Maleimide polymers for electronic laminates

Abstract

Provided herein are compounds of formula (I), wherein X is selected from the group consisting of a bond, a carbonyl group, a methylene group, a C2 to C20 alkanediyl group, and a C2 to C20 alkenediyl group; y is selected from the group consisting of a C2 to C20 alkanediyl group, a moiety of formula (Y1), a moiety of formula (Y2), a moiety of formula (Y3), a group of formula (Y4), and a moiety of formula (Y5), each of R1-R6 is independently selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, an aryl group, and an alkoxy group; and n is an integer greater than or equal to 1. The compounds exhibit good solubility, high thermal stability, and good dielectric properties, and are useful, for example, in the preparation of electronic laminate compositions.

Description

Background Technology

[0001] Bismaleimide (BMI) is a thermosetting resin that, due to its thermal stability and relatively good dielectric properties, is suitable for high-temperature applications. Therefore, BMI can be used in both industrial and consumer electronics. For example, BMI can be used in electronic laminate applications requiring high temperatures and low losses (i.e., the level of energy dissipation or attenuation that occurs when electromagnetic waves or signals pass through the material). Furthermore, BMI is less expensive than polyphenylene ethers (e.g., SA9000 from Sabic), a common component in electronic laminate applications.

[0002] Traditionally, common BMIs are used in electronic lamination processes. Common BMIs are often used as base materials for high-performance thermosetting resins. However, commercially available BMIs (such as 4,4'-diphenylmethane bismaleimide and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide) have poor solubility in ketones (i.e., typically less than 20% at 25°C) and poor viscosity build-up in the pre-curing step of electronic lamination forming processes. Therefore, the percentage of BMI in formulations is usually very small. Thus, there is a need for improved compounds and processes, including maleimide polymers with good solubility, high thermal stability, and good dielectric properties. Invention Overview

[0003] For example, this article provides a compound of formula I, Formula I in X is selected from free bonds, carbonyl groups, methylene groups, and C2 to C2 groups. 20 Alkyl and C2 to C 20 The group composed of alkenyl groups; Y selects from the following groups: C2 to C 20 Alkyl, part of formula Y1, Formula Y1 Part of formula Y2 Formula Y2 Part of formula Y3 Formula Y3 The part of formula Y4 and Formula Y4 Part of formula Y5; Y5 R 1 –R 6 Each is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, and alkoxy groups; and n is an integer greater than or equal to 1.

[0004] This document also provides a method for preparing compounds of formula I, which involves reacting a polyene with a bismaleimide in a liquid reaction medium. Preferably, the liquid reaction medium comprises an organic solvent, such as diethylene glycol dimethyl ether.

[0005] This document also provides curable compositions comprising compounds of formula I. For example, curable compositions can be used to prepare electronic laminates such as printed circuit boards. The curable compositions may further comprise one or more optional components, such as crosslinking components, free radical initiators, and crosslinking catalysts.

[0006] Printed circuit boards containing the curable resin compositions provided herein (e.g., curable resin compositions containing compounds of formula I) are also provided.

[0007] Other purposes and features will be partly obvious and partly noted below. Invention Details

[0008] This document provides compounds that can be used in electronic laminate compositions, exhibiting good solubility, high thermal stability, and good dielectric properties. For example, this document provides maleimide polymers prepared from polyolefins and BMI via a Diels-Alder reaction. Compared to prior art compositions, the compounds disclosed herein exhibit higher solubility in methyl ethyl ketone (MEK) while also providing low-loss performance characteristics suitable for use in electronic laminates.

[0009] Preferably, the compounds provided herein are fluorine-free (and more preferably, halogen-free). For example, the compounds can be used to prepare fluorine-free (and more preferably halogen-free) electronic laminate compositions. definition

[0010] As used herein, the term "alkyl" refers to a straight-chain or branched moiety containing up to about 10 carbon atoms (unless otherwise specified as a different number of carbon atoms). Non-limiting examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. An alkyl group can be a straight-chain alkyl group or a branched alkyl group (e.g., isopropyl).

[0011] As used herein, the term "aryl" refers to a moiety derived by removing a hydrogen atom from a ring carbon atom of an aromatic hydrocarbon. Non-limiting examples of aryl groups include phenyl, o-tolyl, p-tolyl, and naphthyl.

[0012] As used herein, the term "alkoxy" refers to a portion of the form ‒OR', where R' is an alkyl group as defined herein. For example, the group ‒OCH3 may be referred to herein as "methoxy". The group ‒OCH2CH3 may be referred to herein as "ethoxy". Non-limiting examples of alkoxy groups include methoxy, ethoxy, and propoxy. Alkoxy groups may comprise straight-chain alkyl groups or branched-chain alkyl groups (e.g., isopropoxy).

[0013] As used herein, the term "alkenyl" refers to a straight-chain or branched portion containing up to about 10 carbon atoms (unless otherwise specified, a different number of carbon atoms) and comprising at least one double bond between adjacent carbon atoms. Non-limiting examples of alkenyl groups include vinyl, propenyl, and butenyl.

[0014] As used herein, the term "carbonyl" refers to the part of the form ‒C(O)‒, in which the carbon atom and the oxygen atom share a double bond.

[0015] As used herein, the term "alkyldiyl" refers to a straight-chain or branched moiety having two free valences. Typically, an alkyldiyl group can be a straight-chain or branched moiety containing up to about 10 carbon atoms (unless otherwise specified, a different number of carbon atoms is specified), as described above in the general description of "alkyl". Non-limiting examples of alkyldiyl groups include ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and 2-methylpropane-1,3-diyl.

[0016] As used herein, the term "alkenyl" refers to a straight-chain or branched portion having two free valences and one or more carbon-carbon double bonds. Typically, an alkenyl group can be a straight-chain or branched group containing up to about 10 carbon atoms (unless otherwise specified, a different number of carbon atoms is specified), as described above in the general description of "alkenyl". Non-limiting examples of alkenyl groups include ethylene-1,2-diyl, prop-1-en-1,3-diyl, but-1-en-1,4-diyl, and but-2-en-1,4-diyl.

[0017] As used in this article, the term "hydrogen" includes both stable isotopes of hydrogen, namely 1 H (also known as protium) and 2 H (also known as deuterium).

[0018] As used herein, the term "polyene" refers to a polyunsaturated organic compound containing alternating carbon-carbon double and single bonds. polymaleimide compounds

[0019] This article provides a compound of formula I. Formula I in X is selected from free bonds, carbonyl groups, methylene groups, and C2 to C2 groups. 20 Alkyl and C2 to C 20 The group composed of alkenyl groups; Y selects a group consisting of the following: C2 to C 20 Alkyl, part of formula Y1, Formula Y1 Part of formula Y2 Formula Y2 Part of formula Y3 Formula Y3 The part of formula Y4 and Formula Y4 Part of formula Y5; Y5 R 1 –R 6 Each is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, and alkoxy groups; and n is an integer greater than or equal to 1.

[0020] In compounds of Formula I, X can be an alkyldiyl group. For example, X can be an alkyldiyl group having 2 to about 10 carbon atoms, such as 2 to 6 carbon atoms. Non-limiting examples of alkyldiyl groups include ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and 2-methylpropane-1,3-diyl.

[0021] In compounds of Formula I, X can be an alkyl group. For example, X can be an alkyl group having 2 to about 10 carbon atoms, such as 2 to 6 carbon atoms. Non-limiting examples of alkyl groups include ethylene-1,2-diyl, prop-1-en-1,3-diyl, but-1-en-1,4-diyl, and but-2-en-1,4-diyl.

[0022] In compounds of formula I, X can be a carbonyl group.

[0023] In compounds of formula I, Y can be an alkyldiyl group having at least about 2 carbon atoms. For example, Y can be an alkyldiyl group having about 2 to about 10 carbon atoms.

[0024] In compound I, R 1 –R 6Each 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 can be independently selected from the group consisting of hydrogen, methyl, ethyl, phenyl, and methoxy.

[0025] In the compound of formula I, n is preferably greater than 1. In various embodiments, n can be at least 10, at least 100, or at least 1000. Preparation method of polymaleimide compounds

[0026] This article also provides a method for preparing compound I. As discussed above, BMI can be used in electronic laminate applications requiring high temperature resistance and low loss. Without being bound by any specific theory, it is believed that the Diels-Alder reaction of polyolefins with BMI can improve the solubility and low-loss properties of BMI.

[0027] For example, this article provides a method for preparing compounds of formula I, which includes reacting a polyene with BMI.

[0028] Polyenes can be natural products or conjugated tetraenones derived from biological substrates. Non-limiting examples include β-carotene, α-carotene, retinyl palmitate, and dicinnamylacetone.

[0029] BMI can be any BMI. For example, a BMI can be a compound containing an alkyl or aryl linkage between two maleimide groups. Non-limiting examples of BMIs include maleimide groups containing a methylene diphenyl linkage.

[0030] The method may include reacting a polyene with BMI, wherein the molar ratio of BMI to polyene may be from 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.

[0031] The method may include reacting the polyolefin with BMI in a liquid reaction medium containing a solvent. Preferably, the liquid reaction medium contains an organic solvent.

[0032] 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.

[0033] During the reaction, the temperature of the liquid reaction medium can be maintained at at least about 110°C. For example, the temperature of the liquid reaction medium can be maintained at at least about 120°C, at least about 140°C, or at least about 150°C. The temperature of the liquid reaction medium can be maintained at no more than about 160°C, about 150°C, or about 140°C. As a non-limiting example, the temperature of the liquid reaction medium can be maintained at about 110°C to about 130°C or about 140°C to about 160°C. Curable Composition

[0034] This document also provides curable compositions comprising a compound of formula I, which may be selected and / or prepared as described in detail above. For example, curable compositions may be used to prepare electronic laminates such as printed circuit boards.

[0035] The curable composition may contain at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 100% of a compound of formula I by weight of the composition.

[0036] The curable composition may further include one or more of a crosslinking component, a free radical initiator, and a crosslinking catalyst.

[0037] Crosslinking components

[0038] Curable compositions may include 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), polyolefins, cyanates, poly(p-phenylene oxide) (PPO), and polybutadiene.

[0039] Curable compositions may include at least about 5% or at least about 10% of a crosslinking component by weight of the composition. Curable compositions typically include no more than about 40%, no more than about 30%, no more than about 20%, no more than about 10%, or no more than about 5% of a crosslinking component by weight of the composition. For example, a curable composition may include about 0% to about 40% of a crosslinking component by weight of the composition.

[0040] Initiator components

[0041] Curable compositions may include an initiator component comprising one or more free radical initiators. Unbound by any particular theory, the free radical initiator can act at elevated temperatures to release free radicals, thereby initiating crosslinking of all components in the composition.

[0042] Non-limiting examples of free radical initiators include dicumyl peroxide, di-tert-butyl peroxide, and benzoyl peroxide. For example, free radical initiators may comprise peroxide compounds.

[0043] The curable composition may contain one or more free radical initiators, for example, 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, based on the composition by weight.

[0044] Crosslinking catalyst components

[0045] In a preferred embodiment, the curable composition further comprises a crosslinking catalyst. The crosslinking catalyst catalyzes the crosslinking of the cyanate ester. Non-limiting examples of crosslinking catalysts include zinc dioctanoate (C... 16 H 30 (O4Zn). For example, the curable composition may include zinc dioctanoate in an amount of about 0.1% to about 1% by weight of the composition. Electronic laminate

[0046] Electronic laminates comprising the curable resin compositions provided herein are also provided.

[0047] For example, prepregs can be formed from reinforcing components and compositions comprising compounds of Formula I described herein (e.g., curable compositions described above). Prepregs can be obtained by contacting the reinforcing components with the matrix components through roller coating, dipping, spraying, or other such steps.

[0048] 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 fibers, E-glass fibers, C-glass fibers, R-glass fibers, S-glass fibers, T-glass fibers, and combinations thereof. Aramids are organic polymers, and examples include, but are not limited to, Kevlar®, Twaron®, and combinations thereof.

[0049] The reinforcing component can be a fabric. The fabric can be formed from the fibers discussed herein. Non-limiting examples of fabrics include sewn fabrics, woven fabrics, and combinations thereof. The fabric can be unidirectional, multidirectional, or a combination thereof. The reinforcing component can be a combination of fibers and fabric.

[0050] Once the reinforcing component has come into contact with the matrix component, the solvent can be removed by evaporation.

[0051] Volatilization can occur by exposure to temperatures of at least about 60°C. For example, volatiles 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, volatiles can occur at temperatures from about 60°C to about 250°C. As a non-limiting example, volatiles can occur at temperatures from about 100°C to about 200°C or from about 130°C to about 150°C.

[0052] Evaporation may occur for at least about 1 minute. For example, evaporation may occur for a period of at least about 2 minutes, at least about 3 minutes, or at least about 4 minutes. Evaporation may occur for a period of no more than about 30 minutes, about 25 minutes, about 20 minutes, about 15 minutes, about 10 minutes, or about 5 minutes. As a non-limiting example, evaporation may occur for a period of about 2 minutes to about 10 minutes or about 3 minutes to about 5 minutes.

[0053] During and / or after solvent evaporation, the matrix components may be partially cured. The resulting material may be referred to as a prepreg. The prepreg may be layered and / or molded before further curing. For some applications (e.g., in the production of electronic laminates), prepreg layers may alternate with conductive material layers. Non-limiting examples of conductive materials include copper foil.

[0054] Prepregs can be cured (e.g., cured more completely) to obtain a cured product. Prepregs can be cured by applying pressure (i.e., curing force) and / or heat.

[0055] A non-limiting example of a process for obtaining a more fully cured product is pressing. The prepreg can be placed in a press and subjected to curing forces for a predetermined curing time interval to obtain a more fully cured product. The curing temperature of the press can be 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 curing temperature of the press can not exceed about 250°C, about 240°C, or about 230°C. For example, the curing temperature of the press can be from about 60°C to 250°C. Non-limiting examples of the curing temperature of the press include temperatures from about 100°C to about 240°C or from about 150°C to about 230°C.

[0056] For one or more implementations, the curing temperature of the press can be increased from a lower curing temperature to a higher curing temperature within a heating time interval. Furthermore, the curing temperature can vary depending on the presence of the curing agent, the amount of the curing agent, and / or the composition of the curing agent.

[0057] filler components

[0058] In a preferred embodiment, the electronic laminate further comprises a filler component. Without being bound by any particular theory, the presence of the filler component can improve the dimensional stability, mechanical strength, and / or thermal conductivity of the composition.

[0059] Non-limiting examples of suitable filler components include spherical silica, fused silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, boron nitride, mica, talc, and mixtures thereof. In a preferred embodiment, the filler component comprises an inorganic filler. For example, the filler component may comprise silica.

[0060] Electronic laminates may include a filler component in an amount of at least 20%, about 30%, or about 40% by weight. Electronic laminates may also include a filler component in an amount not exceeding about 80%, about 70%, or about 60% by weight. For example, electronic laminates may include a filler component in an amount from about 20% to about 80% by weight. Non-limiting examples of the weight percentage of filler component in an electronic laminate composition include about 30% to about 70% or about 40% to about 60% by weight. Example

[0061] The following non-limiting examples are provided to further illustrate this disclosure.

[0062] Unless otherwise stated, the following materials are used in all the examples below.

[0063] BMI-5100 is 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, which is available from Daiwakasei Industry Co.

[0064] BMI-1000 is 4,4'-diphenylmethane bismaleimide, available from Daiwakasei Industry Co.

[0065] TAIC is triallyl isocyanurate, which is available from Sinopharm Chemical Reagent Co., Ltd.

[0066] DCP is dicumyl peroxide, which can be obtained from Sinopharm Chemical Reagent Co., Ltd.

[0067] BisM cyanate is 4,4'-[1,3-phenylenebis(1-methyl-ethylene)]bisphenyl cyanate, which is available from Yangzhou Techia Material Co., Ltd.

[0068] Example 1: Synthesis of polymaleimide 1

[0069] The polymaleimide of formula I is prepared as follows.

[0070] The first step involved dissolving 43.04 g (0.080 mol) of β-carotene in 120 g (g) of diethylene glycol dimethyl ether at 150°C.

[0071] In the second step, 20.20 g (0.117 mol) of N-phenylmaleimide was added to the mixture from the first step in stages.

[0072] The third step involves heating the reaction mixture from the second step at 150°C for 3 hours to form an intermediate solution.

[0073] Fourth, at 120°C, 57.67 g (0.161 mol) of 4,4'-diphenylmethane bismaleimide was dissolved in 120 g of diethylene glycol dimethyl ether and set aside for later use.

[0074] Fifth, over a period of 45 minutes, slowly add the intermediate solution from step three to the bismaleimide solution from step four.

[0075] The sixth step involves further heating the reaction solution from the fifth step at 150°C for 1.5 hours.

[0076] Step 7: After the reaction in step 6 is completed, add the reaction solution dropwise into 2.5 liters (L) of water to precipitate the product solid.

[0077] Step 8: After vacuum filtration, collect the filter cake. Crush the filter cake into powder and bake it in a vacuum oven at 90°C for 5 hours. The product is a dry powder weighing 120.05 g.

[0078] Step 9: Dissolve the dried product powder from step 8 in methyl ethyl ketone (MEK) to form a 64% (wt / wt) solution.

[0079] Example 2: Synthesis of polymaleimide 2

[0080] The polymaleimide of formula I is prepared as follows.

[0081] The first step involved dissolving 32.33 g (0.060 mol) of β-carotene and 20.72 g (0.120 mol) of N-phenylmaleimide in 120 g of propylene glycol monomethyl ether acetate at 145°C to form a solution.

[0082] The second step involves heating the reaction solution from the first step at 145°C for 3 hours to form an intermediate solution.

[0083] The third step involves dissolving 43.19 g (0.121 mol) of 4,4'-diphenylmethane bismaleimide in 130 g of propylene glycol monomethyl ether acetate at 145°C for later use.

[0084] Fourth, over a period of 25 minutes, slowly add the intermediate solution from step two to the bismaleimide solution from step three.

[0085] The fifth step involves further heating the reaction solution from the fourth step at 145°C for 4 hours.

[0086] Step 6: After the reaction in step 5 is completed, add the reaction solution dropwise into 1.6 L of petroleum ether to precipitate the product solid.

[0087] Step 7: After vacuum filtration, collect the filter cake and wash it twice with 200 ml of petroleum ether.

[0088] Step 8: The filter cake washed in step 7 is baked in a vacuum oven at 100°C for 2 hours. The product is a dry powder weighing 86.80 g.

[0089] Step 9: Dissolve the dried product powder from step 8 in MEK to form a 65% (wt / wt) solution.

[0090] Example 3: Synthesis of polymaleimide 3

[0091] The polymaleimide of formula I is prepared as follows.

[0092] The first step involved dissolving 32.28 g (0.060 mol) of β-carotene in 100 g of 1,3,5-trimethylbenzene at 160°C.

[0093] In the second step, 20.76 g (0.120 mol) of N-phenylmaleimide was added to the solution from the first step in stages.

[0094] The third step involves heating the reaction solution from the second step at 160°C for 2.5 hours to form an intermediate solution.

[0095] Fourth step: At 165°C, 53.08 g (0.120 mol) of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide was dissolved in 100 g of 1,3,5-trimethylbenzene and set aside for later use.

[0096] Fifth, over a period of 35 minutes, slowly add the intermediate solution from step three to the bismaleimide solution from step four.

[0097] The sixth step involves further heating the reaction solution from the fifth step at 165°C for 9 hours.

[0098] Step 7: After the reaction in step 6 is completed, add the reaction solution dropwise into 1.5 L of petroleum ether to precipitate the product solid.

[0099] Step 8: After vacuum filtration, collect the filter cake and wash it three times with 300 mL of petroleum ether.

[0100] Step 9: The filter cake washed in step 8 is baked in a vacuum oven at 100°C for 2 hours. The product is a dry powder weighing 95.20 g.

[0101] Step 10: Dissolve the dried powder from step 9 in MEK to form a 65% (wt / wt) solution.

[0102] Example 4: Synthesis of polymaleimide 4

[0103] The polymaleimide of formula I is prepared as follows.

[0104] The first step involved dissolving 32.25 g (0.060 mol) of β-carotene and 11.80 g (0.120 mol) of maleic anhydride in 160 g of xylene at 130°C.

[0105] The second step involves heating the reaction solution from the first step at 140°C for 3 hours, and then cooling it to 50°C.

[0106] In the third step, 22.15 g (0.120 mol) of 1-dodecaneamine was added to the reaction solution from the second step in stages.

[0107] The fourth step involves heating the solution from the third step at 50°C for 30 minutes to form an intermediate solution.

[0108] The fifth step involves further heating the reaction solution from the fourth step at 140°C for an azeotropic distillation period of 6 hours.

[0109] Step 6: Mix 43.10 g (0.120 mol) of 4,4'-diphenylmethane bismaleimide with 130 g of methyl isobutyl ketone (MIBK) at 115°C and set aside.

[0110] Step 7: Over a period of 20 minutes, slowly add the intermediate solution from step 4 to the bismaleimide solution from step 6.

[0111] The eighth step involves further heating the reaction solution from step seven at 117°C for 3.5 hours.

[0112] Step 9: After the reaction in step 8 is complete, filter and concentrate the reaction solution to remove most of the MIBK.

[0113] Step 10: Dilute the solution obtained in step 9 with MEK to form a 63% (wt / wt) solution.

[0114] Example 5: Synthesis of polymaleimide 5

[0115] The polymaleimide of formula I is prepared as follows.

[0116] The first step involved dissolving 42.12 g (0.080 mol) retinyl palmitate and 49.86 g (0.139 mol) 4,4'-diphenylmethane bismaleimide in 185 g MIBK at 118°C for 7 hours.

[0117] The second step is to filter and concentrate the reaction solution from the first step to remove most of the MIBK.

[0118] The third step is to dilute the obtained crude product with MEK to form a 62% (wt / wt) solution.

[0119] Example 6: Synthesis of polymaleimide 6

[0120] The polymaleimide of formula I is prepared as follows.

[0121] The first step involved dissolving 65.68 g (0.498 mol) cinnamaldehyde and 15.95 g (0.275 mol) acetone in 480 mL of ethanol at room temperature.

[0122] In the second step, a solution of 8.03 g (0.201 mol) sodium hydroxide and 72 g water was slowly added to the solution prepared in the first step. The reaction mixture was stirred at room temperature for 6 hours. During this 6-hour period, a large amount of yellow precipitate gradually formed in the solution.

[0123] Third, add 400 mL of water to dilute the reaction mixture from the second step.

[0124] The fourth step is to neutralize the solution from the third step with a dilute hydrochloric acid (HCl) aqueous solution.

[0125] Fifth, filter the solution from step four. After filtration, wash the filter cake three times with 400 mL of water.

[0126] Step 6 involves baking the filter cake in a vacuum oven at 100°C for 4 hours, yielding 70.15 g of crude product dicinnamylacetone.

[0127] Step 7: Dissolve 28.62 g (0.100 mol) of cinnamylacetone and 75.86 g (0.172 mol) of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide in 200 mL of 1,3,5-trimethylbenzene at 165°C for 8 hours.

[0128] Step 8: Cool the reaction solution from step 7 to a temperature below 100°C and add it dropwise to 400 mL of petroleum ether to precipitate the solid product.

[0129] The ninth step involves dispersing and pulverizing the solids precipitated in the eighth step using a high-speed dispersion process.

[0130] The tenth step is to collect the crushed precipitate by filtration to form a filter cake.

[0131] Step 11: The filter cake was washed four times with 200 mL of petroleum ether and baked in a vacuum oven at 100°C for 2 hours. The product was a dry powder weighing 102.67 g.

[0132] Step 12: Dissolve the dried powder from step 11 in MEK to form a 64% (wt / wt) solution.

[0133] Example 7: Synthesis of polymaleimide 7

[0134] The polymaleimide of formula I is prepared as follows.

[0135] The first step involved dissolving 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'-diphenylmethane bismaleimide in 110 mL of xylene at 140°C for 6 hours.

[0136] The second step is to cool the reaction solution from the first step to a temperature below 50°C.

[0137] The third step involves filtering and concentrating the cooled reaction solution to form a 65-70% (wt / wt) solution. To reduce the solution viscosity, additional MEK is added to form a final 60% (wt / wt) solution.

[0138] The formulations of the various invention examples discussed in this article are summarized in Table 1 below. Table 1

[0139] Example 8: Laminate Application

[0140] Laminate application tests were conducted on the formulations of Examples 1-7 of the invention.

[0141] The varnish was prepared according to the resin formulation described in Table 1, with MEK added (150 g of varnish composition, solids content 57 wt.%). Approximately 150 g of varnish was poured into a tray. A sheet of 2116 E-glass cloth (30 cm × 20 cm) was immersed in the varnish and then manually pulled through a pair of gapped rollers to control the thickness. One side of the prepared glass cloth was secured with a clip, and the cloth was then suspended in a fume hood to allow the varnish to spread evenly and promote solvent evaporation. The glass cloth was then baked at an elevated temperature for a sufficient period of time to remove the solvent and produce a reasonable prepreg gel time; therefore, the temperature and time can be adjusted according to specific circumstances. After baking, the desired prepreg was obtained.

[0142] Six sheets of the obtained prepreg were stacked together, and half of the top and bottom surfaces were covered with standard copper foil. The stack was then laminated in a press at 230°C for 1.5 hours. The resulting laminate composition was then tested for performance, as shown in Table 2 below.

[0143] Table 2 shows the performance of the invention examples. Table 2

[0144] As shown in Table 2, all formulations in the invention examples exhibit good performance with the crosslinking agent TAIC. Each of the invention examples 1-7 demonstrates high-layer pressure plate (dynamic mechanical analysis) T g (Glass transition temperature) (> 200°C) and low (dissipation factor) (0.005~0.006) at 10 GHz.

[0145] Specifically, Examples 1-3 of the invention contain the same structure but are synthesized using different reaction solvents, exhibiting similar lamination properties. Overall, Examples 1-3 of the invention have similar T... g Above 270°C, D at 10 GHz f The values ​​range from 0.0050 to 0.0056, and the copper peel strength is approximately 0.85 N / mm.

[0146] Referring to Example 4 of the invention, a dodecyl group is incorporated into the backbone, and the electronic laminate exhibits a T0 of 208°C. g D at 10GHz is 0.0049 f And a copper peel strength of 0.85 N / mm. Therefore, D f The copper peel strength was not compromised.

[0147] Referring to Example 5 of the invention, it is made of retinyl palmitate having a long dodecyl group, and the electronic laminate exhibits T gD at 221°C and 10 GHz f The coefficient of performance (COP) is 0.0062, and the copper peel strength is 0.87 N / mm. Therefore, the ester group appears to be associated with D... f It has had a negative impact and may have already damaged T. g performance.

[0148] Referring to Example 6 of the invention, it is made of dicinnamyl acetone and BMI-5100, and the electronic laminate exhibits a high T of 280°C. g And a low D of 0.0053 f However, compared to some other invention examples, the copper peel strength decreased to 0.68 N / mm.

[0149] Referring to Invention Example 7, this example also incorporates carotene into the framework, and the electronic laminate exhibits a T... g Above 300°C. Furthermore, its D... f The copper peel strength is similar to that of Examples 1-3 of the Invention.

[0150] Example 9: Evaluation of the polymaleimide formulation of the present invention

[0151] A comparative formulation and two inventive formulations were prepared as described in Table 3 below.

[0152] Example 8 of the invention is made of polymaleimide 2 (prepared as described in Example 2 above) and BisM cyanate in a weight ratio of 70.3:29.7.

[0153] Invention Example 9 is made of polymaleimide 6 (prepared as described in Example 6 above) and BisM cyanate in a weight ratio of 70.2:29.8.

[0154] Comparative Example 1 was prepared from BMI-5100 and BisM cyanate in a weight ratio of 69.4:30.6. Table 3

[0155] Example 9a: Laminate Application

[0156] The comparative and inventive examples prepared according to Example 9 were tested for their use in laminate applications using the same procedures as described in Example 8 above.

[0157] Table 4 illustrates the performance improvements achieved through examples of the invention. Table 4

[0158] As shown in Table 4, Invention Examples 8 and 9 achieved a high T of 268°C. g It is much higher than the T shown in Comparative Example 1. g(188°C). Furthermore, compared to the copper peel strength of 0.65 N / mm shown in Comparative Example 1, the copper peel strengths of Examples 8 and 9 are also higher, at 0.90 N / mm and 0.73 N / mm, respectively. Additionally, compared to the D shown in Example 1... f (0.0053) compared to D in Invention Examples 8 and 9 f They were increased to 0.0058 and 0.0056 respectively.

[0159] When describing elements of this disclosure or its preferred embodiments, the articles “a,” “an,” “the,” and “said” are intended to indicate the presence of one or more of that element. The terms “comprising,” “including,” and “having” are intended to be inclusive and indicate that there may be other elements besides those listed.

[0160] In view of the foregoing, it can be seen that several objectives of this disclosure have been achieved and other favorable results have been obtained.

[0161] Since various changes can be made to the products and methods described above without departing from the scope of this disclosure, it is intended that all content contained in the above description be interpreted as illustrative rather than restrictive.

Claims

1. A compound of formula I, in X is selected from free bonds, carbonyl groups, methylene groups, and C2 to C2 groups. 20 Alkyl and C2 to C 20 The group composed of alkenyl groups; Y selects a group consisting of the following: C2 to C 20 Alkyl, part of formula Y1, Formula Y1 Part of formula Y2 Formula Y2 Part of formula Y3 Formula Y3 The part of formula Y4 and Formula Y4 Part of formula Y5; Y5 R 1 –R 6 Each is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, and alkoxy groups; and n is an integer greater than or equal to 1.

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

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

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

5. The compound according to claim 1, wherein, R 1 –R 6 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. The compound according to any one of claims 1 to 5, wherein n is greater than 1.

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

8. The method according to claim 7, wherein the liquid reaction medium comprises 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 of 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 temperature of the liquid reaction medium is maintained at at least about 110°C during the reaction.

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

13. A curable composition comprising: The compound of any one of claims 1 to 6, wherein the concentration is at least about 20% by weight of the composition; and The crosslinking component comprises at least one crosslinking agent, the concentration of which is from about 10% to about 80% by weight of the composition.

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, poly(p-phenylene oxide), and polybutadiene.

15. The composition according to claim 13 or 14, further comprising zinc dioctanoate, said zinc dioctanoate having 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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