Block copolymers and their use

Abstract

To provide a polymer composition comprising a star-branched copolymer having a plurality of arms.SOLUTION: Each polymer arm has a molecular weight of from 1 kg / mol to 50 kg / mol and comprises: polymerized units (i) derived from a first vinyl aromatic monomer comprising a radical-reactive group; and optionally, polymerized units (ii) comprising hydrogenated and unhydrogenated forms of polymerized units derived from a high Tg monomer, and hydrogenated form of polymerized units (i) or hydrogenated form of polymerized styrene units; and optionally, polymerized units (iii) comprising (a) hydrogenated form of polymerized units derived from one or more acyclic conjugated dienes, and (b) polymerized units derived from one or more of a second vinyl aromatic monomer; wherein less than 10 wt.% of units (a) are unhydrogenated.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to selectively hydrogenated copolymers, curable compositions and cured compositions produced therefrom, and their use including high temperature applications.

Background Art

[0002] The rapid progress of technologies related to various fields such as electronics and automotive applications has caused a demand for high-performance materials. Large-capacity computer systems and networks require high-frequency signal transmission by circuit boards suitable for high frequencies and high-speed transmission. It is desirable for these circuit boards to operate signals with high frequencies and low transmission losses, such as dielectric losses, conductor losses, and radiation losses. Transmission losses weaken electrical signals and impair signal reliability.

[0003] In many commercial fields such as the automotive industry, construction, tool manufacturing, adhesives, and sealants, materials are needed that have good mechanical properties with a low loss factor over a wide temperature range and also have good processing capabilities. Some of the major applications require materials with good mechanical properties regarding strength and sufficient modulus of elasticity or hardness. Existing materials cannot meet such requirements.

[0004] Printed circuit boards have traditionally used epoxy resins, which have a relatively high dielectric constant and a high dielectric tangent. Epoxy resins can be used with phenolic compounds, amine or acid anhydride curing agents for improved properties. It is still difficult for such resin compositions to achieve a low loss factor. Polyphenylene ether resins (polyphenylene oxide resins or PPOs) have been used in laminates due to their low dissipation characteristics, but the use of high-frequency signals in new electronics fields requires even lower dielectric constants and loss factors. There are other plastic solutions based on, for example, fluorinated polymers that have lower loss factors, but these plastic solutions lack easy processability or efficient curability to withstand high temperatures or the presence of solvents. [Overview of the project] [Problems that the invention aims to solve]

[0005] There is still a need for improved compositions having improved properties such as improved mechanical properties, high-temperature performance, and / or improved electrical properties, which are suitable for use in copper-clad laminates and printed circuit boards manufactured therefrom. [Means for solving the problem]

[0006] (Summary of the invention) In one embodiment, a polymer composition comprising a star-branched copolymer is disclosed. The star-branched copolymer has a plurality of polymer arms, each polymer arm having a molecular weight Mp of 1 kg / mol to 50 kg / mol. Each polymer arm comprises polymerization unit (i), and optionally polymerization unit (ii), and optionally polymerization unit (iii). Polymerization unit (i) is derived from a first vinyl aromatic monomer containing a radically reactive group, where more than 10 mol% to 100 mol% of the polymerization unit is unhydrogenated. Polymerization unit (ii) comprises hydrogenated and unhydrogenated polymerization units derived from a high Tg monomer, and the hydrogenated polymerization unit (i) or the hydrogenated polymerized styrene unit, and optionally, polymerization unit (iii). Polymerization unit (iii) comprises (a) a hydrogenated polymerization unit derived from one or more acyclic conjugated dienes, and (b) a polymerization unit derived from one or more second vinyl aromatic monomers, where less than 10 wt% of unit (a) is unhydrogenated. The copolymer contains more than 10% by weight of polymerization unit (i), and polymerization units (i) and (ii) together constitute more than 50% by weight of the total weight of the star-branched copolymer. The copolymer has a molecular weight Mp of 15 kg / mol to 500 kg / mol and a glass transition temperature of over 100°C to 250°C.

[0007] In other embodiments, a curable composition comprising a polymer composition containing a star-branched copolymer, and a curable composition produced from this curable composition are also disclosed. [Modes for carrying out the invention]

[0008] Unless otherwise specified, "molecular weight" refers to the styrene-equivalent molecular weight (kg / mol) of a polymer or block copolymer. Molecular weight can be measured by gel permeation chromatography (GPC) using a polystyrene calibration standard, for example, according to ASTM 5296-19. The chromatograph is calibrated using a commercially available polystyrene molecular weight standard. The molecular weight of a polymer measured using such a calibrated GPC is the styrene-equivalent molecular weight. The detector may be a combination ultraviolet and refractive index detector. Molecular weights as described herein are measured at the peak of the GPC trace, converted to the true molecular weight, and generally referred to as the "peak molecular weight," denoted as Mp. Molecular weight refers to the styrene-equivalent peak molecular weight.

[0009] The loss factor (Df), or tangent delta, is defined as the ratio of the equivalent series resistance (ESR) to the capacitive reactance. The loss factor is also known as the tangent of the loss angle and is typically expressed as a percentage.

[0010] The dielectric constant (Dk), a property of an electrical insulating material (dielectric), is equal to the ratio of the capacitance of a capacitor filled with a given material to the capacitance of the same capacitor without a dielectric material in a vacuum. These aspects of the present disclosure, as well as other features and advantages, will become apparent from the following detailed description.

[0011] <Polymer Composition>: The polymer composition includes a star-branched polymer constituting more than 80% by weight of the polymer composition. In several embodiments, the star-branched polymer constitutes 85-100% by weight, or 90-95% by weight, or 95-100% by weight of the polymer composition. In another embodiment, the polymer composition consists essentially of a star-branched copolymer.

[0012] The star-branched copolymer has multiple polymer arms. Each polymer arm can have a molecular weight of 1 kg / mol to 50 kg / mol. Each polymer arm contains polymerization units (i), optionally polymerization units (ii), and optionally polymerization units (iii). Each of these parts of the star-branched copolymer structure is discussed in detail below.

[0013] Polymerization unit (i) is derived from a first vinyl aromatic monomer. The first vinyl aromatic monomer has a structure containing a radical-reactive group. A radical-reactive group is a chemical group that can form or be induced to form a free radical species. Free radical species can be formed by any known means, including thermal means, photochemical means and chemical reagents. For example, a benzyl carbon having at least one hydrogen substituent can be a radical-reactive group. The benzyl carbon group can also be substituted as long as it has one benzyl hydrogen atom. Another example of a radical-reactive group is the cyclobutane ring, which can be photochemically activated, for example, to form a free radical species. Another example of a radical-reactive group is the allyl group, which can form an allyl free radical.

[0014] In one embodiment, the first vinyl aromatic monomer may be substituted styrene of formula (I), vinylbenzocyclobutene of formula (II), vinyldihydroindene of formula (III), vinyltetrahydronaphthalene of formula (IV), or any combination thereof.

[0015] [Table 1]

[0016] In one embodiment, units (i) in the range of more than 10 mol% to 100 mol% are not hydrogenated. In other embodiments, units (i) in the range of 20 to 90 mol%, or 30 to 80 mol%, or 40 to 70 mol%, or 50 to 60 mol%, are not hydrogenated.

[0017] Examples of monomers of formula (I) include o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, o-isopropylstyrene, para-isopropylstyrene, o-methyl-α-methylstyrene, p-methyl-α-methylstyrene, o-ethyl-α-methylstyrene, p-ethyl-α-methylstyrene, o-isopropyl-α-methylstyrene, para-isopropyl-α-methylstyrene, or any mixture thereof. In one embodiment, the first vinyl aromatic monomer includes p-methylstyrene, p-methyl-α-methylstyrene, or a combination thereof. In another embodiment, the first vinyl aromatic monomer includes p-methylstyrene.

[0018] Polymerization unit (ii) is derived from high-Tg monomers, for example, anionic polymerizable monomers that, when homopolymerized or copolymerized with other comonomers, can produce polymers having high glass transition temperatures (Tg), such as 300°C or less, or 100-250°C, or 110-200°C, or 120-160°C. High-Tg monomers have anionic polymerizable vinyl groups and can have a variety of structures. Non-limiting examples of high-Tg monomers include compounds selected from the group consisting of tert-butylstyrene, 1,3-cyclohexadiene, benzoflubene, 1,1-diphenylethylene, vinylbiphenyl, adamantylstyrene, vinylanthracene, divinylbenzene, bis(vinylphenyl)ethane, and combinations thereof. The aromatic ring in the monomer can also be bicyclic, tricyclic, or polycyclic. The polymerizable vinyl group can also be contained within the ring, for example, indene or its substituted derivatives.

[0019] Other examples of high-Tg monomers include conjugated cyclodienes such as 1,3-cyclohexadiene, 1,3-cycloheptadiene, their substituted derivatives, or combinations thereof. 1,3-cyclohexadiene is preferred because it is relatively more readily available.

[0020] When conjugated cyclodienes are used as high-Tg monomers, anionic polymerization can proceed by varying degrees of 1,4-addition and 1,2-addition mechanisms. The ratio can be influenced not only by the monomer structure but also by other additives present during polymerization. For example, additives can be used to increase 1,2-addition over 1,4-addition. In some embodiments, polymerization units derived from a conjugated cyclodiene such as 1,3-cyclohexadiene, or any of the high-Tg monomers mentioned above, can contain 1,2- and 1,4-polymerization units in relative molar ratios of 90:10 to 10:90, or 85:15 to 15:85, or 80:20 to 20:80, or 70:30 to 30:70, or 60:40 to 40:60, or 55:45 to 45:55. In certain embodiments, the 1,2- and 1,4-polymerization units derived from 1,3-cyclohexadiene can vary in relative molar ratios from 90:10 to 10:90. For example, additives such as TMEDA are known to produce 1,2- and 1,4-polymerization units with relative molar ratios close to 50 / 50 content. Modifiers such as DEP can produce a 1,2 to 1,4 ratio closer to 30 / 70, for example, and modifiers such as DABCO can yield a 1,2 to 1,4 ratio closer to 10 / 90.

[0021] In a polymer composition comprising a star-branched polymer containing polymerization units (i) and (ii), the copolymer may contain more than 10% by weight of polymerization unit (i), and as a result, polymerization units (i) and (ii) together constitute more than 50% by weight, or more than 60% by weight, or more than 70% by weight, or more than 80% by weight, or more than 90% by weight, or essentially 100% by weight of the total weight of the copolymer.

[0022] In another embodiment, the polymer composition comprising the star-branched polymer comprises polymerization units (i), (ii) and (iii), contains more than 10% by weight of the polymerization unit (i), and as a result, the polymerization units (i) and (ii) together constitute more than 50% by weight, or more than 60% by weight, or more than 70% by weight, or more than 80% by weight, or more than 90% by weight of the total weight of the copolymer.

[0023] The polymer composition containing the polymerization unit (i) derived from the first vinyl aromatic monomer containing the radically reactive groups listed in Table 1 exhibits a solution viscosity of less than 5000, or less than 2000 centipoise, or 200 - 1800 centipoise, or 400 - 1500 centipoise, or 600 - 1200 centipoise, or 800 - 1000 centipoise when measured at 25 °C as a 25% by weight solution in toluene.

[0024] In another embodiment, the star-branched copolymer has a molecular weight of more than 30 kg / mol and a solution viscosity measured at 25 °C at a copolymer content of 25% by weight in toluene of less than 2000 centipoise.

[0025] In some embodiments, the star-branched copolymer has a structure in which, before hydrogenation, the polymerization unit of type (i) is a polymerized para-methylstyrene unit. In another embodiment, the copolymer has a structure in which the first vinyl aromatic monomer is para-methylstyrene, and the polymerized unit (ii) includes a hydrogenated form of polymerized para-methylstyrene, polymerized divinylbenzene, polymerized tert-butylstyrene, or a combination thereof, and the polymerization units (i) and (ii) together constitute more than 60% by weight, or 60 - 100% by weight, or 70 - 95% by weight, 75 - 90% by weight, or 80 - 90% by weight of the total weight of the copolymer. In yet another embodiment, the copolymer contains more than 10% by weight of the polymerization unit (i), and as a result, when the polymerization unit (ii) is also present, the units (i) and (ii) together constitute more than 50% by weight of the total weight of the copolymer.

[0026] Star-branched copolymers may also optionally include polymerization units (iii) comprising (a) a hydrogenated form of polymerization units derived from one or more acyclic conjugated dienes and (b) polymerization units derived from one or more second vinyl aromatic monomers, wherein less than 10% by weight of (a) is unhydrogenated. In some embodiments, the conjugated diene is an acyclic 1,3-diene, non-limiting examples of which include 2,3-dimethyl-1,3-butadiene, butadiene, isoprene, 1,3-pentadiene, farnesene, myrcene, 1,3-hexadiene, and combinations thereof. The second vinyl aromatic monomer can be any anionically polymerizable aromatic compound such as styrene, substituted styrene, or other vinyl aromatic compounds. The use of an acyclic 1,3-diene makes it possible to introduce polymer blocks with low glass transition temperatures, i.e., polymer soft blocks at room temperature or the application temperature. In several embodiments, the relative proportion of polymerization units derived from the second vinyl aromatic monomer and the conjugated diene can vary in molar ratio from 100:0 to 0:100. Using the second vinyl aromatic monomer in small amounts, or not at all, for example, less than 50 mol%, may be useful in producing soft polymer blocks with lower Tg.

[0027] The star-branched copolymer has a molecular weight Mp of 15 to 500 kg / mol. In other embodiments, the copolymer has a molecular weight of 30 to 400 kg / mol, or 50 to 200 kg / mol. The copolymer has a Tg of 100 to 250°C. In some embodiments, the Tg can vary in the range of 110 to 225°C or 150 to 200°C.

[0028] In another embodiment, the star-branched copolymer structure may include polymerization units (ii) derived from 1,3-cyclohexadiene and containing 1,2- and 1,4-addition units in a relative molar ratio of 90:10 to 10:90. The ratio of 1,2- to 1,4-addition of the diene monomer can generally be controlled using certain types of additives, as previously described. In yet another embodiment, the star-branched copolymer may have a structure in which more than 50 mol%, or 50 to 100 mol%, or 60 to 90 mol%, or 70 to 80 mol%, of the polymerized 1,3-cyclohexadiene units is hydrogenated. In yet another embodiment, the copolymer may further include polymerization units (iii) in which the second vinyl aromatic monomer is styrene and the acyclic conjugated diene is selected from the group consisting of butadiene, isoprene, and combinations thereof.

[0029] In one embodiment, the star-branched copolymer can be a star-branched block copolymer, where each of a plurality of polymer arms may include one or more polymer blocks comprising polymerization unit (i) derived from a first vinyl aromatic monomer as previously described, and optionally polymerization unit (ii), and optionally polymerization unit (iii). In a particular embodiment, the star-branched block copolymer has a structure in which more than 70% by weight of one or more polymer blocks contains at least 80% by weight of a combination of polymerization units (i) and (ii), and the polymer composition has a hardness greater than 80 Shore A as measured according to ASTM D2240. In another embodiment, the block copolymer has a structure in which 75-100% by weight, or 80-95% by weight, or 85-90% by weight of one or more polymer blocks contains at least 80% by weight of a combination of polymerization units (i) and (ii), and the polymer composition has a hardness greater than 80 Shore A as measured according to ASTM D2240.

[0030] In yet another embodiment, the block copolymer comprises more than 70% by weight of one or more polymer blocks, which consist of a combination of polymerization units (i) and (ii) in 85-100% by weight, or 90-95% by weight, and the polymer composition has a structure having a hardness greater than 80 Shore A as measured according to ASTM D2240.

[0031] In another embodiment, the polymer composition comprises a star-branched copolymer comprising one or more polymer blocks "D" containing polymerization unit (i), one or more polymer blocks "E" optionally containing polymerization unit (ii), and one or more polymer blocks "F" optionally containing polymerization unit (iii), wherein polymerization units (i) and (iii) are as previously described.

[0032] In one embodiment, the star-branched block copolymer comprises one or more blocks "D" containing more than 50% by weight of polymerization units (i), one or more blocks "E" containing more than 50% by weight of polymerization units (ii), and one or more blocks "F" containing more than 50% by weight of polymerization units (iii), and the polymer composition has a structure having one or more structures selected from the group consisting of (D-)nX, (DE-)nX, (DF-)nX, (ED-)nX, (FD-)nX, (DED-)nX, (DFE-)nX, (DEF-)nX, (EFD-)nX and (EDF-)nX, where "n" is an integer from 2 to 50 and X is a coupling agent residue.

[0033] In one embodiment, block "D" comprises a hydrogenated form of polymerized para-methylstyrene units. The high-Tg monomer of polymerization unit (ii) can be 1,3-cyclohexadiene, as it is relatively more readily available. In another embodiment, block "E" may further include polymerization units derived from acyclic 1,3-dienes such as 2,3-dimethyl-1,3-butadiene, isoprene, butadiene, 1,3-pentadiene, farnesene, myrcene, 1,3-hexadiene, and combinations thereof.

[0034] In another embodiment, block "E" comprises a hydrogenated polymer unit (ii) derived from the high-Tg monomer 1,3-cyclohexadiene, para-methylstyrene, or divinylbenzene.

[0035] One or more polymer blocks "F" may contain hydrogenated polymer units derived from butadiene or isoprene. As previously mentioned, the relative molar ratio of the second vinyl aromatic monomer to the acyclic conjugated diene can vary from 100:0 to 0:100, or 90:10 to 10:90, or 80:20 to 20:80, or 70:30 to 30:70.

[0036] In one embodiment, a star-branched block copolymer having one or more blocks "D", optionally one or more blocks "E", and optionally one or more blocks "F" has a total molecular weight of 25 kg / mol to 300 kg / mol and a polymer arm molecular weight of 1 kg / mol to 30 kg / mol. In another embodiment, a copolymer having one or more blocks "D", optionally one or more blocks "E", and optionally one or more blocks "F" has a total molecular weight of 50 to 250 kg / mol, or 100 to 200 kg / mol, or 125 to 150 kg / mol. Furthermore, the polymer arm molecular weight can vary in the range of 3 to 25 kg / mol, or 6 to 20 kg / mol, or 10 to 18 kg / mol.

[0037] The star-branched copolymers described above can be obtained from various precursor copolymers that are similarly star-branched. Several examples of precursor copolymers are shown in Table 2, where the following abbreviations and notations are used: X: residue of divinylbenzene (DVB) used as a coupling agent; p-MeS: para-methylstyrene; DPE: 1,1-diphenylethylene; CHD: 1,3-cyclohexadiene; p-tBuS: para-tert-butylstyrene; p-AdS: para-adamantylstyrene; S: styrene; VBCB: 4-vinylbenzocyclobutene; BD: 1,3-butadiene; TMOS: tetramethoxysilane

[0038] [Table 2]

[0039] The above precursor copolymer can be selectively hydrogenated to provide a desired star-branched copolymer having polymerization units (i) in various levels of hydrogenated and unhydrogenated forms, and optionally (ii), and optionally (iii). In one embodiment, polymerization units derived from the above-described first vinyl monomer can be selectively hydrogenated, where more than 10 mol% to 100 mol%, or 20 mol% to 90 mol%, or 30 mol% to 70 mol%, or 40 mol% to 60 mol%, of the polymerization units is in an unhydrogenated form. In copolymers where polymerization unit (ii) is derived from 1,3-cyclodiene, selective hydrogenation can also result in structures in which some or all of the diene double bonds in the polymerized cyclodiene unit are reduced. In copolymers containing polymerization unit (iii), selective hydrogenation can reduce essentially all acyclic diene double bonds without essentially reducing the aromatic double bonds, i.e., by hydrogenation of 10 mol% or less, or 5 mol% or less, or 2 mol% or less of aromatic double bonds. When producing unhydrogenated copolymers using more than one type of vinyl aromatic monomer, selective hydrogenation can proceed to varying degrees for each type of polymerized vinyl aromatic unit.

[0040] Table 3 shows examples of selectively hydrogenated copolymers that can be obtained from the precursor copolymers listed in Table 2. In Table 3, the selectively hydrogenated form of polymerization unit is indicated by the prefix "h" placed before the abbreviation for the polymerization unit to which hydrogenation is applied. For example, "hpMeS" means the selectively hydrogenated form of polymerized para-methylstyrene unit.

[0041] [Table 3]

[0042] <Preparation of Copolymers>: Copolymers are prepared by anionic polymerization using methods known in the art. Polymerization initiators are generally organometallic compounds such as organolithium compounds, for example ethyl-, propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl-, phenyl-, hexylbiphenyl-, hexamethylenedi-, butadienyl-, isoprenyl-, 1,1-diphenylhexyllithium, or polystyrenelithium. The amount of initiator required is calculated based on the molecular weight to be achieved and is generally 0.002 to 5 mol percent based on the amount of monomer to be polymerized. Suitable solvents include aliphatic, alicyclic, or aromatic hydrocarbons having 4 to 12 carbon atoms, such as pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclohexane, decalin, isooctane, benzene, alkylbenzene, for example toluene, xylene, or ethylbenzene, or suitable mixtures. Polymer chain termination is carried out using an anionic quenching agent, such as methanol, or a coupling agent, such as a di- or polyfunctional compound, such as divinylbenzene; aliphatic or aromatic aliphatic hydrocarbon halogen, such as 1,2-dibromoethane, bis(chloromethyl)benzene, or silicon tetrachloride, dialkyl- or diarylsilicon dichloride, alkyl- or arylsilicon trichloride, tin tetrachloride, alkylsilicon methoxide, alkylsilicon ethoxide, polyfunctional aldehyde, such as terephthalic acid dialdehyde, ketone, ester, anhydride, or epoxide. Polyfunctional coupling agents, such as divinylbenzene, are preferred because they produce the desired star-branched copolymer structure.

[0043] If desired, Lewis base additives that affect polymerization parameters such as the relative ratio of 1,2-addition to 1,4-addition may also be used. Examples of Lewis bases include dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, 1,2-diethoxypropane, diethylene glycol dimethyl ether, tetrahydrofuran, tetrahydrofurfuryl ether, e.g., tetrahydrofurfuryl methyl ether, and tertiary amines.

[0044] Hydrogenation of double bonds within polymerization units can be carried out under controlled conditions to obtain selectively hydrogenated copolymers having a desired percentage of hydrogenation. Suitable catalysts based on nickel, cobalt, or titanium are used in the hydrogenation process. The hydrogenated polymer can be isolated and recovered by solvent evaporation at relatively high temperatures under high vacuum to thoroughly remove the captured solvent used in hydrogenation. The conditions can be modified to achieve any of the selectively hydrogenated copolymers described above. In one embodiment, if a diene monomer is involved in producing the copolymer, the hydrogenation can be carried out such that at least 80 mol%, at least 90 mol%, or at least 98 mol% of the double bonds in the polymerization diene units are reduced, and 0-10 mol% of the arene double bonds are reduced. Similarly, if selective hydrogenation of aromatic double bonds in the polymerized vinyl aromatic monomer is desired, the reaction conditions can be adjusted to produce selectively hydrogenated copolymers.

[0045] <Curable Composition>: The above copolymer can be used to produce a curable composition and a curable composition produced therefrom. The curable composition comprises the above polymer composition, a curing agent, a co-curing agent, and optionally one or more additives.

[0046] The curable composition contains a sufficient amount of copolymer to have desirable properties such as elastic modulus, toughness, viscosity, glass transition temperature, gel content, hardness, Dk, Df, and flame retardancy. The amount is in the range of 1 to 99.5% by weight, 7 to 50% by weight, or 10 to 25% by weight of the polymer, based on the total weight of the curable composition. Depending on the desired end use, the curable composition may further contain various components described below.

[0047] <Curing Agent / Curing Initiator>: The curable composition further comprises at least one curing agent / curing initiator. Examples include, but are not limited to, azides, peroxides, sulfur, and sulfur derivatives. Free radical initiators are particularly desirable as curing initiators. Examples of free radical initiators include peroxides, hydroperoxides, and non-peroxide initiators, such as 2,3-dimethyl-2,3-diphenylbutane. Examples of peroxide curing agents include dicumyl peroxide, alpha,alpha-di(t-butylperoxy)-m,p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexine, as well as mixtures containing one or more of the above curing initiators.

[0048] In several embodiments, the curing initiator is used in an amount of 0.1 to 10 parts, 0.3 to 7 parts, 1 to 5 parts, or 0.1 to 5 parts per 100 parts of the curable composition.

[0049] Co-curing agents may also be used if necessary. Examples include styrene, bromostyrene, divinylbenzene, 1,2-bis(vinylphenyl)ethane, triallyl cyanurate, triallyl isocyanurate, vinyl-functionalized polyphenylene ether resins, bismaleimide resins, liquid or solid diene polymers, acrylates such as trimethylolpropane triacrylate, diallyl phthalate, epoxy resins, diene polymer components, solid diene polymers, styrene-butadiene diblock resins, and polybutadiene resins.

[0050] Diene polymers can be, for example, homopolymers of dienes having double bonds in the polymer main chain, or copolymers of various alkenes and / or dienes (including triblock copolymers). Diene polymers can be in a liquid or solid state at room temperature and can be, for example, unsaturated resins for dielectric substrates, such as polybutadiene polymers, or copolymers of butadiene with styrene or similar styrene-based monomers.

[0051] Examples include polybutadiene rubber containing (meth)acryloyl groups, polyisoprene rubber containing (meth)acryloyl groups, butadiene-isoprene copolymer rubber containing (meth)acryloyl groups, butadiene-n-butene copolymer rubber containing (meth)acryloyl groups, and so on. In several embodiments, the diene polymer is selected from polybutadiene, polyisoprene, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-styrene-methacrylate tri-block copolymer, butadiene-styrene-divinylbenzene, butadiene-styrene-acrylonitrile copolymer, butadiene-styrene-maleic anhydride copolymer, and any combination thereof.

[0052] Examples of liquid butadiene copolymers are butadiene-co-styrene and butadiene-co-acrylonitrile. Polymers containing unsaturated butadiene or isoprene may also contain second block copolymers similar to the first, except that polybutadiene or polyisoprene blocks are hydrogenated to form polyethylene blocks (in the case of polybutadiene) or ethylene-propylene copolymers (in the case of polyisoprene).

[0053] In several embodiments, the diene resin optionally includes a functionalized liquid polybutadiene or polyisoprene resin, an unhydrogenated block copolymer containing residues of one or more acid-functionalizing agents such as epoxy, maleate, hydroxyl, carboxyl, and methacrylate.

[0054] All diene polymers may be present in the curable composition in amounts ranging from 1 to 99% by weight, 30 to 70% by weight, 5 to 25% by weight, 7 to 20% by weight, or 10 to 15% by weight, based on dry weight.

[0055] <Filler Components>: The curable composition further comprises at least inorganic and / or organic fillers. Inorganic fillers can be used to suppress the coefficient of thermal expansion and improve the toughness of the laminate. Organic fillers can be used to reduce the dielectric constant of the laminate. Fillers with a low coefficient of thermal expansion are preferred.

[0056] Typical fillers, used alone or in combination, include titanium dioxide (rutile and anatase), barium titanate, strontium titanate, silica (e.g., fused amorphous silica), corundum, wollastonite, aramid fibers, fiberglass, and Ba2Ti9O2O2. 20 These include glass spheres, quartz, boron nitride, aluminum nitride, silicon carbide, beryllia, alumina, magnesia, magnesium hydroxide, melamine polyphosphate, melamine cyanurate, Melam, Melon, Melem, guanidine, phosphazan, silazane, DOPO(9,10-dihydro-9-oxa-10 phosphenathrene-10-oxide), DOPO(10-5 dihydroxyphenyl, 10-H-9 oxaphosphaphenanthrenelo-oxide), mica, talc, nanoclay, aluminosilicate (natural and synthetic), and fumed silicon dioxide.

[0057] Examples of organic fillers include fluorine-based, polystyrene-based, divinylbenzene-based, and polyimide-based fillers. Examples of fluorine-based fillers include polytetrafluoroethylene (PTFE), polyperfluoroalkoxy resins, polyfluoroethylene-propylene resins, polytetrafluoroethylene-polyethylene copolymers, polyvinylidene fluoride, and polychlorotrifluoroethylene resins.

[0058] In several embodiments, the filler may be treated with one or more coupling agents, such as silane, zirconate, or titanate. The filler may be pretreated, or the coupling agent may be added to the curable composition.

[0059] The amount of filler is in the range of 75% by weight or less, or 0 to 60% by weight, or 5 to 50% by weight, or at least 20% by weight.

[0060] <Flame retardant>: In several embodiments, the curable composition includes a flame retardant selected from phosphorus-containing flame retardants and brominated flame retardants. Examples of brominated flame retardants include ethylene-bis(tetrabromophthalimide), 1,2-bis(pentabromophenyl)ethane, and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine. Examples of phosphorus-containing flame retardants include bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tri(2-carboxyethyl)phosphine (TCEP), tri(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis(dixylenyl phosphate), phosphazene, melamine polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives or resins, melamine cyanurate, and trihydroxyethyl isocyanurate. In several embodiments, the flame retardant compound may be a DOPO compound, a DOPO resin (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, and DOPO-BPN), and a DOPO-containing epoxy resin, where DOPO-BPN may be a bisphenol novolac compound such as DOPO-BPAN, DOPO-BPFN, and DOPO-BPSN.

[0061] In several embodiments, the flame retardant is a non-reactive flame retardant that does not contain reactive functional groups in its chemical structure. The amount of the flame retardant is in the range of 2 to 30% by weight relative to the total amount of the curable composition.

[0062] <Solvent>: During manufacturing, solvents are added to change the solid content of the curable composition and adjust its viscosity. Suitable solvents include, for example, ketones such as methyl ethyl ketone, ethers such as dibutyl ether, esters such as ethyl acetate, amides such as dimethylformamide, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorinated hydrocarbons such as trichloroethylene, and each solvent can be used alone or in combination.

[0063] Preferred solvents are selected from the group consisting of methanol, ethanol, ethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, propylene glycol methyl ether, gamma-butyrolactone (GBL), and diisobutyl ketone (DIBK).

[0064] In one embodiment, a formulation containing the curable composition having the star-branched copolymer can be prepared using a suitable solvent such as toluene, methyl ethyl ketone, or ketone. In another embodiment, the formulation has 10% to 60% by weight, or 15% to 40% by weight, or 20% to 30% by weight of the curable composition, where the formulation has a solution viscosity measured at 25°C of less than 5000 cP, or less than 2000 cP, or 200 to 1800 centipoise, or 400 to 1500 centipoise, or 600 to 1200 centipoise, or 800 to 1000 centipoise. The formulation can then be converted into a curable composition. The amount of solvent used depends on the solubility of the components, the amount of filler, the method of application, and other factors.

[0065] <Other Additives>: In some embodiments, the curable composition may further contain at least one additive having a glass transition temperature of 100°C to 200°C, such as polyolefins, aromatic resins, rubbers, antioxidants, UV stabilizers, UV radical initiators, shrinkage inhibitors, adhesion promoters, colorants and combinations thereof, toughening agents, adhesion promoters, e.g., silanes, shrinkage inhibitors, etc. The selection of additives depends on the application and the desired properties, such as dielectric constant, loss factor, dielectric loss and / or other desired properties, which are selected to enhance the electrical properties of the circuit subassembly or to avoid substantially harmful effects. In several embodiments, the polymer composition comprises a curing agent, a co-curing agent, and one or more additives, wherein the co-curing agent is selected from the group consisting of divinylbenzene, 1,2-bis(vinylphenyl)ethane, triallyl cyanurate, triallyl isocyanurate, vinyl-functionalized polyphenylene ether resins, bismaleimide resins, and liquid or solid diene polymers, and the additives are selected from the group consisting of fillers, flame retardants, polyolefins having a glass transition temperature of 100°C to 200°C, aromatic resins, rubbers, antioxidants, UV stabilizers, UV radical initiators, shrinkage prevention additives, adhesion promoters, colorants, and combinations thereof.

[0066] Curing accelerators can be added to increase the reaction rate of the curable composition. Surfactants help ensure a uniform distribution of inorganic fillers in the curable composition and help avoid aggregation of the inorganic fillers. Toughening agents help improve the toughness of the curable composition.

[0067] Toughening agents may be rubber resins, carboxyl-terminated polybutadiene acrylonitrile, and / or core-shell polymers. Typical antioxidants include radical scavengers and metal deactivators. Coupling agents may be present to promote or be involved in the formation of covalent bonds that bind the polymer to the metal surface or filler surface. Typical coupling agents include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and hexamethylenedisilazane.

[0068] The curable composition may contain catalysts such as Lewis bases or Lewis acids. Lewis bases include imidazole, boron trifluoride amine complexes, ethyltriphenylphosphonium chloride, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, and / or 4-dimethylaminopyridine. Lewis acids include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, or zinc metal salt compounds, preferably metal catalysts, such as zinc caprylate or cobalt caprylate. The coupling agent may be a silane and / or siloxane compound. Preferably, the coupling agent is at least one of aminosilane compounds, aminosiloxane compounds, styrene-based silane compounds, styrene-based siloxane compounds, acrylic silane compounds, acrylic siloxane compounds, methacrylic silane compounds, methacrylic siloxane compounds, alkylsilane compounds, and alkylsiloxane compounds.

[0069] In several embodiments, the amount of the optional component is in the range of 0.01 to 5% by weight, or 0.001 to 0.1% by weight, or 5 to 10% by weight, or less than 20% by weight.

[0070] <Curable Resin Compositions and Their Applications>: Curable compositions can be processed, dried, and further cured into cured products. The cured products have desirable properties such as fixed shape, good resistance to solvents and temperatures, high gel content, low swelling ratio, and low Dk / Df. The resin compositions are useful for copper-clad laminates (CCLs), printed circuit boards, LEDs, other electronic coatings, tires, textiles, polymer molding materials, and medical molding materials. Printed circuit boards are manufactured by impregnating a support or reinforcing material (e.g., glass fiber, textile, cross-ply laminate) with resin, and then partially or completely curing the resin to form a prepreg. The prepregs are then laminated with copper foil in between at a temperature of 150°C to 250°C and a curing rate of 25 kg / cm². 2 ~70 kg / cm 2 The circuit board is formed by curing under pressure. To manufacture the laminate, one or more layers of prepreg are laminated together with one or more layers of copper.

[0071] <Properties and Uses>: The above polymer compositions have very good dielectric properties, and these properties make them useful for producing curable compositions and cured compositions for various applications. In one embodiment, the composition has a dielectric constant Dk of less than 3 measured at 1 GHz and a loss factor Df of less than 0.002 measured at 1 GHz. In other embodiments, the composition has a Dk of 0.5 to 4, or 1 to 3, or 1.5 to 2.5 measured at 1 GHz. The Df value measured at 1 GHz can be 0.0005 to 0.002, or 0.001 to 0.0018.

[0072] Curable resin compositions suitable for electronics applications have low viscosity and good solubility in solvents, such as hydrocarbon solvents, including cyclohexane, toluene, and xylene. The curable resins can be rapidly cured and gelled, providing cured resins with a high Tg, for example, a Tg higher than 100°C, and a low swelling ratio when immersed in a solvent.

[0073] The cured compositions are characterized by low dielectric loss, particularly loss coefficients of 0.03 or less, 0.02 or less, or less than 0.003, all measured at 1 gigahertz. The dielectric materials also have low CTEs (coefficient of thermal expansion) of 80 ppm / °C or less, 60 ppm / °C or less, or 50 ppm / °C or less, all measured over a range of 0 to 150°C.

[0074] In several embodiments, the cured composition has a gel content of 80% to 100% by weight relative to the total weight of the cured composition, a swelling ratio of less than 10, or 1 to 5, or 1.5 to 3, a hardness of 90 to 100 Shore A as measured according to ASTM D2240, a dielectric constant Dk of less than 4, or 0.5 to 4, or 1 to 3.7, or 1.5 to 2.5 as measured at 1 GHz, and a loss factor Df of less than 0.004, or 0.0005 to 0.003, or 0.001 to 0.0018 as measured at 1 GHz. In another embodiment, the swelling ratio is less than 3.

[0075] The curing composition also has good thermal conductivity of approximately 0.2 to 0.7 watts / meter-kelvin (W / mK), or 0.3 to 0.5 W / mK.

[0076] The cured composition can have even lower moisture absorption, resulting in a package substrate that is less susceptible to environmental conditions both during use and storage. In one embodiment, moisture absorption is 0.05 to 0.3 percent after immersion in water at 23°C for 24 hours.

[0077] The cured composition exhibits good flame retardancy. In one embodiment, the composition can achieve a V-0 UL 94 rating. In another embodiment, the composition exhibits a V-0 rating in the absence of brominated or chlorinated flame retardants.

[0078] The cured composition also has a relatively low modulus of elasticity and high elongation. This is particularly beneficial for the reliability of copper interconnects, as it prevents excessive stress from being placed on the walls of copper-plated vias when the components are subjected to thermal cycling. In one embodiment, the tensile modulus is less than 3000 MPa. In another embodiment, the elongation is greater than 5%.

[0079] The curing composition is used in a variety of applications, including copper-clad laminates, printed circuit boards, LEDs, electronic coatings, textiles, polymer molding materials, and medical molding materials.

[0080] The curable resin composition can also be combined with a tire rubber mixture and co-cured to provide a tire rubber composition. Tire components manufactured using the composition have good properties, such as good wet traction, dry handling, good skid resistance, and low rolling resistance. [Examples]

[0081] The following embodiments are provided to illustrate the present disclosure and are not intended to limit the scope of the present disclosure.

[0082] [Example 1] <Polymer composition 1> Preparation of star-branched coupled block copolymer (PMeS)xDVB. 400 ml of purified and dehydrated cyclohexane solvent was charged into a glass pressure vessel, and 7.1 ml of 0.0036 molar sec-Buli was added. The mixture was then heated to 50°C, and 25 g of purified and dehydrated p-methylstyrene was added. The reaction was allowed to proceed for 2 hours, and a small first sample was collected from the solution for GPC analysis and NMR. NMR confirmed the completion of polymerization of this first monomer. Next, 1.5 ml of divinylbenzene was added, and the reaction was allowed to proceed for 1 hour, after which the reaction was terminated with methanol. The polymer was precipitated in excess alcohol and isolated, and dried under vacuum at elevated temperature. GPC calibrated with polystyrene yielded a main peak molecular weight of Mp = 6400 g / mol for the collected sample and Mp = 41690 g / mol for the final product.

[0083] [Example 2] <Polymer composition 2> Star-shaped branched coupling block copolymer (PMeS-PCH DPreparation of xDVB. 300 ml of purified and dehydrated cyclohexane solvent was placed in a thoroughly washed and cleaned glass pressure bottle. 16 ml of 1.6 molar concentration sec-Buli was added, and the mixture was heated to 50°C. 5.7 g of purified and dehydrated p-methylstyrene was added. The reaction was allowed to proceed for 45 minutes, and a small sample of the first monomer was collected from the solution for GPC analysis and NMR. NMR confirmed that the polymerization of the first monomer was complete. The mixture was then cooled to 30°C, 0.4 ml of 1,2-diethoxypropane was added, followed by the addition of 18.7 g of purified 1,3-cyclohexadiene to the solution, and polymerization was allowed for 2 hours. A small sample was collected from the solution for GPC and NMR analysis. NMR confirmed that the polymerization of the second monomer was nearly complete. Next, 5.5 ml of divinylbenzene was added, and the reaction was allowed to proceed for 17 hours. After that, the reaction was terminated with 4 ml of 2-ethylhexanol, and the final sample was collected. The polymer solution was transferred to a hydrogenation reactor, where it was converted to a 40% CHD olefin species at 70°C for 48 hours using a homogeneous cobalt catalyst and 40 barg of hydrogen. The solution was washed to remove the catalyst, stabilized with an antioxidant, and the sample was isolated by precipitation in excess alcohol and dried under vacuum at a rising temperature. By GPC calibrated with polystyrene, the main peak molecular weights Mp=420 g / mol, Mp=1166 g / mol, and Mp=44520 g / mol were obtained for each of the three collected samples.

[0084] [Example 3] <Polymer composition 3> Star-shaped branched coupling block copolymer (PMeS-PCH DPreparation of xDVB. In a thoroughly washed and cleaned stainless steel reactor, 1 liter of purified and dehydrated cyclohexane solvent was charged, and 78 ml of 0.51 molar concentration sec-Buli was added. The mixture was then heated to 50°C, and 45 g of purified and dehydrated p-methylstyrene was added. The reaction was allowed to proceed for 35 minutes, and a small sample of the first monomer was collected from the solution for GPC and NMR analysis. NMR confirmed that the polymerization of this first monomer was complete. The mixture was then cooled to 30°C, 1.2 ml of 1,2-diethoxypropane was added, followed by the addition of 87 g of purified 1,3-cyclohexadiene to the solution, and polymerization was allowed for 3.5 hours. A small sample of the second monomer was collected from the solution for GPC and NMR analysis. NMR confirmed that the polymerization of the second monomer was nearly complete. Next, 17 ml of divinylbenzene was added, and the mixture was heated to 60°C. The reaction was allowed to proceed for 2.5 hours, after which 5.5 ml of 2-ethylhexanol was added to terminate the reaction. A sample was taken, and the polymer solution was transferred to a hydrogenation reactor, where it was converted to a 70% CHD olefin species over 15 hours using a homogeneous cobalt catalyst and 40 barg of hydrogen. The solution was washed to remove the catalyst, stabilized with an antioxidant, and the sample was isolated by precipitation in excess alcohol and dried under vacuum at a rising temperature. By GPC calibrated with polystyrene, the main peak molecular weights Mp=1103 g / mol, Mp=4050 g / mol, and Mp=108800 g / mol were obtained for each of the three collected samples.

[0085] [Example 4] <Polymer composition 4> Linear PCH D-Preparation of PS: 5.5 liters of purified and dehydrated cyclohexane solvent were charged into a dry stainless steel reactor and heated to 30°C. 7.3 ml of 1,2-diethoxypropane was added, followed by 700 g of purified 1,3-cyclohexadiene, and then 383 ml of 0.91 molar solution was added to initiate the reaction, which was polymerized for 2.5 hours. Small samples were collected from the solution for GPC and NMR analysis. NMR confirmed that polymerization of the second monomer was nearly complete. Next, 300 g of purified and dehydrated styrene was added, and the reaction was allowed to proceed for 35 minutes. The second sample was collected for GPC and NMR analysis. NMR confirmed that polymerization of the third monomer was nearly complete. The living solution was then terminated by the addition of 11 g of methanol. The polymer solution was transferred to a hydrogenation reactor, where it was converted to a 90% CHD olefin species at 80°C for 2 hours using a homogeneous cobalt catalyst and 40 barg of hydrogen. The solution was washed to remove the catalyst, stabilized with an antioxidant, and the sample was isolated by precipitation in excess alcohol and dried under vacuum at elevated temperature. GPC calibrated with polystyrene yielded a main peak molecular weight Mp = 2476 g / mol for the first block of each of the three collected samples and Mp = 4200 g / mol for the final sample. NMR analysis of the final product revealed a styrene content of 30 wt.%.

[0086] [Example 5] <Polymer composition 5> Preparation of linear PMeS polymer. In a stainless steel reactor, 1 liter of purified and dehydrated cyclohexane was charged, and 15 ml of 0.3 molar sec-Buli was added. The mixture was then heated to 60°C, and 50 g of purified and dehydrated p-methylstyrene was added. The reaction was allowed to proceed for 30 minutes, and small samples were collected from the solution for GPC analysis and NMR. After confirming the completion of polymerization of this first monomer by NMR, the reaction was terminated with methanol. The polymer was stabilized and dried under vacuum at elevated temperature. GPC calibrated with polystyrene yielded a main peak molecular weight Mp = 13200 g / mol.

[0087] [Example 6] <Polymer composition 6> Preparation of the linear polymer PMeS. 400 ml of purified and dehydrated cyclohexane solvent was charged into a glass pressure vessel, and 2.5 ml of 0.00125 molar sec-Buli was added. The mixture was then heated to 50°C, and 25 g of purified and dehydrated p-methylstyrene was added. The reaction was allowed to proceed for 2 hours, and a small first sample was collected from the solution for GPC analysis and NMR. NMR confirmed the completion of polymerization of this first monomer. The polymer was isolated by precipitation in excess alcohol and dried under vacuum at elevated temperature. GPC calibrated with polystyrene yielded a main peak molecular weight Mp = 22670 g / mol for the collected sample.

[0088] The GPC block molecular weight Mp or block ΔMp is calculated as the difference between the GPC block Mp of the linear copolymer measured at the completion of the block under consideration and the GPC peak molecular weight of the same linear polymer measured immediately before polymerization of the block under consideration. The GPC is calibrated with a polystyrene standard, and therefore the Mp value is expressed as the polystyrene equivalent molecular weight.

[0089] The glass transition temperature (Tg) of a polymer or curing material is determined as the midpoint transition temperature by differential scanning calorimetry (DSC) on a second heating lamp with a heating rate of +20°C / min, measured according to ASTM D3418. The DSC thermal cycle consists of a first heating lamp from 30°C to 200°C at +20°C / min, maintained at 200°C for 2 minutes, followed by a first cooling lamp from 200°C to 20°C at -20°C / min, maintained at 20°C for 2 minutes, and then a second heating lamp from 20°C to 250°C at +20°C / min.

[0090] Copolymer-based compositions are mixed according to the following procedure: The copolymer and other components are mixed with toluene until a homogeneous, pourable solution or varnish is achieved. The solution is poured into a tray coated with an anti-adhesion coating and slowly evaporated overnight to form a thin layer of the composition. The evaporated layer is then dried under vacuum at 60°C for 4 hours. The sample may be further dried under vacuum at a higher temperature. Higher drying temperatures and drying times are chosen so as not to exceed the copolymer's Tg but not to achieve conditions that lead to premature curing.

[0091] The composition is cured using a Vacuum Plate Vulcanizing Machine (MDR). The sample is introduced into a machine mold pre-set to 110°C (or the copolymer Tg if it is higher) to form a 0.7 mm thick plate. The mold is closed under vacuum and maintained at that temperature for 2 minutes. The mold temperature is then raised to 180°C. The sample is kept at 180°C under vacuum for 30 minutes of curing. Finally, the mold is cooled, allowing for the recovery of the cured composition. The maximum torque value of the MDR (expressed as dN*m) is recorded during the curing process at 180°C and corresponds to the maximum torque recorded during that curing period. The time required to reach 90% of the maximum torque value is recorded as tc90, expressed in minutes and seconds.

[0092] The cured sample is analyzed for gel content and swelling ratio. The initial weight (Wi) of the cured sample is measured before the sample is immersed in a large amount of toluene for one day. The solution containing the sample is then filtered, and the weight (Ws) of the filtered swollen gel is recorded. The swollen gel is then dried under vacuum at 60°C until a certain weight, which is the dry weight (Wd), is achieved. The gel content (gel%) is calculated using the following formula: gel% = 100 * Wd / Wi. The swelling ratio is calculated using the following formula: swelling ratio = Ws / Wd.

[0093] Ingredients description: DCP: Dicumyl peroxide; BIPB: Bis-(t-butylperoxyisopropyl)benzene; TAC: Triaryl cyanurate; TAIC: Triaryl isocyanurate.

[0094] [Table 4]

[0095] Hydrogenated units have the prefix "h" before them. pMeS is para-methylstyrene, DVB is divinylbenzene, CHD is 1,3-cyclohexadiene, H2(CHD) is hydrogenated cyclohexadiene, and St is styrene.

[0096] [Table 5]

[0097] [Table 6]

[0098] [Table 7]

[0099] The comparison did not show high gel content at either low or high levels of curing agent addition. One comparison showed high gel content, but despite this high gel content, the cured composition was not resistant to swelling and had a curing-swelling ratio greater than 5. Examples 10-14 showed good curing levels even with low curing agents, and the low swelling ratio resulted in good solvent resistance after curing.

Claims

1. A polymer composition comprising a star-shaped branched copolymer, wherein the star-shaped branched copolymer has a plurality of polymer arms, Each polymer arm has a peak molecular weight of 1 kg / mol to 50 kg / mol. Each polymer arm Polymerization unit (i) is derived from a first vinyl aromatic monomer containing a radical-reactive group, wherein the radical-reactive group is a benzyl carbon having at least one hydrogen substituent. It is a polymerization unit (ii), Polymerization units in hydrogenated or non-hydrogenated forms derived from high-Tg monomers, wherein the high-Tg monomer is selected from the group consisting of tert-butylstyrene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, benzoflubene, 1,1-diphenylethylene, vinylbiphenyl, adamantylstyrene, vinylanthracene, divinylbenzene, bis(vinylphenyl)ethane and combinations thereof, and the polymerization unit derived from 1,3-cyclohexadiene contains 1,2- and 1,4-addition units in a relative molar ratio of 90:10 to 10:90, and Hydrogenated polymerized unit (i), or hydrogenated polymerized styrene unit The polymerization unit (ii), including, Optionally, it is a polymerization unit (iii), (a) Polymerization units derived from one or more acyclic conjugated dienes in which less than 10% by weight is not hydrogenated, and (b) Polymerization units derived from one or more second vinyl aromatic monomers Polymerization unit (iii) Includes, The copolymer contains more than 10% by weight of polymerization units (i), and polymerization units (i) and (ii) together constitute more than 50% by weight of the total weight of the copolymer. A polymer composition in which the copolymer has a peak molecular weight of 15 kg / mol to 500 kg / mol and a glass transition temperature of over 100°C to 250°C.

2. The first vinyl aromatic monomer is Substituted styrene of formula (I), 【Chemistry 1】 (In the formula, R １ is H or CH ３ Therefore, R2 and R2' are independently H or CH ３ It is.) The polymer composition has a molecular weight Mp greater than 30 kg / mol, and a solution viscosity of less than 2,000 centipoise when measured at a polymer composition content of 25% by weight in toluene at 25°C. The polymer composition according to claim 1, wherein the star-shaped branched copolymer constitutes more than 80% by weight of the entire polymer composition.

3. The polymer composition according to claim 1 or 2, wherein the polymerization unit (ii) is present in an amount of more than 1% by weight relative to the total weight of the polymer composition.

4. The polymer composition according to claim 2, wherein the star-branched copolymer is a star-branched block copolymer comprising a plurality of polymer arms, each polymer arm comprising one or more polymer blocks, and more than 70% by weight of one or more polymer blocks comprising at least 80% by weight of a combination of polymerization units (i) and (ii), and the polymer composition has a Shore A hardness greater than 80 as measured according to ASTM D2240.

5. The polymer composition according to claim 3, wherein more than 50 mol% of the polymerized 1,3-cyclohexadiene units are hydrogenated.

6. The polymer composition according to claim 3, wherein the first vinyl aromatic monomer is para-methylstyrene, and the polymerization unit (ii) comprises polymerized para-methylstyrene in a hydrogenated form, polymerized divinylbenzene, polymerized tert-butylstyrene, or a combination thereof, and polymerization units (i) and (ii) together constitute more than 60% by weight of the total weight of the polymer composition.

7. The polymer composition according to claim 1 or 2, wherein each polymer arm contains a polymerization unit (iii), the second vinyl aromatic monomer is styrene, and the acyclic conjugated diene is selected from the group consisting of butadiene, isoprene, and combinations thereof.

8. The star-shaped branched block copolymer comprises one or more polymer blocks "D", optionally one or more polymer blocks "E", and optionally one or more polymer blocks "F". One or more blocks "D" contain more than 50% by weight of polymerization units (i), One or more blocks "E" contain more than 50% by weight of polymerization units (ii), One or more "F" blocks contain more than 50% by weight of polymerization units (iii), The polymer composition has (D-) ｎ X, (D-E-) ｎ X, (E-D-) ｎ X, (D-E-D-) ｎ X, (D-F-E-) ｎ X, (D-E-F-) ｎ X, (E-F-D-) ｎ X and (E-D-F-) ｎ has one or more structures selected from the group consisting of X, where "n" is an integer from 2 to 50, and X is a coupling agent residue. The star-shaped branched block copolymer has a total peak molecular weight of 25 kg / mol to 300 kg / mol. Each of the aforementioned multiple arms has a peak molecular weight of 1 kg / mol to 30 kg / mol. The polymer composition according to claim 4.

9. The polymer composition according to claim 8, wherein one or more polymer blocks "D" contain polymerized para-methylstyrene units.

10. The polymer composition according to claim 8 or 9, further comprising one or more polymer blocks "E", wherein the polymerization unit (ii) comprises a hydrogenated form of polymerization unit derived from 1,3-cyclohexadiene, para-methylstyrene, or divinylbenzene.

11. The polymer composition according to claim 8 or 9, further comprising one or more polymer blocks "F", wherein the polymerization unit (iii) comprises a hydrogenated form of polymerization unit derived from styrene and butadiene or isoprene.

12. The polymer composition according to claim 1 or 2, wherein the composition has a dielectric constant Dk of less than 3 as measured at 1 GHz and a loss factor Df of less than 0.002 as measured at 1 GHz.

13. A curable composition comprising the polymer composition, curing agent, co-curing agent and one or more additives according to claim 1 or 2, The co-curing agent is selected from the group consisting of divinylbenzene, 1,2-bis(vinylphenyl)ethane, triallyl cyanurate, triallyl isocyanurate, vinyl-functionalized polyphenylene ether resin, bismaleimide resin, and liquid or solid diene polymers. A curable composition in which the additive is selected from the group consisting of fillers, flame retardants, polyolefins having a glass transition temperature of 100°C to 200°C, aromatic resins, rubbers, antioxidants, UV stabilizers, UV radical initiators, shrinkage prevention additives, adhesion promoters, colorants, and combinations thereof.

14. A cured composition produced from the curable composition according to claim 13, wherein the cured composition has a gel content of 80% to 100% by weight relative to the total weight of the cured composition, a swelling rate of less than 5, a Shore A hardness of 90 to 100 as measured according to ASTM D2240, a dielectric constant Dk of less than 3.7 as measured at 1 GHz, and a loss factor Df of less than 0.003 as measured at 1 GHz.

15. The curing composition according to claim 14, which is used in copper-clad laminates, printed circuit boards, LEDs, electronic coatings, textiles, polymer molding materials, or medical molding materials.

Images