Maleimide polymer for electrolaminated boards

Abstract

In this specification, formula (I) [Formula 1] JPEG2026530629000024.jpg83136 (In the formula, X is a bond, carbonyl, methylene, C2~C) 20 Alkanedyls, and C2~C 20 Selected from the group consisting of alkenziels; Y is C2~C 20 Selected from the group consisting of the alkanediyl, part of formula (Y1), part of formula (Y2), part of formula (Y3), part of formula (Y4), and part of formula (Y5), R 1 ~R 6 Compounds are provided in which each is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, and alkoxy (where n is an integer of 1 or more). The compounds exhibit good solubility, high thermal stability, and good dielectric properties, and are useful, for example, in the preparation of electrolaminated board compositions.

Description

[Background technology]

[0001] Bismaleimide (BMI) is a thermosetting resin that can be used in high-temperature applications due to its thermal stability and relatively good dielectric properties. Therefore, BMI can be used in both industrial and household electrical appliances. For example, BMI can be useful in electrolaminated laminate applications requiring high-temperature resistance with low loss (i.e., the level at which energy dissipation or attenuation occurs as electromagnetic waves or signals pass through the material). Furthermore, BMI is less expensive than polyphenylene ethers (e.g., SA9000 from Sabic), which are common components in electrolaminated laminate applications.

[0002] Conventionally, ordinary BMIs are used in electrolamination processes. Ordinary BMIs are typically used as base materials for higher-performance thermosetting resins. However, commercially available BMIs (e.g., 4,4'-diphenylmethanebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide) may have low solubility for ketones (i.e., typically less than 20% at 25°C) and may exhibit poor viscosity increase during the pre-curing step of the electrolamination process. Therefore, the percentage of BMI in formulations is usually low. Consequently, improved compounds and processes are needed that include maleimide polymers with good solubility, high thermal stability, and good dielectric properties. [Overview of the project]

[0003] For example, in this specification, Formula I

[0004] [ka] (In the formula, X is a bond, carbonyl, methylene, C2~C 20 Alkanedyls, and C2~C 20 Selected from a group consisting of alkenziels, Y is C2 to C 20 alkanediyl, a moiety of formula Y1

[0005]

Chemical Formula

[0006]

Chemical Formula

[0007]

Chemical Formula

[0008]

Chemical Formula

[0009]

Chemical Formula

[0010] Also provided herein is a method for producing a compound of formula I, comprising the step of reacting a polyene and a bismaleimide in a liquid reaction medium. Preferably, the liquid reaction medium comprises an organic solvent such as diethylene glycol dimethyl ether.

[0011] Furthermore, this specification provides a curable composition comprising a compound of formula I. The curable composition may be useful, for example, for preparing electrolaminated boards such as printed circuit boards. The curable composition may further comprise one or more optionally selected components, such as a crosslinking component, a free radical initiator, and a crosslinking catalyst.

[0012] Furthermore, a printed circuit board comprising a curable resin composition (for example, a curable resin composition comprising a compound of formula I) provided herein is also provided.

[0013] Other purposes and features are, in part, self-evident, and in part, noted below. [Modes for carrying out the invention]

[0014] This specification provides compounds useful in electrolaminated laminate compositions exhibiting good solubility, high thermal stability, and good dielectric properties. For example, this specification provides maleimide polymers produced from the Diels-Alder reaction of polyenes and BMI. The compounds disclosed herein exhibit higher solubility in methyl ethyl ketone (MEK) compared to prior art compositions and may provide low-loss performance characteristics suitable for use in electrolaminated laminates.

[0015] Preferably, the compounds provided herein are fluorine-free (more preferably halogen-free). For example, the compounds can be used to prepare fluorine-free (more preferably halogen-free) electrolaminated laminate compositions.

[0016] definition As used herein, the term "alkyl" refers to a linear or branched chain portion containing up to approximately 10 carbon atoms (unless otherwise specified, a different number of carbon atoms). Non-exclusive examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. Alkyl groups may be linear or branched alkyl groups (e.g., isopropyl).

[0017] As used herein, the term "aryl" refers to a moiety derived from an arene by removing a hydrogen atom from a ring carbon atom. Non-exclusive examples of aryl groups include phenyl, o-tolyl, p-tolyl, and naphthyl.

[0018] As used herein, the term “alkoxy” refers to the part in the form of -OR', where R' is an alkyl group as defined herein. For example, the -OCH3 group may be referred to herein as “methoxy,” and the -OCH2CH3 group may be referred to herein as “ethoxy.” Non-exclusive examples of alkoxy groups include methoxy, ethoxy, and propoxy. The alkoxy moiety may include a linear alkyl group or a branched alkyl group (e.g., isopropoxy).

[0019] As used herein, the term “alkenyl” refers to a linear or branched chain portion containing up to approximately 10 carbon atoms (unless otherwise specified) and at least one double bond between adjacent carbon atoms. Non-exclusive examples of alkenyl groups include vinyl, propenyl, and butenyl.

[0020] As used herein, the term "carbonyl" refers to a part in the form -C(O)-, where the carbon atom shares a double bond with the oxygen atom.

[0021] As used herein, the term “alkanediyl” refers to a linear or branched chain portion having two free valencies. Generally, an alkanediyl group can be a linear or branched chain portion containing up to approximately 10 carbon atoms (unless otherwise specified, a different number of carbon atoms), as outlined above with respect to “alkyl.” Non-limiting examples of alkanediyl groups include ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and 2-methylpropane-1,3-diyl.

[0022] As used herein, the term "alkenediyl" refers to a straight or branched chain moiety having two free valences and one or more carbon-carbon double bonds. Generally, an alkenediyl group may be a straight or branched chain moiety comprising up to about 10 carbon atoms (unless a different number of carbon atoms is otherwise specified), as outlined above with respect to "alkenyl". Non-limiting examples of alkenediyl groups include ethene-1,2-diyl, prop-1-ene-1,3-diyl, but-1-ene-1,4-diyl, and but-2-ene-1,4-diyl.

[0023] As used herein, the term "hydrogen" refers to the stable isotopes of hydrogen, that is 1 H (also known as protium) and 2 H (also known as deuterium), and includes both.

[0024] As used herein, the term "polyene" refers to a polyunsaturated organic compound comprising a chain of alternating carbon-carbon double bonds and single bonds.

[0025] Polymaleimide compound In the present specification, Formula I

[0026]

Chemical Formula

[0027]

Chemical Formula

[0028]

Chemical Formula

[0029] [ka] The part, formula Y4

[0030] [ka] The portion of equation Y5

[0031] [ka] Selected from a group consisting of parts, R 1 ~R 6 Each of these is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, and alkoxy. n is an integer greater than or equal to 1. The compound is provided.

[0032] In the compound of formula I, X may be an alkanediyl group. For example, X may be an alkanediyl group having 2 to about 10 carbon atoms, for example, 2 to 6 carbon atoms. Non-limiting examples of alkanediyl groups include ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and 2-methylpropane-1,3-diyl.

[0033] In the compound of formula I, X may be an alkenediyl group. For example, X may be an alkenediyl group having 2 to about 10 carbon atoms, for example, 2 to 6 carbon atoms. Non-restrictive examples of alkenediyl groups include ethene-1,2-diyl, propa-1-ene-1,3-diyl, buta-1-ene-1,4-diyl, and buta-2-ene-1,4-diyl.

[0034] In the compound of formula I, X may be a carbonyl group.

[0035] In the compound of formula I, Y may be an alkanediyl group having at least about 2 carbon atoms. For example, Y may be an alkanediyl group having about 2 to about 10 carbon atoms.

[0036] In the compound of formula I, R 1 ~R 6 Each of these can be independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, vinyl, propynyl, butenyl, phenyl, naphthyl, methoxy, ethoxy, propoxy, and butoxy. For example, R 1 ~R 6 Each of these can be independently selected from the group consisting of hydrogen, methyl, ethyl, phenyl, and methoxy.

[0037] In the compound of formula I, n is preferably greater than 1. In various embodiments, n may be at least 10, at least 100, or at least 1000.

[0038] Method for producing polymaleimide compounds This specification also provides a method for preparing the compound of formula I. As discussed above, BMI can be useful in electrolaminated laminate applications requiring low loss and high-temperature resistance. Although not bound by any particular theory, it is thought that the Diels-Alder reaction of polyenes and BMI may improve the solubility and low-loss performance of BMI.

[0039] For example, this specification provides a method for producing a compound of formula I, comprising the step of reacting a polyene and BMI.

[0040] The polyene may be a conjugated tetraenic ketone derived from a natural product or a bio-based material. Non-limiting examples include β-carotene, α-carotene, retinyl palmitate, and disinnamyrideneacetone.

[0041] A BMI can be any BMI. For example, a BMI may be a compound containing an alkyl or aryl linkage between two maleimide groups. A non-limiting example of a BMI is one containing a maleimide group with a methylenediphenyl linkage.

[0042] The method may include a step of reacting the polyene with BMI, and the molar ratio of BMI to polyene may be about 1:1 to about 4:1. For example, the molar ratio of BMI to polyene may be at least about 1:1, at least about 2:1, at least about 3:1, or at least about 4:1.

[0043] The method may include the step of reacting the polyene and BMI in a liquid reaction medium containing a solvent. Preferably, the liquid reaction medium contains an organic solvent.

[0044] Non-limiting examples of suitable organic solvents include diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, 1,3,5-trimethylbenzene, xylene, and methyl isobutyl ketone. For example, the organic solvent may include diethylene glycol dimethyl ether.

[0045] The liquid reaction medium may be maintained at a temperature of at least about 110°C during the reaction. For example, the liquid reaction medium may be maintained at a temperature of at least about 120°C, at least about 140°C, or at least about 150°C. The liquid reaction medium may be maintained at a temperature not exceeding about 160°C, about 150°C, or about 140°C. As a non-limiting example, the liquid reaction medium may be maintained at a temperature of about 110°C to about 130°C, or about 140°C to about 160°C.

[0046] curable composition This specification also provides curable compositions comprising compounds of Formula I, which may be selected and / or prepared as described in detail above. For example, curable compositions are useful for preparing electrolaminated boards such as printed circuit boards.

[0047] The curable composition may contain the compound of formula I in an amount of at least about 60% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, or at least about 100% by weight of the composition.

[0048] The curable composition may further contain one or more of the following: a crosslinking component, a free radical initiator, and a crosslinking catalyst.

[0049] crosslinking component The curable composition may contain a crosslinking component comprising one or more crosslinking agents. The crosslinking agent may be a resin. Non-limiting examples of suitable crosslinking agents include triallyl isocyanurate (TAIC), polyenes, cyanate esters, poly(p-phenylene oxide) (PPO), and polybutadiene.

[0050] The curable composition may contain a crosslinking component in an amount of at least about 5% by weight, or at least about 10% by weight, of the composition. Typically, the curable composition contains a crosslinking component in an amount of about 40% by weight or less, about 30% by weight or less, about 20% by weight or less, about 10% by weight or less, or about 5% by weight or less, of the composition. For example, the curable composition may contain a crosslinking component in an amount of about 0% to about 40% by weight of the composition.

[0051] Initiator component The curable composition may contain an initiator component comprising one or more free radical initiators. While not bound by any particular theory, free radical initiators may function to release free radicals at high temperatures, thereby inducing crosslinking of all components in the composition.

[0052] Non-limiting examples of free radical initiators include dicumyl peroxide, di-tert-butyl peroxide, and benzoyl peroxide. For example, free radical initiators may include peroxide compounds.

[0053] The curable composition may contain, for example, one or more free radical initiators in amounts of about 0.5% to about 5% by weight, about 0.5% to about 4% by weight, about 0.5% to about 3% by weight, about 1% to about 2% by weight, or about 1.5% to about 2.5% by weight of the composition.

[0054] Crosslinking catalyst components In a preferred embodiment, the curable composition further comprises a crosslinking catalyst. The crosslinking catalyst may catalyze the crosslinking of cyanate esters. Non-limiting examples of crosslinking catalysts include Zn(C) dioctanoate. 16 H 30 It contains (O4Zn). For example, the curable composition may contain Zn dioctanoate in an amount of about 0.1% to about 1% by weight of the composition.

[0055] Electrolaminated board An electrolaminated laminate containing a curable resin composition provided herein is also provided.

[0056] For example, a prepreg can be formed from a composition comprising a reinforcing component and a compound of Formula I provided herein (e.g., from the curable composition described above). The prepreg can be obtained by contacting the reinforcing component and the matrix component via rolling, dipping, spraying, or other such procedures.

[0057] The reinforcing component may be a fiber. Examples of fibers include, but are not limited to, glass, aramid, and combinations thereof. Examples of glass fibers include, but are not limited to, A glass fiber, E glass fiber, C glass fiber, R glass fiber, S glass fiber, T glass fiber, and combinations thereof. Aramid is an organic polymer, and examples of it include, but are not limited to, Kevlar®, Twaron®, and combinations thereof.

[0058] The reinforcing component may be a fabric. The fabric may be formed from fibers as discussed herein. Non-limiting examples of fabrics include sutures, woven fabrics, and combinations thereof. The fabric may be unidirectional, multiaxial, and combinations thereof. The reinforcing component may be a combination of fibers and fabrics.

[0059] After the reinforcing components come into contact with the matrix components, the solvent may be removed by evaporation.

[0060] Volatilization can occur upon exposure to a temperature of at least about 60°C. For example, volatilization can occur at temperatures of at least about 80°C, at least about 100°C, or at least about 130°C. Volatilization can be maintained at temperatures not exceeding about 150°C, about 200°C, or about 250°C. For example, volatilization can occur at temperatures between about 60°C and about 250°C. As a non-limiting example, volatilization can occur at temperatures between about 100°C and about 200°C, or between about 130°C and about 150°C.

[0061] Volatilization can occur for a period of at least approximately 1 minute. For example, volatilization can occur for a period of at least approximately 2 minutes, at least approximately 3 minutes, or at least approximately 4 minutes. Volatilization can occur for a period not exceeding approximately 30 minutes, approximately 25 minutes, approximately 20 minutes, approximately 15 minutes, approximately 10 minutes, or approximately 5 minutes. As a non-limiting example, volatilization can occur over a period of approximately 2 minutes to approximately 10 minutes, or approximately 3 minutes to approximately 5 minutes.

[0062] The matrix components may be partially cured while the solvent is evaporating and / or after it has evaporated. The resulting material may be called a prepreg. The prepreg may be layered and / or molded into a certain shape before further curing. In some applications (e.g., when electrolaminated boards are manufactured), layers of prepreg may be alternating with layers of conductive material. Non-limiting examples of conductive materials include copper foil.

[0063] The prepreg may be cured (e.g., more completely cured) to obtain a cured product. The prepreg may be cured by applying pressure (i.e., curing force) and / or heat.

[0064] An unrestricted example of a process for obtaining a more completely cured product is pressurization. The prepreg may be placed in a press, where it is subjected to curing forces over a predetermined curing interval to obtain a more completely cured product. The press may have a curing temperature of at least about 60°C, at least about 75°C, at least about 100°C, at least about 125°C, or at least about 150°C. The press may have a curing temperature not exceeding about 250°C, about 240°C, or about 230°C. For example, the press may have a curing temperature of about 60°C to 250°C. Unrestricted examples of the curing temperature of the press include temperatures of about 100°C to about 240°C, or about 150°C to about 230°C.

[0065] In one or more embodiments, the press may have a curing temperature that slopes from a lower curing temperature to a higher curing temperature over a gradient period interval. Furthermore, the curing temperature may vary depending on the presence of a curing agent, the amount of curing agent, and / or the composition of the curing agent.

[0066] Filler components In a preferred embodiment, the electrolaminated board further comprises a filler component. While not bound by any particular theory, the presence of a filler component may improve dimensional stability, mechanical strength, and / or thermal conductivity of the composition.

[0067] Non-limiting examples of suitable filler components include spherical silica, fused silica, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, boron nitride, mica, talc, and mixtures thereof. In preferred embodiments, the filler component includes an inorganic filler. For example, the filler component may include silica.

[0068] The electrolaminated laminate may contain at least about 20% by weight, about 30% by weight, or about 40% by weight of filler components. The electrolaminated laminate may also contain filler components in amounts not exceeding about 80% by weight, about 70% by weight, or about 60% by weight. For example, the electrolaminated laminate may contain filler components in amounts from about 20% by weight to about 80% by weight. Non-limiting examples of the weight percentage of filler components in the electrolaminated laminate composition include about 30% by weight to about 70% by weight, or about 40% by weight to about 60% by weight. [Examples]

[0069] The following non-limiting embodiments are provided to further illustrate the present disclosure.

[0070] Unless otherwise specified, the materials described below were used in each of the following embodiments.

[0071] BMI-5100 is a 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide available from Yamato Chemical Industries, Ltd.

[0072] BMI-1000 is a 4,4'-diphenylmethanebismaleimide available from Yamato Chemical Industries, Ltd.

[0073] TAIC is triallyl isocyanurate available from Sinopharm Chemical Reagent Co., Ltd.

[0074] DCP is dicumyl peroxide, available from Sinopharm Chemical Reagent Co., Ltd.

[0075] BisM cyanate is 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisphenylcyanate, available from Yangzhou Techia Material Co., Ltd.

[0076] [Example 1] Synthesis of polymaleimide 1 The polymaleimide of formula I was prepared as described below.

[0077] In the first step, 43.04 g (0.080 mol) of β-carotene was dissolved in 120 g (g) of diethylene glycol dimethyl ether at a temperature of 150°C.

[0078] In the second step, 20.20 g (0.117 mol) of N-phenylmaleimide was gradually added to the mixture from the first step.

[0079] In the third step, the reaction mixture from the second step was heated at a temperature of 150°C for 3 hours to form an intermediate solution.

[0080] In the fourth step, 57.67 g (0.161 mol) of 4,4'-diphenylmethanebismaleimide was dissolved in 120 g of diethylene glycol dimethyl ether at a temperature of 120°C and allowed to stand.

[0081] In the fifth step, the intermediate solution from the third step was gradually added to the bismaleimide solution from the fourth step over a period of 45 minutes.

[0082] In the sixth step, the reaction solution from the fifth step was further heated at a temperature of 150°C for a period of 1.5 hours.

[0083] In the seventh step, after the reaction from the sixth step was complete, the reaction solution was added dropwise to 2.5 liters of water to precipitate the solid product.

[0084] In the eighth step, the filter cake was recovered after vacuum filtration. The filter cake was ground into a powder and baked in a vacuum furnace at 90°C for 5 hours, resulting in a dry powder weighing 120.05 g.

[0085] In the ninth step, the dried product powder from the eighth step was dissolved in methyl ethyl ketone (MEK) to form a 64% (by weight) solution.

[0086] [Example 2] Synthesis of polymaleimide 2 The polymaleimide of formula I was prepared as described below.

[0087] In the first step, 32.33 g (0.060 mol) of β-carotene and 20.72 g (0.120 mol) of N-phenylmaleimide were dissolved in 120 g of propylene glycol monomethyl ether acetate at a temperature of 145°C to form a solution.

[0088] In the second step, the reaction solution from the first step was heated at a temperature of 145°C for 3 hours to form an intermediate solution.

[0089] In the third step, 43.19 g (0.121 mol) of 4,4'-diphenylmethanebismaleimide was dissolved in 130 g of propylene glycol monomethyl ether acetate at a temperature of 145°C and allowed to stand.

[0090] In the fourth step, the intermediate solution from the second step was gradually added to the bismaleimide solution from the third step over a period of 25 minutes.

[0091] In the fifth step, the reaction solution from the fourth step was further heated at a temperature of 145°C for a period of 4 hours.

[0092] In the sixth step, after the reaction from the fifth step was complete, the reaction solution was added dropwise to 1.6 L of petroleum ether to precipitate the solid product.

[0093] In step 7, after vacuum filtration, the filter cake was collected and washed twice with 200 ml (mL) of petroleum ether.

[0094] In the eighth step, the washed filtered cake from the seventh step was baked in a vacuum oven at 100°C for 2 hours, resulting in a dry powder weighing 86.80 g.

[0095] In the ninth step, the dried product powder from the eighth step was dissolved in MEK to form a 65% (by weight) solution.

[0096] [Example 3] Synthesis of polymaleimide 3 The polymaleimide of formula I was prepared as described below.

[0097] In the first step, 32.28 g (0.060 mol) of β-carotene was dissolved in 100 g of 1,3,5-trimethylbenzene at a temperature of 160°C.

[0098] In the second step, 20.76 g (0.120 mol) of N-phenylmaleimide was gradually added to the solution from the first step.

[0099] In the third step, the reaction solution from the second step was heated at 160°C for 2.5 hours to form an intermediate solution.

[0100] In the fourth step, 53.08 g (0.120 mol) of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide was dissolved in 100 g of 1,3,5-trimethylbenzene at a temperature of 165°C and allowed to stand.

[0101] In the fifth step, the intermediate solution from the third step was gradually added to the bismaleimide solution from the fourth step over a period of 35 minutes.

[0102] In the sixth step, the reaction solution from the fifth step was further heated at a temperature of 165°C for a period of 9 hours.

[0103] In the seventh step, after the reaction from the sixth step was complete, the reaction solution was added dropwise to 1.5 L of petroleum ether to precipitate the solid product.

[0104] In step 8, after vacuum filtration, the filter cake was collected and washed three times with 300 mL of petroleum ether.

[0105] In the ninth step, the washed filtered cake from the eighth step was baked in a vacuum oven at 100°C for 2 hours, resulting in a dry powder weighing 95.20 g.

[0106] In the tenth step, the dried powder from the ninth step was dissolved in MEK to form a 65% (by weight) solution.

[0107] [Example 4] Synthesis of polymaleimide 4 The polymaleimide of formula I was prepared as described below.

[0108] In the first step, 32.25 g (0.060 mol) of β-carotene and 11.80 g (0.120 mol) of maleic anhydride were dissolved in 160 g of xylene at a temperature of 130°C.

[0109] In the second step, the reaction solution from the first step was heated at a temperature of 140°C for 3 hours, and then cooled to a temperature of 50°C.

[0110] In the third step, 22.15 g (0.120 mol) of 1-dodecylamine was gradually added to the reaction solution from the second step.

[0111] In the fourth step, the solution from the third step was heated at 50°C for 30 minutes to form an intermediate solution.

[0112] In the fifth step, the reaction solution from the fourth step was further heated at 140°C for 6 hours for azeotropic distillation.

[0113] In the sixth step, 43.10 g (0.120 mol) of 4,4'-diphenylmethanebismaleimide was mixed with 130 g of methyl isobutyl ketone (MIBK) at a temperature of 115°C and allowed to stand.

[0114] In the seventh step, the intermediate solution from the fourth step was gradually added to the bismaleimide solution from the sixth step over a period of 20 minutes.

[0115] In the eighth step, the reaction solution from the seventh step was further heated at a temperature of 117°C for a period of 3.5 hours.

[0116] In the ninth step, after the reaction in the eighth step was completed, the reaction solution was filtered and concentrated to remove most of the MIBK.

[0117] In the tenth step, the solution obtained in the ninth step was further diluted with MEK to form a 63% (by weight) solution.

[0118] [Example 5] Synthesis of polymaleimide 5 The polymaleimide of formula I was prepared as described below.

[0119] In the first step, 42.12 g (0.080 mol) of retinyl palmitate and 49.86 g (0.139 mol) of 4,4'-diphenylmethanebismaleimide were dissolved in 185 g of MIBK at a temperature of 118°C for 7 hours.

[0120] In the second step, the reaction solution from the first step was filtered and concentrated to remove most of the MIBK.

[0121] In the third step, the obtained crude product was diluted with MEK to form a 62% (by weight) solution.

[0122] [Example 6] Synthesis of polymaleimide 6 The polymaleimide of formula I was prepared as described below.

[0123] In the first step, 65.68 g (0.498 mol) of cinnamaldehyde and 15.95 g (0.275 mol) of acetone were dissolved in 480 mL of ethanol at room temperature.

[0124] In the second step, 8.03 g (0.201 mol) of sodium hydroxide (NaOH) and 72 g of water were gradually added to the solution prepared in the first step. The reaction mixture was stirred at room temperature for 6 hours. Over the course of 6 hours, a large amount of yellow precipitate was gradually formed in the solution.

[0125] In the third step, 400 mL of water was added to dilute the reaction mixture from the second step.

[0126] In the fourth step, the solution from the third step was neutralized with dilute hydrochloric acid (HCl) in aqueous solution form.

[0127] In the fifth step, the solution from the fourth step was filtered. After filtration, the filter cake was washed three times with 400 mL of water.

[0128] In the sixth step, the filtered cake was baked in a vacuum oven at 100°C for 4 hours, and the crude product was 70.15 g of disinnamyrideneacetone.

[0129] In the seventh step, 28.62 g (0.100 mol) of disinnamyrideneacetone and 75.86 g (0.172 mol) of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide were dissolved in 200 mL of 1,3,5-trimethylbenzene at a temperature of 165°C for 8 hours.

[0130] In the eighth step, the reaction solution from the seventh step was cooled to a temperature below 100°C and added dropwise to 400 mL of petroleum ether to precipitate the solid product.

[0131] In the ninth step, the solid precipitated in the eighth step was pulverized by high-speed dispersion.

[0132] In the tenth step, the crushed precipitate was collected by filtration to form a filtration cake.

[0133] In the 11th step, the filtered cake was washed four times with 200 mL of petroleum ether and then baked in a vacuum oven at 100°C for 2 hours, resulting in a dry powder weighing 102.67 g.

[0134] In the 12th step, the dried powder from the 11th step was dissolved in MEK to form a 64% (by weight) solution.

[0135] [Example 7] Synthesis of polymaleimide 7 The polymaleimide of formula I was prepared as described below.

[0136] In the first step, 19.33 g (0.036 mol) of β-carotene and 44.20 g (0.100 mol) of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide were dissolved in 110 mL of xylene at a temperature of 140°C for 6 hours.

[0137] In the second step, the reaction solution from the first step was cooled to a temperature below 50°C.

[0138] In the third step, the cooled reaction solution was filtered and concentrated to form a 65-70% (by weight) solution. To reduce the viscosity of the solution, additional MEK was added to form a final 60% (by weight) solution.

[0139] The formulations of each example of the present invention discussed herein are summarized in Table 1 below.

[0140] [Table 1]

[0141] [Example 8] Laminate applications The formulations of Examples 1 to 7 of the present invention were tested for use in laminate applications.

[0142] Varnish was prepared using additional MEK according to the resin formulations listed in Table 1 (150 g of varnish composition with a solid content of 57 wt%). Approximately 150 g of varnish was poured into a tray. One piece of 2116E glass cloth (30 cm × 20 cm) was immersed in the varnish and then pulled out by hand through a pair of spaced rollers to control the thickness. One side of the prepared glass cloth was secured with a clamp and then suspended in a fume hood to spread the varnish evenly and promote solvent evaporation. The glass cloth was then fired at a high temperature for a period sufficient to remove the solvent and provide a reasonable prepreg gel time; the temperature and time could be adjusted according to the specific case. After firing, the desired prepreg was obtained.

[0143] Six pieces of the obtained prepreg were stacked, and half of the top and bottom surfaces were covered with a standard copper foil sheet. This stack was then laminated in a press at 230°C for 1.5 hours. The resulting laminate composition was then tested for the properties shown in Table 2 below.

[0144] Table 2 demonstrates the performance of the embodiments of the present invention.

[0145] [Table 2]

[0146] As shown in Table 2, all formulations of the examples of the present invention showed good performance together with the crosslinking agent TAIC. Examples 1 to 7 of the present invention each showed high performance in laminate (dynamic mechanical analysis) T g It exhibited a glass transition temperature of >200°C and a low dissipation coefficient of 0.005-0.006 at 10 GHz.

[0147] In particular, Examples 1-3 of the present invention, which have the same structure but were synthesized using different reaction solvents, showed similar laminate performance. Generally, Examples 1-3 of the present invention performed at temperatures higher than 270°C. g , D at 10GHz from 0.0050 to 0.0056 f It also had a copper peel strength of approximately 0.85 N / mm.

[0148] Referring to Example 4 of the present invention, in which a dodecyl group is incorporated into the framework, the electrolaminated board is heated to 208°C. g , 0.0049 at 10GHz D f , and it showed a copper peel strength of 0.85 N / mm. Therefore, D f Furthermore, the copper peel strength was not impaired.

[0149] Referring to Example 5 of the present invention, which is made from retinyl palmitate having a long dodecyl group, the electrolaminated board is heated to 221°C. g , 0.0062 at 10GHz D f , and it showed a copper peel strength of 0.87 N / mm. Therefore, the ester group is D f It has a negative impact on T g It appears that performance may have been compromised.

[0150] Referring to Example 6 of the present invention, which was manufactured from disinnamyrideneacetone and BMI-5100, the electrolaminated board was subjected to a high temperature of 280°C. g and a low D of 0.0053 f This was shown. However, the copper peel strength decreased to 0.68 N / mm compared to some of the other examples of the present invention.

[0151] Referring to Example 7 of the present invention, in which carotene is also incorporated into the framework, the electrolaminated board can withstand temperatures higher than 300°C. g This was shown. Furthermore, D f The copper peel strength was the same as that of Examples 1 to 3 of the present invention.

[0152] [Example 9] Evaluation of the polymaleimide formulation of the present invention As shown in Table 3 below, one comparative formulation and two formulations of the present invention were prepared.

[0153] Example 8 of the present invention was prepared from polymaleimide 2 (prepared as described in Example 2 above) and BisM cyanate ester in a weight ratio of 70.3:29.7.

[0154] Example 9 of the present invention was prepared from polymaleimide 6 (prepared as described in Example 6 above) and BisM cyanate ester in a weight ratio of 70.2:29.8.

[0155] Comparative Example 1 was prepared from BMI-5100 and BisM cyanate ester in a weight ratio of 69.4:30.6.

[0156] [Table 3]

[0157] [Example 9a] Laminate applications The comparative examples and embodiments of the present invention prepared as described in Example 9 were tested for use in laminate applications using the same procedure as described above in Example 8.

[0158] Table 4 demonstrates the improved performance of the embodiments of the present invention.

[0159] [Table 4]

[0160] As shown in Table 4, Examples 8 and 9 of the present invention have a high temperature of 268°C. g This was achieved, but this is a T of 188℃ g The copper peel strength of Examples 8 and 9 of the present invention was also higher than that of Comparative Example 1, which showed a copper peel strength of 0.65 N / mm, at 0.90 N / mm and 0.73 N / mm, respectively. Furthermore, the D of Examples 8 and 9 of the present invention f D is 0.0053 f Compared to Example 1 of the present invention, which showed the values, these values ​​increased to 0.0058 and 0.0056, respectively.

[0161] When introducing elements of this disclosure or its preferred embodiments, the articles “a,” “an,” “the,” and “said” are intended to mean that one or more of those elements exist. The terms “equip,” “include,” and “have” are intended to be inclusive and mean that additional elements other than those listed may exist.

[0162] In light of the above, it is clear that several of the objectives of this disclosure have been achieved and other favorable results have been obtained.

[0163] Various modifications may be made to the above products and methods without departing from the scope of this disclosure; therefore, all things included in the above description are intended to be illustrative and not to be construed as restrictive.

Claims

1. Equation I 【Chemistry 1】 (In the formula, X is a bond, carbonyl, methylene, C ２ ~C ２０ Alkanedyl and C ２ ~C ２０ Selected from a group consisting of alkenziels, Y is C ２ ~C ２０ Alkandiil, formula Y １ 【Chemistry 2】 The part of formula Y ２ 【Transformation 3】 the moiety of, formula Y ３ 【Chemistry 4】 The part of formula Y ４ 【Transformation 5】 The part of, and formula Y ５ 【Transformation 6】 Selected from a group consisting of parts, R １ ~R ６ Each of these is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, and alkoxy. n is an integer greater than or equal to 1. A compound of [unclear].

2. The compound according to claim 1, wherein X is an alkanediyl group having 2 to about 10 carbon atoms.

3. The compound according to claim 1, wherein X is an alkenediyl group having 2 to about 10 carbon atoms.

4. The compound according to claim 1, wherein Y is an alkanediyl group having 2 to about 10 carbon atoms.

5. R １ ~R ６ The compound according to claim 1, wherein each is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, vinyl, propenyl, butenyl, phenyl, naphthyl, methoxy, ethoxy, propoxy, and butoxy.

6. A compound according to any one of claims 1 to 5, wherein n is greater than 1.

7. A method for producing a compound according to any one of claims 1 to 6, comprising the step of reacting a polyene and a bismaleimide in a liquid reaction medium.

8. The method according to claim 7, wherein the liquid reaction medium includes an organic solvent.

9. The method according to claim 7, wherein the liquid reaction medium comprises an organic solvent selected from the group consisting of diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, 1,3,5-trimethylbenzene, xylene, and methyl isobutyl ketone.

10. The method according to claim 7, wherein the liquid reaction medium comprises diethylene glycol dimethyl ether.

11. The method according to any one of claims 7 to 10, wherein the liquid reaction medium is maintained at a temperature of at least about 110°C during the reaction.

12. The method according to claim 11, wherein the liquid reaction medium is maintained at a temperature of about 120°C to about 160°C during the reaction.

13. A curable composition, The compound according to any one of claims 1 to 6, in a concentration of at least about 20% by weight of the composition, A crosslinking component comprising at least one crosslinking agent in a concentration of about 10% to about 80% by weight of the aforementioned composition. A composition containing the following:

14. The composition according to claim 13, wherein the crosslinking component comprises at least one crosslinking agent selected from the group consisting of triallyl isocyanurate, polyene, cyanate ester, poly(p-phenylene oxide), and polybutadiene.

15. The composition according to claim 13 or 14, further comprising zinc dioctanoate in a concentration of about 0.1% to about 1% by weight of the composition.

16. A printed circuit board comprising the curable composition according to any one of claims 13 to 15.

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