JP6231067B2 - Curable composition - Google Patents

Description

  Embodiments of the present disclosure relate to a curable composition, particularly a curable composition comprising a terpolymer, and a method of making the curable composition.

  A curable composition is a composition comprising a thermosetting monomer that can be crosslinked. Crosslinking, also called curing, can be used to crosslink curable compositions into cross-linked polymers (ie, cured products) that are useful in various fields, such as composites, electrical laminates, and coatings. Convert. Some properties of curable compositions and cross-linked polymers that can be considered for a particular application include other physical properties, but mechanical, thermal, electrical, optical, processing properties Is mentioned.

  For example, glass transition temperature, dielectric constant and dissipation factor can be properties that are considered to be very relevant for curable compositions used in electrical laminates. For example, having a sufficiently high glass transition temperature for an electrical laminate can be very important in making the electrical laminate effective for use in a high temperature environment. Similarly, the reduction in dielectric constant and dissipation factor of electrical laminates can assist in the separation of conductive regions from other regions.

  In order to achieve the desired changes in glass transition temperature, dielectric constant and dissipation factor, various materials have been added to the curable composition in previous approaches. For example, materials have been added to curable compositions to reduce the dielectric constant and dissipation factor. The addition of these materials to the curable composition can reduce the dielectric constant and dissipation factor, which is desirable, but these materials can also adversely alter other properties, such as lowering the glass transition temperature. It is possible and this is undesirable. Therefore, additional materials are added to increase the glass transition temperature. For example, in previous approaches, cyanate has been added to increase the glass transition temperature. However, cyanates are expensive and can increase the cost of manufacturing electrical laminates. Therefore, an affordable electrical laminate having desirable thermal and electrical properties is advantageous.

  In embodiments of the present disclosure, a hardener component is provided that can be used in a curable epoxy system as discussed herein. Specifically, embodiments of the present disclosure include a curable composition comprising an epoxy resin and a curing agent compound for curing with the epoxy resin, the curing agent compound having the formula (I):

A first structural unit of formula (II):

A second structural unit of formula (III):

A terpolymer having a third structural unit of
Wherein each m, n and r is independently a real number representing the mole fraction of each constituent unit in the terpolymer, and each R is independently hydrogen, an aromatic group or An aliphatic group, Ar is an aromatic group, and the epoxy group to the second building block has a molar ratio in the range of 1.0: 1.0 to 2.7: 1.0; A curable composition is included.

For the various embodiments, the curable composition does not contain cyanate groups. For various embodiments, the cured product of the curable composition has a glass transition temperature of at least 150 degrees Celsius (° C.). For various embodiments, the cured product of the curable composition has a dielectric constant (D _k ) of 3.1 or less at a frequency of 1 gigahertz (GHz) and a dissipation factor (D _f of 0.01 or less at a frequency of 1 GHz). ).

  Embodiments of the present disclosure also include a prepreg that includes a reinforcing component and a curable composition, as described herein.

  Embodiments of the present disclosure further include an electrical laminate structure that includes a reaction product of the curable composition, as described herein.

  Furthermore, embodiments of the present disclosure also include a method of preparing a curable composition comprising the steps of preparing an epoxy resin and reacting the epoxy resin with a curing agent compound, the curing agent compound comprising: Formula (I):

A first structural unit of formula (II):

A second structural unit of formula (III):

A terpolymer having a third structural unit of
Wherein each m, n and r is independently a real number representing the mole fraction of each constituent unit in the terpolymer, and each R is independently hydrogen, an aromatic group or An aliphatic group, Ar is an aromatic group, and the epoxy group to the second building block has a molar ratio in the range of 1.0: 1.0 to 2.7: 1.0; Methods are included.

  The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows illustrates specific embodiments in more detail. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each case, the enumerated list serves only as a representative group and should not be interpreted as an exclusive list.

  In an embodiment of the present disclosure, a curable composition is provided. For various embodiments, the curable composition of the present disclosure has a hardener component that includes a terpolymer. As discussed herein, the terpolymer is a styrene maleic anhydride (SMA) copolymer modified with an aromatic amine such as aniline. The curable composition of the present disclosure provides a cured product having desirable thermal and electrical properties. Desirable thermal properties can include glass transition temperature and decomposition temperature, and desirable electrical properties can include dielectric constant and dissipation factor. The cured product of the curable composition of the present disclosure may be useful for electroencapsulation materials, composites, electrolaminates, adhesives, prepregs and / or powder coatings.

  Copolymers derived from styrene and maleic anhydride have been used as curing agents for epoxy systems, including use in electrical applications where the copolymer is used as a matrix component (eg, printed circuit boards). Copolymers of styrene and maleic anhydride can provide an acceptable combination of properties that can include low dielectric constants or high glass transition temperatures. The ratio of styrene to maleic anhydride can be adjusted to change the properties of the cured product. In general, as the ratio of styrene to maleic anhydride increases, the dielectric constant decreases, which is desirable, but the glass transition temperature decreases simultaneously, which is undesirable.

  As discussed herein, materials have been added to curable compositions to increase the glass transition temperature. For example, previous approaches have included cyanate in a curable composition comprising a copolymer derived from styrene and maleic anhydride to combat the reduction in glass transition temperature. However, cyanates are expensive and can increase the cost of producing products (eg, electrical laminates) formed from curable compositions.

  However, unlike previous approaches, the curable compositions of the present disclosure do not contain cyanate groups, but still provide cured products that have desirable thermal and electrical properties. In other words, the curable compositions of the present disclosure can provide similar thermal and electrical properties as those containing cyanate groups, but are less expensive because they do not contain cyanate.

  For various embodiments, the styrene maleic anhydride copolymer is modified to include an aromatic amine compound (eg, aniline). Aromatic amine compounds (eg, aniline) can be used to react with some of the maleic anhydride groups in the styrene maleic anhydride copolymer. Modified styrene maleic anhydride copolymers (also referred to herein as “terpolymers”) can be incorporated into curable compositions to provide desirable thermal and electrical properties. For various embodiments, the curable compositions of the present disclosure have an epoxy group to terpolymer second building block in the range of 1.0: 1.0 to 2.7: 1.0, preferably 1. It is formed to have a molar ratio in the range of 1: 1.0 to 1.9: 1.0, more preferably in the range of 1.3: 1.0 to 1.7: 1.0. As provided herein, formation of a curable composition having a molar ratio of epoxy groups to second building blocks in the range of 1.0: 1.0 to 2.7: 1.0 is desirable. A cured product having thermal and electrical properties is provided. As used herein, a “building block” is the smallest building block (group of atoms that forms part of the macromolecular's essential structure), the repetition of which forms a macromolecule, eg, a polymer, Or refers to a monomer.

  As used herein, “a”, “an”, “the”, “at least one”, and “one or more” “One or more” is used interchangeably. The term “and / or” means one, one or more, or all of the items listed. The recitation of numerical ranges by endpoints includes all numbers subsumed within that range (eg 1 to 5 is 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.) including).

  Furthermore, the curable compositions of the present disclosure are free of cyanate and can still provide similar thermal and electrical properties as curable compositions containing cyanate, but may be less expensive to manufacture. There is.

  For various embodiments, the curable composition includes an epoxy resin and a curing agent compound for curing with the epoxy resin. For various embodiments, the curing agent compound has the formula (I):

A first structural unit of formula (II):

A second structural unit of formula (III):

A terpolymer having a third structural unit of
Wherein each m, n and r is independently a real number representing the mole fraction of each constituent unit in the terpolymer, and each R is independently hydrogen, an aromatic group or Is an aliphatic group, Ar is an aromatic group, and the epoxy group to the second building block has a molar ratio in the range of 1.0: 1.0 to 2.7: 1.0. In various embodiments, each R is hydrogen and Ar is a phenyl group.

  For various embodiments, the mole fraction m is 0.50 or more, and the mole fractions n and r are each independently 0.45 to 0.05, where (m + n + r) = 1 .00. For various embodiments, the first building block to the second building block has a molar ratio in the range of 1: 1 to 20: 1; for example, the moles of the first building block to the second building block. The ratio can have a range of 3: 1 to 15: 1.

  For various embodiments, the second building block comprises 0.1 percent (%) to 41% by weight of the terpolymer. In one embodiment, the second building block comprises 5% to 20% by weight of the terpolymer. For various embodiments, the third building block comprises 0.1% to 62.69% by weight of the terpolymer. In one embodiment, the third building block comprises 0.5% to 50% by weight of the terpolymer.

  For various embodiments, examples of aromatic groups include, but are not limited to, phenyl, biphenyl, naphthyl, substituted phenyl or biphenyl, and substituted naphthyl. Examples of aliphatic groups include, but are not limited to alkyl and alicyclic alkyl. Examples of aromatic radicals include, but are not limited to, phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, and substituted naphthyl.

  For the various embodiments, the terpolymer comprises three building blocks. The terpolymer can be obtained by combining a copolymer and a monomer via a chemical reaction, for example, by reacting a styrene maleic anhydride copolymer with an amine compound. Furthermore, the terpolymer can be obtained by combining three or more monomers via a chemical reaction (for example, reacting a styrene compound, maleic anhydride, and a maleimide compound). The reacted monomer and / or copolymer forms a terpolymer building block. A compound is a substance composed of atoms or ions of two or more elements in a chemical bond.

Styrene compounds as used herein include compounds having the chemical formula C ₆ H ₅ CH═CH ₂ and compounds derived therefrom (eg, styrene derivatives), unless expressly specified otherwise. . Maleic anhydride, which may also be referred to as cis-butenedioic anhydride, toxylic anhydride, or dihydro-2,5-dioxofuran, has the chemical formula: C ₂ H ₂ (CO) ₂ O.

  As discussed herein, styrene maleic anhydride copolymers have been used in curable compositions. Commercial examples of such styrene maleic anhydride copolymers include, but are not limited to, SMA® EF-40, SMA® EF-60, and SMA® EF- 80 (all of which are available from Sartomer Company, Inc.), as well as SMA® EF-100 (which is available from Elf Atochem, Inc.).

  For various embodiments, the styrene maleic anhydride copolymer can be reacted with an aromatic amine compound such as aniline to form a terpolymer. For various embodiments, the styrene maleic anhydride copolymer has a molar ratio of styrene to maleic anhydride of 1: 1 to 8: 1; for example, the copolymer is 3: 1 to 6: 1 styrene to maleic anhydride. It can have a molar ratio of acids.

  For various embodiments, the styrene maleic anhydride copolymer can have a weight average molecular weight of 2,000 to 20,000; for example, the copolymer can have a weight average molecular weight of 3,000 to 11,500. it can. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

  For various embodiments, the styrene maleic anhydride copolymer can have a molecular weight distribution from 1.1 to 6.1; for example, the copolymer can have a molecular weight distribution from 1.2 to 4.0.

  For various embodiments, the styrene maleic anhydride copolymer can have an acid number from 100 milligrams potassium hydroxide (mg KOH / g) to 480 mg KOH / g per gram; for example, the copolymer can be from 120 mg KOH / g to 285 mg KOH / g. g, or an acid number from 156 mg KOH / g to 215 mg KOH / g.

  For various embodiments, the styrene maleic anhydride copolymer is modified with an aromatic amine compound. Specific examples of the aromatic amine compound include, but are not limited to, aniline, substituted aniline, naphthalene amine, substituted naphthalene amine, and combinations thereof. Other aromatic amine compounds are also possible.

  As discussed herein, the terpolymers of the present disclosure are obtained by modifying a styrene maleic anhydride copolymer with an aromatic amine compound. The method of modifying the styrene maleic anhydride copolymer can include imidization.

  For one or more embodiments, the curable composition comprises an epoxy compound. Epoxy compounds are compounds in which an oxygen atom is directly bonded to two adjacent or non-adjacent carbon atoms of a carbon chain or ring system. The epoxy compound can be selected from the group consisting of an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, and combinations thereof.

  For one or more embodiments, the curable composition comprises an aromatic epoxy compound. Examples of aromatic epoxy compounds include, but are not limited to, glycidyl ether compounds of polyphenols such as hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, phenol novolac, cresol novolac, tris. Phenol (tris- (4-hydroxyphenyl) methane), 1,1,2,2-tetra (4-hydroxyphenyl) ethane, tetrabromobisphenol A, 2,2-bis (4-hydroxyphenyl) -1,1 , 1,3,3,3-hexafluoropropane, 1,6-dihydroxynaphthalene, and combinations thereof.

  For one or more embodiments, the curable composition comprises an alicyclic epoxy compound. Examples of alicyclic epoxy compounds include, but are not limited to, epoxidizing a polyglycidyl ether of a polyol having at least one alicyclic ring or a compound containing a cyclohexene ring or a cyclopentene ring with an oxidizing agent. And a compound containing cyclohexene oxide or cyclopentene oxide obtained by the above method. Some specific examples include, but are not limited to, hydrogenated bisphenol A diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate; 3,4-epoxy-1- Methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate; 3,4-epoxy-3-methyl Cyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate; 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate; bis (3,4-epoxycyclohexylmethyl ) Adipate; 2,2-bis (3,4-epoxycyclohexyl) propane; dicyclopentadiene diepoxide; ethylene-bis (3,4-epoxycyclohexanecarboxylate); dioctyl epoxy hexa Hydrophthalate; di-2-ethylhexyl epoxy hexahydrophthalate; and combinations thereof.

  For one or more embodiments, the curable composition comprises an aliphatic epoxy compound. Examples of aliphatic epoxy compounds include, but are not limited to, polyglycidyl ethers of aliphatic polyols or alkylene-oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, vinyl of glycidyl acrylate or glycidyl methacrylate. Homopolymers synthesized by polymerization, and copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers. Some specific examples include, but are not limited to, glycidyl ethers of polyols, such as 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; triglycidyl ether of glycerin. Triglycidyl ether of trimethylolpropane; tetraglycidyl ether of sorbitol; hexaglycidyl ether of dipentaerythritol; diglycidyl ether of polyethylene glycol; and diglycidyl ether of polypropylene glycol; one or more alkylene oxides are aliphatic Polyglycidyl ethers of polyether polyols obtained by adding to polyols (such as propylene glycol, trimethylolpropane, and glycerin); aliphatic Diglycidyl ester of chain dibasic acids; and combinations thereof.

  As discussed herein, the use of a styrene maleic anhydride copolymer having a high ratio of styrene to maleic anhydride (eg, 4: 1 or higher) reduces the dielectric constant, which is desirable, but glass transition The temperature decreases at the same time, which is undesirable. However, the curable compositions of the present disclosure can incorporate styrene maleic anhydride copolymers having a styrene to maleic anhydride ratio of 4: 1 or higher without reducing the glass transition temperature. For example, a styrene maleic anhydride copolymer is modified with an amine compound and the curable composition of the present disclosure has a molar ratio of epoxy groups to second building blocks of 1.0: 1.0 to 2.7: 1.0. Is used in the curable composition to have within. For various embodiments, the curable composition of the present disclosure provides a molar ratio of epoxy groups to second building blocks in the range of 1.1: 1.0 to 1.9: 1.0, more preferably 1 .3: 1.0 to 1.7: 1.0. As discussed herein, the cured product of the curable composition of the present disclosure exhibits desirable thermal and electrical properties without incorporating cyanate into the curable composition.

  For various embodiments, the curable composition may include a solvent. Solvents include methyl ethyl ketone (MEK), toluene, xylene, N, N-dimethylformamide (DMF), propylene glycol methyl ether (PM), cyclohexanone, propylene glycol methyl ether acetate (DOWANOL ™ PMA), and combinations thereof. May be selected from the group consisting of For various embodiments, the solvent can be used in an amount of 30% to 60% by weight, based on the total weight of the curable composition.

  For various embodiments, the curable composition may include a catalyst. Examples of catalysts include, but are not limited to, 2-methylimidazole (2MI), 2-phenylimidazole (2PI), 2-ethyl-4-methylimidazole (2E4MI), 1-benzyl-2-phenylimidazole (1B2PZ), boric acid, triphenylphosphine (TPP), tetraphenylphosphonium-tetraphenylborate (TPP-k), and combinations thereof. For various embodiments, the catalyst (10% solution by weight) can be used in an amount of 0.01% to 2.0% by weight, based on the weight of the solid component in the curable composition.

  For various embodiments, the curable composition may include a co-curing agent. The co-curing agent can be reactive to the epoxide group of the epoxy compound. The co-curing agent may be selected from the group consisting of novolaks, amines, anhydrides, carboxylic acids, phenols, thiols, and combinations thereof. For various embodiments, the co-curing agent may be used in an amount of 1% to 90% by weight, based on the weight of the terpolymer.

  For one or more embodiments, the curable composition includes an additive. Additives include dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, fluidity improvers, drip retardants, flame retardants, antiblocking agents, release agents. It can be selected from the group consisting of molds, toughening agents, low-profile additives, stress-relief additives, and combinations thereof. The additive may be used in an effective amount for a particular application, as will be appreciated by those skilled in the art. For different applications, the effective amount can have different values. As discussed herein, the curable compositions of the present disclosure do not contain cyanate groups.

  For one or more embodiments, the curable composition has a gel time of 200 seconds (s) to 400 s at 171 ° C., including individual values and / or all subranges therein. For example, the curable composition may have a gel time of 205 to 395 s at 171 ° C., or 210 to 390 s at 171 ° C.

  Gelation time can indicate the reactivity of the curable composition (eg, at a particular temperature) and can be expressed as the number of seconds to gel point. The gel point refers to the point of network formation of the initial polymer, where the structure is substantially branched so that each unit of the network is essentially linked to each other unit of the network. ing. When the curable composition reaches the gel point, the remaining solvent becomes incorporated into the substantially branched structure. When the entrapped solvent reaches its boiling point, bubbles can form in the structure (eg, prepregs that lead to undesirable products).

  As discussed herein, for one or more embodiments, the curable composition has a gel time of 200 s to 400 s at 171 ° C. In some cases, a curable composition having a gel time greater than 400 s at 171 ° C. has a gel time of 200 s to 400 s at 171 ° C., 200 s to 375 s at 171 ° C., or as discussed herein, or It can be modified by adding catalysts and / or additives to adjust from 200 s to 350 s at 171 ° C. Depending on the application, a curable composition having a gel time of less than 200 s at 171 ° C. may be considered too reactive.

  Embodiments of the present disclosure provide a prepreg comprising a reinforcing component and a curable composition, as discussed herein. The prepreg can be obtained by a method including a step of impregnating a matrix component into a reinforcing component. The matrix component surrounds and / or supports the reinforcing component. The disclosed curable composition can be used for matrix components. The matrix component and the reinforcing component of the prepreg provide a synergistic effect. This synergy defines that the prepreg and / or product obtained by curing the prepreg has mechanical and / or physical properties not achieved with the individual components alone.

  The reinforcing component can be a fiber. Examples of fibers include, but are not limited to, glass, aramid, carbon, polyester, polyethylene, quartz, metal, ceramic, biomass, and combinations thereof. The fiber can be coated. An example of a fiber coating includes, but is not limited to boron.

  Examples of glass fibers include, but are not limited to, A-glass fibers, E-glass fibers, C-glass fibers, R-glass fibers, S-glass fibers, T-glass fibers, and combinations thereof. Can be mentioned. Aramid is an organic polymer, examples of which include, but are not limited to, Kevlar®, Twaron®, and combinations thereof. Examples of carbon fibers include, but are not limited to, fibers formed from polyacrylonitrile, pitch, rayon, cellulose, and combinations thereof. Examples of metal fibers include, but are not limited to, stainless steel, chromium, nickel, platinum, titanium, copper, aluminum, beryllium, tungsten, and combinations thereof. Examples of ceramic fibers include, but are not limited to, fibers formed from aluminum oxide, silicon dioxide, zirconium dioxide, silicon nitride, silicon carbide, boron carbide, boron nitride, silicon boride, and combinations thereof. Can be mentioned. Examples of biomass fibers include, but are not limited to, fibers formed from wood, non-wood, and combinations thereof.

  The reinforcing component can be a fabric. The fabric may be formed from fibers as discussed herein. Examples of fabrics include, but are not limited to, sutures, wovens, and combinations thereof. The fabric can be unidirectional, multiaxial, and combinations thereof. The reinforcing component can be a combination of fibers and fabrics.

  The prepreg can be obtained by impregnating the matrix component into the reinforcing component. Impregnation of the matrix component into the reinforcing component can be accomplished by various methods. The prepreg may be formed by contacting the reinforcing component and the matrix component by rolling, dipping, spraying, or other such operation. After the prepreg reinforcing component has been contacted with the prepreg matrix component, the solvent can be removed by volatilization. During and / or after the solvent is volatilized, the prepreg matrix component may be cured, eg, partially cured. Solvent volatilization and / or partial curing may be referred to as B-staging. The B-staged product may be referred to as a prepreg.

  For some applications, B-staging can occur by exposure to temperatures from 60 ° C to 250 ° C; for example, B-staging is from 65 ° C to 240 ° C, or from 70 ° C to 230 ° C. Can be caused by exposure. For some applications, B-staging can occur in a period of 1 minute (min) to 60 minutes; for example, B-staging may be in a period of 2 minutes to 50 minutes, or 5 minutes to 40 minutes Can happen. However, for some applications, B-staging can occur at different temperatures and / or different time periods.

  One or more prepregs may be cured (eg, more fully cured) to obtain a cured product. The prepreg may be layered and / or formed into a shape before being further cured. For some applications (eg, when an electrical laminate is being manufactured), the layers of prepreg can be alternated with layers of conductive material. An example of the conductive material includes, but is not limited to, copper foil. The prepreg layer can then be exposed to conditions such that the matrix component is more fully cured.

  One example of a method for obtaining a more fully cured product is pressing. One or more prepregs can be placed in a press where it undergoes a curing force for a predetermined curing time interval to obtain a more fully cured product. The press can have a curing temperature of 80 ° C. to 250 ° C .; for example, the press can have a curing temperature of 85 ° C. to 240 ° C., or 90 ° C. to 230 ° C. For one or more embodiments, the press has a cure temperature that is ramped over a ramp time interval from a lower cure temperature to a higher cure temperature.

  During pressing, one or more prepregs can be subjected to a curing force by pressing. The curing power may have a value that is from 10 kilopascals (kPa) to 350 kPa; for example, the curing power may have a value that is from 20 kPa to 300 kPa, or from 30 kPa to 275 kPa. The predetermined cure time interval may have a value that is 5 seconds to 500 seconds; for example, the predetermined cure time interval has a value that is 25 seconds to 540 seconds, or 45 seconds to 520 seconds. Also good. Other cure temperatures, cure power values, and / or predetermined cure time intervals are possible for other methods of obtaining a cured product. Further, in this method, the prepreg may be further cured to obtain a cured product.

  For various embodiments, as discussed herein, a cured product formed from a curable composition of the present disclosure may have a glass transition temperature of at least 150 ° C.

  For various embodiments, as discussed herein, a cured product formed from a curable composition of the present disclosure can have a thermal decomposition temperature of 300 ° C. to 500 ° C .; The decomposition temperature can be 359 ° C. to 372 ° C., or 363 ° C. to 368 ° C.

  For various embodiments, as discussed herein, a cured product formed from a curable composition of the present disclosure can have a dielectric constant of less than 3.1 at 1 GHz; for example, 1 GHz The dielectric constant at can be 2.92 to 3.02, or 2.91 to 2.89.

  For various embodiments, as discussed herein, a cured product formed from a curable composition of the present disclosure can have a dissipation factor of less than 0.01 at 1 GHz; for example, 1 GHz The dissipation factor at can be 0.003 to 0.01, or 0.004 to 0.007.

  The following examples are presented to illustrate the scope of the present disclosure, but are not intended to limit the scope of the present disclosure. The examples provide methods and specific embodiments of curable compositions comprising the terpolymers of the present disclosure. As provided herein, curable compositions can provide desirable thermal and electrical properties, among other things, without incorporating cyanate groups.

  material

  SMA® EF-40 (SMA 40), (styrene compound-maleic anhydride copolymer), Sartomer Company, Inc. Available from SMA 40 has a 4: 1 styrene to maleic anhydride molar ratio of 10,500, a weight average molecular weight of 2.3, a molecular weight distribution of 2.3, and an acid number of 215 mg KOH / mg.

  SMA® EF-60 (styrene compound-maleic anhydride copolymer), Sartomer Company, Inc. Available from SMA 60 has a 6: 1 styrene to maleic anhydride molar ratio, a weight average molecular weight of 11,500, a molecular weight distribution of 2.1, and an acid number of 156 mg KOH / mg.

  SMA® EF-100 (styrene compound maleic anhydride copolymer), Elf Atochem, Inc. Available from

  N, N-dimethylformamide (DMF) (solvent), Sinopharm Chemical Co. Available from

  Aniline (amine compound), (purity of 99.0% or higher), available from Sigma Aldrich.

  Methanol (analytical grade), Sinopharm Chemical Co. Available from

  Acetic anhydride (analytical grade), available from Sigma Aldrich.

  Sodium acetate (analytical grade), available from Sigma Aldrich.

  Tetrahydrofuran (curing agent) (THF) (HPLC), available from Sigma Aldrich.

  Maleic anhydride (97% purity), Sinopharm Chemical Co. Available from

  Cyclohexanone (solvent), (analytical grade), Sinopharm Chemical Co. Available from

  Methyl ethyl ketone (solvent), (analytical reagent), Sinopharm Chemical Co. Available from

  2-Methylimidazole (catalyst), (analytical grade), Sinopharm Chemical Co. Available from

  D. E. R. 560 (epoxy resin), available from Dow Chemical Company.

  DCPD EPICLONE HP7200L ™ (HP7200) (epoxy resin), available from Dai Nippon Chemical.

  Triethanolamine (TEA) (curing agent), available from Dow Chemical Company.

  Modification of styrene-maleic anhydride copolymer

  To form the terpolymers of the present disclosure, styrene-maleic anhydride (SMA) copolymers were modified with aniline. Modified styrene maleic anhydride (ie, terpolymer) is referred to as “AN-SMA”. Terpolymers were formed using styrene maleic anhydride copolymers SMA 40 and SMA 60. In modifying the styrene-maleic anhydride copolymer, various mole percent (theoretical ratio) of maleic anhydride groups are reacted with aniline.

  In the following, “SMA 40-60” indicates that SMA 40 was used as a styrene maleic anhydride copolymer and 60 mole percent of the maleic anhydride groups were reacted with aniline. Similarly, “AN-SMA 60-60” indicates that SMA 60 was used as a styrene maleic anhydride copolymer and reacted with 60 mole percent of maleic anhydride groups. In other words, the first number of “AN-SMA 40-60” (ie, “40”) indicates which styrene-maleic anhydride copolymer was used, and the second number of “AN-SMA 40-60” ( That is, “60”) indicates the mole percent of maleic anhydride groups reacted with aniline.

  The terpolymer formulation (ie, modified styrene-maleic anhydride copolymer) is summarized in Table I.

  Preparation of AN-SMA 40-60

  SMA 40 is added to a 250 ml three neck flask equipped with a reflux condenser, thermometer and nitrogen inlet. In order to maintain a constant nitrogen pressure in the flask, the nitrogen outlet is sealed with silicone oil through a U-tube. 125 milliliters (ml) of N, N-dimethylformamide (DMF) is poured into the flask to dissolve SMA40. Nitrogen is added to the flask and the air is removed for 5 minutes. The SMA 40 and DMF solution is heated and maintained at 50 ° C. To this solution, 1.65 grams (g) of aniline is added after SMA 40 is completely dissolved in DMF. After 2 hours (hrs), the temperature is increased from 50 ° C to 100 ° C. When the temperature reaches 100 ° C., 7.26 g acetic anhydride and 1.50 g sodium acetate are added to the flask. Five hours after addition of acetic anhydride and sodium acetate, the heat source is removed to terminate the reaction and the flask contents are allowed to cool to approximately 20 ° C. The AN-SMA 40-60 product is precipitated in methanol by dropping the reactants into excess methanol under magnetic stirring (reactant solution to methanol volume ratio is 1 to 10). The final AN-SMA 40-60 product was collected after filtration. The polymer was then placed in a fume hood for several hours to further remove methanol residues. Finally, the AN-SMA 40-60 terpolymer was dried in a vacuum oven at 120 ° C. for 12 hours.

  Preparation of AN-SMA 40-100

  The procedure in AN-SMA 40-60 is repeated with the following changes: use of 2.75 g aniline, 12.1 g acetic anhydride, and 2.5 g sodium acetate.

  Preparation of AN-SMA 40-80

  The procedure in AN-SMA 40-60 is repeated with the following changes: use of 2.20 g aniline, 9.68 g acetic anhydride, and 2.0 g sodium acetate.

  Preparation of AN-SMA 40-40

  Repeat the procedure in AN-SMA 40-60 with the following changes: 1. Use 10 g aniline, 4.84 g acetic anhydride, and 1.0 g sodium acetate.

  Preparation of AN-SMA 60-100

  The procedure in AN-SMA 40-60 is repeated with the following changes: use of SMA 60 instead of SMA 40, 1.93 g aniline, 7.85 g acetic anhydride, and 1.70 g sodium acetate.

  Preparation of AN-SMA 60-60

  The procedure in AN-SMA 40-60 is repeated with the following changes: use of SMA 60 instead of SMA 40, 1.16 g aniline, 4.71 g acetic anhydride, and 1.02 g sodium acetate.

  Preparation of AN-SMA 60-40

  The procedure in AN-SMA 40-60 is repeated with the following changes: use of SMA 60 instead of SMA 40, 0.77 g aniline, 3.14 g acetic anhydride, and 0.368 g sodium acetate.

  Glass-transition temperature

The glass transition temperature (T _g ) of unmodified SMA 40 copolymer, unmodified SMA 60 copolymer, and modified styrene maleic anhydride polymer (ie, terpolymer) was determined.

  The glass transition temperatures for the modified and unmodified SMA 40 and SMA 60 polymers were determined by a differential scanning calorimeter (DSC) (TA Instruments Q2000). Samples of modified and unmodified polymer (approximately 6.0-10.0 mg) were placed in the DSC in the following cycle. Cycle 1: Initial temperature: 20 ° C., final temperature: 180 ° C., and ramp rate = 20 ° C./min. Cycle 2: initial temperature: 180 ° C., final temperature: 20 ° C., ramp rate = minus (−) 20 ° C./min. Cycle 3: Initial temperature: 23 ° C., final temperature: 200 ° C., and ramp rate = 10 ° C./min. The glass transition temperature was determined by the inflection point of the DSC curve.

  The glass transition temperatures of the unmodified and modified SMA 40 and SMA 60 polymers are shown in Table II.

  Maleic anhydride content

The concentration of maleic anhydride building blocks of the modified and unmodified SMA 40 and SMA 60 polymers was determined using Fourier Transform Infrared Spectroscopy (FTIR) (Nicolet 6700 FTIR spectrometer) and the results are shown in Table II. A calibration curve sample was prepared by separately dissolving maleic anhydride in tetrahydrofuran that had been dried by molecular sieves. SMA 40, AN-SMA 40-100, AN-SMA 40-80, AN-SMA 40-60, AN-SMA 40-40, SMA 60, AN-SMA 60-100, AN-SMA 60-60, and AN-SMA 60-40 are 100 parts. Test samples were prepared by placing in a vacuum oven at ° C for 120 minutes, cooling the portions in a desiccator, and dissolving each of the cooled portions in the respective tetrahydrofuran portion. A Nicolet ™ 6700 equipped with a liquid cell was used for calibration curve preparation and unknown maleic anhydride concentration tests. The 1780 cm ⁻¹ peak of the FTIR spectrum was assigned to the vibration of the carbonyl maleate. The peak height is proportional to the maleic anhydride concentration and was used to establish a calibration curve. The data shown in Table II was determined using a calibration curve.

As can be seen from Table II, the modified styrene-maleic anhydride polymer exhibits an increase in glass transition temperature. For example, when comparing the T _{g of} an unmodified SMA 40 sample with the T _g of a modified SMA 40 sample, the modified SMA 40 sample shows an increase in T _g from 7 ° C to 18 ° C. Furthermore, if the _{T g} of the unmodified SMA60 sample compared to the _{T g} of the modified SMA60 sample, modified SMA60 samples show an increase in _{T g} of the 18 ° C. from 16 ° C..

  Examples 1-4 and Comparative Examples AB

  Examples 1-4 are curable compositions comprising a terpolymer (ie, a modified styrene-maleic anhydride polymer). Comparative Examples A to B show curable compositions comprising unmodified SMA 40 and unmodified SMA 60. The formulations of Examples 1-4 are shown in Table III, and the formulations of Comparative Examples A-B are shown in Table IV.

  Examples 1-4

  Each portion of the terpolymer (ie, the modified styrene-maleic anhydride polymer) is dissolved separately in each portion of methyl ethyl ketone and / or cyclohexanone, and then each of the respective portions is D.D. E. R. Examples 1-4 (curable compositions) by adding (trademark) 560 and then 2-methylimidazole dissolved in methanol to form a 10 wt% solution to each of the portions. ) Was formed. Examples 1-4 had 50% non-volatile organic wt%. Table III shows the compositions of Examples 1-4.

  Comparative Examples A to B

  For Comparative Examples A to B, Comparative Examples A to B were formed as in Examples 1 to 4 except that unmodified SMA 40 and SMA 60 were used, respectively (where Examples 1 to 2 were Using modified SMA 40, Examples 3-4 use modified SMA 60). Table IV shows the compositions of Comparative Examples A-B.

  Gelation time test

  Examples 1-4 and Comparative Examples A-B were evaluated for gelatin time by stroke hardening on a 171 ° C hot plate. The results of gelation times for Examples 1-4 are shown in Table V, and the results for Comparative Examples A-B are shown in Table VI.

  The data in Table V shows that the curable compositions (Examples 1-4) have a gel time of 247 s to 280 at a temperature of 171 ° C. The gel times of Examples 1-4 are slightly higher than Comparative Examples A-B (which have gel times of 242s and 247s, respectively, as shown in Table VI). Thus, although the gel times of Examples 1-4 are slightly higher than Comparative Examples A-B, the gel times are still substantially less than 400 s.

  Laminate samples for thermal characterization

  The curable compositions of Examples 1 to 4 and Comparative Examples A to B were brush-coated on the surface of the E-glass fiber mat. This glass fiber mat was put in a 177 ° C. oven having a good air flow for 180 s to obtain a prepreg. The prepreg was hot pressed at 200 ° C. for 1 to 4 hours to obtain a laminate for thermal property analysis. The curing conditions, glass transition temperatures, and decomposition temperatures of Examples 1 to 4 and Comparative Examples A to B are shown in Table VII and Table VIII, respectively.

  Epoxy plaque samples for electrical characterization

  The prepregs of Examples 1-4 and Comparative Examples A-B were ground into powder to form a prepreg powder, which was placed on a piece of flat aluminum foil and then aluminum foil with the prepreg powder Was placed on a metal plate. This assembly was heated to 195 ° C. until the prepreg powder melted. The molten prepreg powder was covered with another aluminum foil, and then a metal plate was placed on the aluminum foil. This assembly was hot-pressed at 195 ° C. for 1 hour. A bubble-free epoxy plaque having a thickness of 0.3 millimeter (mm) was obtained. The values of dielectric constant and dissipation factor of Examples 1 to 4 and Comparative Examples A to B are shown in Table VII and Table VIII, respectively.

  Thermal property analysis

  Glass transition temperature: The glass transition temperature of the laminate samples of Examples 1 to 4 and Comparative Examples A to B was determined. An RSA III dynamic mechanical thermal analyzer (DMTA) (TA Instruments) was used to determine the glass transition temperatures of Examples 1-4 and Comparative Examples AB, and the results are shown in Table VII and Table VII, respectively. Shown in VIII. DMTA used a frequency of 6.28 radians / s, an initial temperature of 30.0 ° C., a final temperature of 350.0 ° C., and a ramp rate of 3.0 ° C./min.

  Decomposition temperature: Thermal stability analysis was used to determine the decomposition temperatures of the cured products of Examples 1-4 and Comparative Examples AB, and the results are shown in Table VII and Table VIII, respectively. Thermal stability analysis was performed using a Q5000 machine available from TA Instruments and a heating rate of 20.0 ° C./min. The decomposition temperature was determined as the temperature at which a 5% weight loss of the material occurred.

  Electrical characteristic analysis

  Dielectric constant: The dielectric constant of each 0.3 millimeter (mm) thick sample of the cured products of Examples 1-4 and Comparative Examples AB was measured by ASTM D-150 using an Agilent E4991A RF impedance / material analyzer. The results are determined in Table VII and Table VIII, respectively.

  Dissipation rate: The dissipation factor of each 0.3 mm thick sample of the cured products of Examples 1-4 and Comparative Examples A-B was determined by ASTM D-150 using an Agilent analyzer and the results were Table VII and Table VIII.

The data in Table VII shows that the cured products of Examples 1-4 had a glass transition temperature from 169 ° C to 193 ° C. The data in Table VIII shows that Comparative Examples A-B had glass transition temperatures of 162 ° C. and 152 ° C., respectively. It can be seen that 1-4 curable compositions incorporating the terpolymers of the present disclosure increase the _Tg as compared to curable compositions that do not incorporate the terpolymer.

  The data in Table VII shows that Examples 1-4 had decomposition temperatures from 362 ° C to 372 ° C. The data in Table VIII shows that Comparative Examples A-B had decomposition temperatures of 354 ° C. and 343 ° C., respectively.

  The data in Table VII show that each 0.3 mm thick sample of Examples 1-4 had a dielectric constant of 2.83 to 3.06 at 1 GHz. The data in Table VIII shows that Comparative Examples A-B had dielectric constants of 2.91 and 3.02 at 1 GHz, respectively.

  The data in Table VII show that each 0.3 mm thick sample of Examples 1-4 had a dissipation factor of 0.004 to 0.009 at 1 GHz. The data in Table VIII shows that Comparative Examples A-B had a dissipation factor of 0.006 and 0.011 at 1 GHz, respectively.

  In order to determine the effect of different curing temperatures, Example 4 was cured at two different curing conditions. As can be seen in Table VII, comparing the results between the two cured products using Example 4 shows that different curing conditions can have a slight effect on the properties of the cured product.

  Laminate properties: Table IX shows the curing conditions, resin content, glass transition temperature, dielectric constant, dissipation factor, and peel strength of the laminates prepared from Example 3 and Comparative Example B. The peel strength is determined by WILA008.

  The data in Table IX shows that the laminate prepared from Example 3 (including modified SMA (AN-SMA 60-60)) has a 20 ° C. higher glass transition temperature than Comparative Example B (including unmodified SMA 60). Indicates. The dielectric constant and dissipation factor of Example 3 show a slight improvement over Comparative Example B. Furthermore, the peel strength of the laminate formed from Example 3 shows an improvement of 26.06% over the laminate prepared from unmodified SMA60.

  Examples 5 to 16: Effect of change in molar quota of epoxy groups to MAH

  Examples 5-16 show the effect of changing the molar ratio of epoxy group to maleic anhydride in forming the curable composition. For Examples 5-16, curable compositions were prepared by using AN-SMA 60-40 and DCPD-epoxy (HP7200).

  Examples 5-16 are cured products formed from curable compositions containing terpolymers. Examples 5-16 are formed by dissolving portions of the AN-SMA 60-40 terpolymer separately in each portion of MEK, then adding HP7200 to each of the portions and then adding TEA. did. The formulations of Examples 5-16 are shown in Table X.

Glass transition temperature ( _Tg )

The T _g of the cured resins of Examples 5-16 were measured by DSC from TA Instruments (Q2000 V24.7) with a nitrogen flow. The software was “Universal Analysis V4.5A”. Samples of each example (6-10 mg) were placed in an aluminum pan, covered with a pan lid and crimped. The sample was placed in a DSC Q2000 instrument. Three identical heating cycles were performed. The initial temperature was set to 40 ° C. The sample was heated from 40 to 250 ° C. with a ramp rate of 10 ° C./min. After tilting, the sample was held at 250 ° C. for 5 minutes and then the sample was cooled to 40 ° C. at a ramp rate of −20 ° C./min. This was repeated two more times. The T _g, determined by DSC software for transition at the third temperature cycle on heating ramp. The results of Examples 5-16 are shown in Table XI.

Dielectric constant (D _k ) / Dissipation rate (D _f )

  The dielectric constant and dissipation factor of Examples 5-16 were determined using the methods described herein with respect to Examples 1-4. The results of Examples 5-16 are shown in Table XI.

  Maleic anhydride content

  The maleic anhydride content of the cured products formed from the curable compositions of Examples 5-16 was determined by the method described herein with respect to Examples 1-4. The results of Examples 5-16 are shown in Table XI.

  The data in Table XI shows that the molar ratio of epoxy groups to maleic anhydride affects the glass transition temperature. For example, a cured product of a curable composition having a molar ratio in the range of 1.0: 1.0 to 2.7: 1.0 has a glass transition temperature of greater than 150 ° C. Furthermore, the cured product of the curable composition having a molar ratio ranging from 1.3: 1.0 to 1.9: 1.0 has a glass transition temperature of 173 ° C. As can be seen in Table XII, once the molar ratio of epoxy to maleic anhydride is outside the range of 1.0: 1.0 to 2.7: 1.0, the glass transition temperature, dielectric constant, and dissipation factor are Reduce to 140 ° C and 141 ° C.

  Comparative modified styrene maleic anhydride A (AN-SMA1000)

  Comparative modified styrene maleic anhydride A (AN-SMA1000) was prepared by modifying SMA1000 with aniline. 202 g SMA 1000 and 134 g cyclohexanone are added to the reactor. The contents are heated to 100 ° C. and then 46.5 g of aniline is added to the reactor while maintaining the resulting mixture at 97 ° C. to 103 ° C. After completion of the aniline addition, the reaction was carried out at 100 ° C. for 4 hours, and then the reaction mixture was heated to 160 ° C. and reacted under reflux for 12 hours. The reaction mixture was cooled to 100 ° C., and 159 g of toluene was added thereto to obtain a solution containing a terpolymer of styrene, maleic anhydride and N-phenylmaleimide. The solid content of this solution was 48% by weight.

  Residual aniline analysis

  Residual aniline and maleic anhydride (MAH) content was determined for AN-SMA 60-40 and comparatively modified styrene maleic anhydride A prepared herein. Residual aniline was determined by Head Space (Apparatus: Agilent G1888 Headspace Sampler / GCMS (Apparatus: Agilent 6890N Gas Chromatography System with DB-VRX column). Samples of comparative modified styrene maleic anhydrides AB (0. 5 ± 0.05 g) was added to a Head Space (HS) sample vial and sealed for HS / GCMS analysis, pure aniline was used as an external standard, which was about 0.1 g / 5 mL in DMF. A solution of aniline (10 microliters (μl)) was injected into the HS sample vial and the aniline concentration was calculated by one spot external calibration made as described above. Acid content is described in this specification It was determined as. Results are shown in Table XII.

  As can be seen in Table XII, residual aniline in comparatively modified styrene maleic anhydride A (AN-SMA 1000) is much higher than AN-SMA 60-40.

  Comparative Examples C-F

  Comparative Examples C-F are curable compositions comprising a modified styrene maleic anhydride copolymer, where the styrene maleic anhydride copolymer is SMA 1000. The formulations of Comparative Examples C-F are shown in Table XIII.

  Comparative Example C

  Comparative Example C is data taken from Comparative Example 13 of US Pat. No. 6,667,107.

  Comparative Example D

  The resulting comparatively modified styrene maleic anhydride A (AN-SMA 1000) as discussed above is used. The procedure is as follows: Mix epoxy resin (100 parts by weight) and AN-SMA 1000 (100 parts by weight). The catalyst (2-MI) is added to adjust the gel time in the range of 200s to 300s.

  Comparative Example E

  15 ml of the resulting comparatively modified styrene maleic anhydride A (AN-SMA 1000) (48% solution in cyclohexanone and toluene) was added dropwise to 150 ml of methanol and a white solid precipitated. After stirring for 10 minutes, the white solid was filtered off and then dried in a vacuum oven at 100 ° C. for 6 hours. The resulting white solid was solid AN-SMA1000, which was then used to cure HP7200 using methyl ethyl ketone as the solvent. The resulting epoxy to MAH molar ratio is 5.8: 1.0.

  Comparative Example F

  Comparative Example E is repeated with the following changes: The resulting epoxy to MAH molar ratio is 1.0: 1.0.

  Laminate samples for thermal characterization

  The curable composition of Comparative Examples D-F (Comparative Example C is data taken from Comparative Example 13 of US Pat. No. 6,667,107) was brushed onto the E-glass fiber mat surface. This glass fiber mat was placed in a 177 ° C. oven with good airflow for 180 s to obtain a prepreg. This prepreg was hot pressed at 200 ° C. for 1 to 4 hours to obtain a laminate for thermal characteristic analysis. The glass transition temperatures of Comparative Examples C-F are shown in Table XIV.

  Epoxy plaque samples for electrical characterization

  The prepreg of Comparative Examples D to F (Comparative Example C is data taken from Comparative Example 13 of US Pat. No. 6,667,107) is pulverized into powder to form a prepreg powder. An aluminum foil with a prepreg powder was then placed on a flat metal foil. This assembly was heated to 195 ° C. until the prepreg powder melted. The molten prepreg powder was covered with another aluminum foil, and then a metal plate was placed on the aluminum foil. This assembly was hot-pressed at 195 ° C. for 1 hour. A bubble-free epoxy plaque having a thickness of 0.3 millimeter (mm) was obtained. The dielectric constant and dissipation factor values for Comparative Examples C-F are shown in Table XIV.

Glass transition temperature ( _Tg )

The T _g of the cured resins of Comparative Examples C-F were measured using the method described herein with respect to Examples 5-16. The results of Comparative Examples C-F are shown in Table XIV.

Dielectric constant (D _k ) / Dissipation rate (D _f )

  The dielectric constant and dissipation factor of Comparative Examples C-F were determined using the methods described herein for Examples 1-4. The results of Comparative Examples C-F are shown in Table XIV.

  Maleic anhydride content

  The maleic anhydride content of the cured products formed from the curable compositions of Comparative Examples C-F was determined by the method described herein with respect to Examples 1-4. The results of Comparative Examples C-F are shown in Table XIV.

The data in Table XIV of Comparative Examples C-E shows that the comparative modified styrene maleic anhydride A (ie, AN-SMA 1000) does not give a glass transition temperature comparable to that of Examples 5-16. Comparative Example F shows that by changing the molar ratio of epoxy groups to maleic anhydride, T _g may rise significantly. Thus, an inappropriate stoichiometric ratio of epoxy to hardener can reduce the glass transition temperature.

  Examples 17-18 and Comparative Examples GH

  Examples 17-18 demonstrate the desired properties obtained by using the terpolymers described herein in the range of 1.0: 1.0 to 2.7: 1.0. Comparative Example G shows the effect of adding cyanate groups to the curable composition, Comparative Example H has no cyanate and terpolymer from 1.0: 1.0 to 2.7: 1.0. The effect included outside the range of.

  Examples 17-18

  Examples 17-18 are cured products formed from curable compositions containing a terpolymer. Examples 17-18 were prepared by dissolving the AN-SMA 60-60 terpolymer portion separately in each portion of MEK, then adding DER ™ 560 to each of the portions, then 10 wt% Formed by adding 2-methylimidazole dissolved in methanol to each of the portions to form a solution. The formulations of Examples 17-18 are shown in Table XV.

  Comparative Examples G to H

  Comparative Examples GH separately dissolve portions of the comparatively modified styrene-maleic anhydride polymer in each portion of tetrahydrofuran, and then add DCPD EPICLONE HP7200L ™ and bisphenol A cyanate to each of the portions. Formed by. The formulations of Comparative Examples GH are shown in Table XV.

Glass transition temperature ( _Tg )

The T _g of the cured resins of Examples 17-18 and Comparative Examples GH were measured using the methods described herein with respect to Examples 1-4. The results of Examples 17-18 and Comparative Examples G-H are shown in Table XVI.

Dielectric constant (D _k ) / Dissipation rate (D _f )

  The dielectric constant and dissipation factor of Examples 17-18 and Comparative Examples GH were determined using the methods described herein for Examples 1-4. The results of Examples 17-18 and Comparative Examples G-H are shown in Table XVI.

  Maleic anhydride content

  The maleic anhydride content of the cured products formed from the curable compositions of Examples 17-18 and Comparative Examples GH was determined by the method described herein with respect to Examples 1-4. The results of Examples 17-18 and Comparative Examples G-H are shown in Table XVI.

  Examples 17-18 each have a molar ratio of epoxy to maleic anhydride that is in the range of 1.0: 1.0 to 2.7: 1.0. As can be seen in Table XVI, the glass transition temperatures of Examples 17-18 exceed 150 ° C. and do not contain cyanate.

Comparative Example G shows the cured product of a curable composition using AN-SMA 1000 with cyanate. The glass transition temperature of Comparative Example G is 197 ° C., which indicates that cyanate increases the glass transition temperature of the cured product. Comparative Example H had no cyanate and had a molar ratio of epoxy group to second building block of 3.77: 1 (which was outside the range of 1.0: 1.0 to 2.7: 1.0). 2 shows a cured product of a curable composition using AN-SMA 1000. As can be seen in Table XVI, the glass transition temperature of Comparative Example H is 143 ° C., which is significantly lower than Comparative Example G containing cyanate and lower than the glass transition temperatures of Examples 17-18.

Claims (18)

A curable composition comprising: an epoxy resin; and a curing agent compound for curing with the epoxy resin, wherein the curing agent compound comprises:
Formula (I):

A first structural unit of formula (II):

A second structural unit of formula (III):

A terpolymer having a third structural unit of
Wherein each m, n and r is independently a real number representing the mole fraction of each constituent unit in the terpolymer, and each R is independently hydrogen, aromatic group or fatty acid. a family group, Ar is an aromatic group, and epoxy groups to the second structural unit is 1.3: 1.0 to 2.7: have a 1.0 molar ratio in the range of,
A curable composition, wherein the curable composition does not contain a cyanate group .   The curable composition of claim 1, wherein the epoxy group to the second building block has a molar ratio in the range of 1.3: 1.0 to 1.9: 1.0.   The curable composition of claim 1 or 2, wherein the epoxy group to second structural unit has a molar ratio in the range of 1.3: 1.0 to 1.7: 1.0.   The mole fraction m is 0.50 or more, the mole fractions n and r are each independently 0.45 to 0.05, and (m + n + r) = 1.00. The curable composition as described in any one of -3. The curable composition according to any one of claims 1 to 4 , wherein the cured product of the curable composition has a glass transition temperature of at least 150C. The curable composition according to any one of claims 1 to 5 , wherein the cured product of the curable composition has a dielectric constant ( _Dk ) of 3.1 or less at a frequency of 1 GHz. The curable composition according to any one of claims 1 to 6 , wherein a cured product of the curable composition has a dissipation factor ( _Df ) of 0.01 or less at a frequency of 1 GHz. Each R is independently hydrogen, aromatic or aliphatic group, Ar is a monocyclic or polycyclic aromatic or heteroaromatic group representing the ring, according to claim 1 to 7 The curable composition as described in any one of these. The first structure units to the second structural unit is from 1: 1 to 20: a molar ratio of 1, and the curable composition according to any one of claims 1-8. The curable composition according to any one of claims 1 to 9 , wherein the molar ratio of the first structural unit to the second structural unit is in the range of 3: 1 to 15: 1. The curable composition according to any one of claims 1 to 10 , wherein the second structural unit comprises 0.1 percent (%) to 41% by weight of the terpolymer. The curable composition according to any one of claims 1 to 11 , wherein the second structural unit constitutes 5% to 20% by weight of the terpolymer. The curable composition according to any one of claims 1 to 12 , wherein the third structural unit constitutes 0.1% to 62.69% by weight of the terpolymer. The curable composition according to any one of claims 1 to 13 , wherein the third structural unit constitutes 0.5% to 50% by weight of the terpolymer. The curable composition according to any one of claims 1 to 14 , wherein the epoxy resin is selected from the group consisting of an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, and combinations thereof. A prepreg comprising a reinforcing component and the curable composition according to any one of claims 1 to 15 . An electrical laminate structure comprising the reaction product of the curable composition according to any one of claims 1 to 15 . A method of preparing a curable composition comprising: preparing an epoxy resin; and reacting the epoxy resin with a curing agent compound, wherein the curing agent compound comprises:
Formula (I):

A first structural unit of formula (II):

A second structural unit of formula (III):

A terpolymer having a third structural unit of
Wherein each m, n and r is independently a real number representing the mole fraction of each constituent unit in the terpolymer, and each R is independently hydrogen, aromatic group or fatty acid. a family group, Ar is an aromatic group, and epoxy groups to the second structural unit is 1.3: 1.0 to 2.7: have a 1.0 molar ratio in the range of the The method wherein the curable composition does not contain cyanate groups .