) less than 2.7 and a dielectric loss tangent (Df) less than 0.

006. A cured polymer composition characterized by having the following:

13. The curable polymer composition according to claim 12, wherein the curable polymer composition is cured at a temperature at least 30°C higher than the curing temperature of the polymer composition that does not contain the scorch inhibitor.

14. Swelling content of less than 30%; and Gel content greater than 95% A cured polymer composition according to claim 12, having at least one of the above.

15. The cured polymer composition according to claim 13, wherein both have a dielectric constant (Dk) of <2.6 and a dielectric loss tangent (Df) of <0.005, as measured at 10 GHz by ASTM D2520.