CN113045897B - Bismaleimide resin composition, preparation method of composition, cured product and application of cured product - Google Patents

Bismaleimide resin composition, preparation method of composition, cured product and application of cured product Download PDF

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CN113045897B
CN113045897B CN202110284377.4A CN202110284377A CN113045897B CN 113045897 B CN113045897 B CN 113045897B CN 202110284377 A CN202110284377 A CN 202110284377A CN 113045897 B CN113045897 B CN 113045897B
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bismaleimide resin
bis
allyloxy
resin composition
bismaleimide
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CN113045897A (en
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魏玮
张子龙
李小杰
刘晓亚
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Jiangnan University
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    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a bismaleimide resin composition, a preparation method of the bismaleimide resin composition, a cured product and application of the cured product, and belongs to the technical field of modification of bismaleimide resin. The bismaleimide resin composition consists of bismaleimide resin and a modifier, wherein the modifier is resveratrol derivative 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene. The modifier is derived from a bio-based raw material, reduces the dependence on petroleum-based compounds, and has the advantages of greenness and reproducibility; meanwhile, the bismaleimide resin composition disclosed by the invention has higher glass transition temperature, good flame retardant property and mechanical property after being cured, and has good application prospects in the fields of aerospace, composite materials, high-temperature-resistant adhesives, copper-clad plates, third-generation semiconductor packaging materials and the like.

Description

Bismaleimide resin composition, preparation method of composition, cured product and application of cured product
The technical field is as follows:
the invention relates to the technical field of bismaleimide resin modification, in particular to a bismaleimide resin composition with high glass transition temperature, good flame retardant property and good mechanical property.
Background art:
bismaleimide (BMI) resins, as a typical high performance thermosetting resin, are resin systems derived from polyimide resins, are bifunctional compounds with a maleimide ring as an active group at a terminal group, and usually further comprise a plurality of aryl moieties to enhance the performance of cured products thereof. The highly crosslinked network structure of the BMI resin cured product imparts high heat resistance, excellent mechanical properties, and the like, and thus is widely used as a matrix material in the fields of aerospace, electrical insulation, electronic information, and the like. However, the cross-linking density of the product of the unmodified bismaleimide resin after curing is very high, so that the material has the defects of large brittleness and poor toughness, and the bismaleimide resin monomer has the defects of high melting point, narrow processing window and the like, so that the application of the bismaleimide resin monomer is greatly limited. Therefore, the modification of BMI resin becomes one of the main research directions for preparing high-performance bismaleimide resin materials.
In academic research and industrial application, modification of bismaleimide is mostly around the combination of allyl compound and BMI, wherein the BMI resin system is modified with 2,2' -Diallyl Bisphenol A (DBA) with the most success, linear chain extension is provided by alkene reaction, and then Diels-Alder reaction is carried out at high temperature. This chain extension forms a tougher network with minimal reduction in thermal properties. Compared with an aromatic amine DDM/BMI system, the DBA/BMI system has excellent toughness and ensures the thermal property and the processability. However, in the industrial synthesis of DBA, petroleum-based bisphenol A is used as a raw material to generate allyl etherification, and then Claisen rearrangement occurs at high temperature, so that the production of DBA is very dependent on petroleum resources and is not suitable for the concept of green sustainable development of society; and studies have shown that bisphenol a, an estrogen-like structure, may predispose the body to disease, reduce fertility and cause various cancers. Therefore, in order to meet the requirements of regeneration, low toxicity, energy conservation, environmental protection and sustainable development, the synthetic bio-based polyallyl compound replaces the traditional DBA to modify BMI, and finally, the high-performance thermosetting resin is very necessary to be prepared.
In addition, in the fields of aerospace, electricity, communications, and the like, there is an increasing demand for high-performance thermosetting resins having high temperature resistance and excellent flame retardancy. Therefore, the development of a green, flame-retardant and high-glass-transition-temperature bismaleimide resin system has important research significance and value.
The invention content is as follows:
the invention provides a bismaleimide resin composition, a preparation method of the composition, a cured product and application of the cured product, and aims to overcome the defects in the prior art, and particularly provides the bismaleimide resin composition taking a polyallyl compound of bio-based molecular Resveratrol (RES) as a modifier, and further provides the preparation method and the application of the polyallyl compound of the bio-based molecular Resveratrol (RES). The bismaleimide resin composition disclosed by the invention has high glass transition temperature, good flame retardant property and mechanical property after being cured.
As one aspect of the present invention, there is provided a bismaleimide resin composition comprising a bismaleimide resin and a modifier, the modifier being a resveratrol derivative 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene (ARE) having a structure represented by the following formula (1);
Figure BDA0002979831400000021
further, the bismaleimide resin at least contains two maleimide groups, and the bismaleimide resin comprises one of the chemical structures shown in the following formulas (2) and (3):
Figure BDA0002979831400000022
r in the formula (2)1Is an organic group having 1 to 30 carbon atoms and containing an aromatic ring structure, R1Containing one or more oxygen, nitrogen, sulfur, phosphorus or halogen atoms;
Figure BDA0002979831400000023
r in different positions in formula (3)2Each independently is any one of a hydrogen atom, a hydrocarbon group containing 1 to 4 carbon atoms or a halogen atom; n is an integer of 0 to 5.
Further, the bismaleimide resin may be 4,4' -methylenebis (N-phenylmaleimide), an oligomer of phenylmethaneimide, N ' -m-phenylenebismaleimide, N ' -m-xylylenebismaleimide, N ' -p-xylylenebismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, bis (3-ethyl-5-methyl-4-maleimidobenzene) methane, N- (4-methyl-1, 3-phenylene) bismaleimide, 4' -diphenylether bismaleimide, 4' -diphenylsulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, N ' -p-xylylene bismaleimide, N ' -bis (4-methyl-1, 3-phenylene) bismaleimide, N-bis (4-methyl-1, 3-phenylene) bismaleimide, 4' -diphenylether bismaleimide, 4' -diphenylsulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, N ' -p-xylylene bismaleimide, N ' -maleimidophenoxy, N, or N, P, N, S, P, or N, S, or N, S, or N, S, or N, S, or N, each being a bis (3, each being a mixture of a monomer, S, each of a monomer, S, a monomer, a, 1, 3-bis (4-maleimidophenoxy) benzene, N ' -p-benzophenone maleimide, N ' - (methylene-bistetrahydrophenyl) bismaleimide, N ' - (3,3' -dichloro) -4,4' -diphenylmethane bismaleimide, N ' -tolidine bismaleimide, N ' -isophorone bismaleimide, N ' -p, p ' -diphenyldimethylsilyl bismaleimide, N ' -naphthalene bismaleimide, N ' -4,4' - (1,1' -diphenyl-cyclohexane) bismaleimide, N ' -3,5- (1,2, 4-triazole) bismaleimide, N ' -bis (4-methyl) maleimide), N ' -bis (2, 4-triazole) bismaleimide, N ' -bis (4-methyl-bis (p-methyl) maleimide), N ' -bis (3, N ' -bis (4-methyl-phenyl) bismaleimide), N ' -bis (4-bis (1,2, 4-triazole) bismaleimide, N ' -bis (4-bis) maleimide), N ' -isophorone bismaleimide, N ' -bis (2-bis (4-bis (maleimide), N-bis (2-bis) bismaleimide), N-bis (1, N-bis (2-bis (1-bis) maleimide), N-bis (1, 4-bis (2-bis) maleimide), N-bis (2-bis (1, 4-bis) maleimide), bis (1, 4-bis (2-bis) maleimide), bis (1-bis (2-bis) bismaleimide), or (1-bis (2-bis) bismaleimide), bis (2-bis (2) maleimide), bis (2) bismaleimide), or (2) bismaleimide), bis (2) bismaleimide), or (2-bis (2) imide), or (2) bis (2) imide) bis (2) imide) bis (2-bis (2) imide) bis (2, 4) bis (2-bis (2) imide) bis (2) imide, 4) bis (2) imide) bis (2, 4) or (2) bis (2) or (2) bis (2) or (2) bis (2) or (2) bis (2) or (2), N, N ' -pyridine-2, 6-diylbismaleimide, N ' -maleimide of 4,4' -diamino-triphenyl phosphate, 2-bis [ 3-chloro-4-maleimidophenoxy ] phenyl ] propane, 2-bis [ 3-methoxy-4- (4-maleimidophenoxy) phenyl ] propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane, or a combination of two or more thereof, but the present invention is not limited to the above exemplified ranges; the bismaleimide resin of the present invention is preferably used in combination with one or more of N, N '-4,4' -diphenylmethane bismaleimide, an oligomer of phenylmethaneimide, N '-m-phenylenebismaleimide, NN' -m-xylylenebismaleimide, N '-p-xylylenebismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane and bis (3-ethyl-5-methyl-4-maleimidobenzene) methane.
Further, the molar ratio of maleimide groups of the bismaleimide resin to allyl double bonds of the modifier is 1: 0.2-1: 1.
As a second aspect of the present invention, there is provided a method for preparing the bismaleimide resin composition, comprising the steps of:
(1) preparation of the modifier: under the protection of inert gas, taking resveratrol and an acid-binding agent, stirring and mixing in an organic solvent, then dropwise adding allyl halohydrocarbon, and performing nucleophilic substitution reaction on the allyl halohydrocarbon and the resveratrol to prepare 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene;
(2) preparation of the composition: and (2) mixing the bismaleimide resin and the 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene obtained in the step (1) to obtain the bismaleimide resin composition.
Further, the acid binding agent comprises one of triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate, sodium hydroxide, calcium hydroxide, potassium hydroxide, iron hydroxide, calcium carbonate, cesium carbonate, sodium phosphate and sodium acetate or any combination thereof.
Further, the allyl halohydrocarbon includes one of allyl iodide, allyl chloride, allyl bromide, and allyl fluoride, or any combination thereof.
Further, the organic solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, ethanol, propanol, acetone and 2-butanone.
Further, the molar ratio of the resveratrol to the acid-binding agent to the allyl halogenated hydrocarbon in the step (1) is 1: 3-6; the temperature of the nucleophilic substitution reaction is 40-200 ℃, and the reaction time is 4-48 h.
In a third aspect of the present invention, there is provided a cured product obtained by curing the bismaleimide resin composition.
The invention provides an application of a cured product, wherein the cured product has high glass transition temperature, good flame retardant property and mechanical property, and can be applied to the fields of aerospace, composite materials, high-temperature-resistant adhesives, copper-clad plates, third-generation semiconductor packaging materials and the like.
Has the advantages that: compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention utilizes 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene as a bismaleimide resin modifier, which contains a stilbene structure, wherein the benzene ring is in a large conjugated system, the structure is difficult to damage, the bismaleimide resin modifier has three crosslinking reaction sites, and the crosslinking density of a formed cured material network is higher, so that the heat resistance of the resin and the rigidity of the material can be greatly improved, the flame retardant property of the material is improved, and the bismaleimide resin obtained by modification has high glass transition temperature, good flame retardant property and mechanical property, can be widely applied to the fields of aerospace, composite materials, high temperature resistant adhesives, copper clad plates, third-generation semiconductor packaging materials and the like, and has wide application prospect.
2. The modifier 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene synthesized by the method is a target product synthesized by a one-step method through the nucleophilic substitution reaction of resveratrol and allyl halohydrocarbon, and has the advantages of few synthesis steps, simple process and contribution to industrial generation and large-scale preparation; meanwhile, the modifier is mainly prepared from resveratrol which is a bio-based raw material, reduces the dependence on petroleum-based compounds and has the advantages of greenness and reproducibility.
Drawings
FIG. 1 is a schematic diagram of a synthetic route for the preparation of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene according to the present invention;
FIG. 2 is a Fourier transform infrared spectrum of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene obtained in example 1 of the present invention;
FIG. 4 is a graph showing the results of comparing storage modulus-temperature curves of modified bismaleimide resins provided in examples 1 to 3 of the present invention and comparative examples 1 to 3;
FIG. 5 is a graph showing the results of comparing the loss factor-temperature curves of the modified bismaleimide resins provided in examples 1 to 3 of the present invention and comparative examples 1 to 3;
FIG. 6 is a graph showing the results of comparing the residual mass-temperature curves of the modified bismaleimide resins provided in examples 1 to 3 of the present invention and comparative examples 1 to 3;
FIG. 7 is a graph showing the comparative results of limiting oxygen index of the modified bismaleimide resins provided in examples 1 to 3 of the present invention and comparative examples 1 to 3;
FIG. 8 is a graph showing the results of comparison of the flexural strengths of the modified bismaleimide resins provided in examples 1 to 3 of the present invention and comparative examples 1 to 3.
Detailed Description
The present invention will be further illustrated by the following preferred examples, which are carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally carried out according to conventional conditions or according to conditions suggested by manufacturers.
Example 1
(1) Preparation of modifier 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene
In this embodiment, the acid-binding agent is potassium carbonate, the solvent is N, N-dimethylformamide, and the allyl halogenated hydrocarbon is allyl bromide, i.e., bromopropene. Referring to the attached figure 1, the reaction principle diagram of the synthesis of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene according to the technical scheme of the invention is shown. The process steps provided according to the attached figure 1 are as follows:
under the protection of nitrogen, 114.1g of resveratrol is dissolved in 50mL of N, N-dimethylformamide, 70g of anhydrous potassium carbonate is added into the solution, the obtained mixture is stirred for 1h, and then 211.7g of bromopropylene is dripped into the reaction system within 2h by using a syringe pump at 50 ℃. After the addition was complete, the reaction mixture was allowed to continue at 80 ℃ under nitrogen for 12 h. After the reaction is finished, carrying out rotary evaporation concentration on the reaction mixture at 50 ℃, dropwise adding the liquid obtained by concentration into deionized water, stirring and dispersing, then extracting with chloroform, carrying out rotary evaporation concentration on the extracted organic layer, washing the obtained concentrated product with the deionized water for 3-5 times, adding anhydrous magnesium sulfate, and carrying out vacuum drying at 50 ℃ overnight to obtain the target product 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene.
The Fourier infrared spectrum and nuclear magnetic resonance hydrogen spectrum of the 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene prepared in the example are shown in the attached figures 2 and 3 respectively.
FIG. 2 is a Fourier transform infrared spectrum of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene prepared in this example, and a Fourier transform infrared spectrum of Resveratrol (RES) and 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene (ARE) is shown in FIG. 2, 3196cm-1The absorption peak of (A) is ascribed to the phenolic hydroxyl group of RESWhen the stretching was vibrated, it was observed that the phenolic hydroxyl group completely disappeared after the reaction. And at 1240cm-1The peak of stretching vibration of aromatic ether bond is appeared at 2919cm-1A stretching vibration peak attributed to the methylene group on the ARE appeared. The above characteristic absorption peaks demonstrate the successful synthesis of ARE.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE and resveratrol RES obtained in this example, in the nuclear magnetic resonance image of ARE, the characteristic peaks at Hh, Hi, He and Hd ARE attributed to protons on two benzene rings of ARE, and the characteristic peak of double bond is found to be shifted to Hg and Hf due to strong conjugation with two benzene rings. In addition, characteristic absorption peaks attributed to allyl protons were observed at Hb, Ha, and Hc; in nuclear magnetic images of RES, characteristic peaks of Hh and Ha are attributed to protons on phenolic hydroxyl groups on resveratrol RES, Hf, Hg, Hb, and Hc are attributed to hydrogen protons on RES benzene rings, and Hd and He are attributed to double bond proton characteristic peaks connecting two benzene rings. Characteristic peaks at 9.57 and 9.24ppm were assigned to the H proton on the phenolic hydroxyl group on resveratrol RES, and in the nmr hydrogen spectrum of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE, the characteristic peak of the phenolic hydroxyl group H proton disappeared completely. And H proton characteristic peaks ascribed to the ARE allyl groups appear at 6.06, 5.43, 5.30, and 4.54ppm, and since the phenolic hydroxyl group is converted to an allyl ether bond, so that the characteristic peaks of all protons on the benzene ring shift to higher wavenumbers, the double bond farthest from the allyl ether bond finally obtains the smallest chemical shift change, which indicates that the ARE synthesized successfully.
As shown in the attached figures 2 and 3, the embodiment of the invention successfully synthesizes the bio-based allyl etherate 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene.
(2) Bismaleimide resin composition and preparation of cured product thereof
Blending according to the molar ratio of maleimide group to allyl double bond of 1:1, namely, melting and mixing 134.4g of N, N '-4,4' -diphenylmethane Bismaleimide (BMI) and 87.08g of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene (ARE) uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for defoaming for 30min, pouring the prepolymer into a preheated mold, and defoaming for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition. The storage modulus-temperature curve, the loss factor-temperature curve, the residual mass-temperature curve, the limiting oxygen index and the bending strength are shown in attached figures 4, 5, 6, 7 and 8 respectively.
Comparative example 1 preparation of a, 2,2' -diallylbisphenol a modified bismaleimide resin:
blending according to the molar ratio of maleimide group to allyl double bond of 1:1, melting and mixing 134.4g of N, N ' -4,4' -diphenylmethane Bismaleimide (BMI) and 115.7g of 2,2' -Diallyl Bisphenol A (DBA) uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition. The storage modulus-temperature curve, the loss factor-temperature curve, the residual mass-temperature curve, the limiting oxygen index and the bending strength are shown in attached figures 4, 5, 6, 7 and 8 respectively.
Example 2
(1) Preparation of modifier 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene:
the same as in example 1.
(2) Bismaleimide resin composition and preparation of cured product thereof
Blending according to the molar ratio of maleimide group to allyl double bond of 1:0.8, melting and mixing 134.4g of N, N '-4,4' -diphenylmethane bismaleimide BMI and 69.75g of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for defoaming for 30min, pouring the prepolymer into a preheated mold, and defoaming for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition. The storage modulus-temperature curve, the loss factor-temperature curve, the residual mass-temperature curve, the limiting oxygen index and the bending strength are shown in attached figures 4, 5, 6, 7 and 8 respectively.
Comparative example 2 preparation of 2,2, 2' -diallylbisphenol a modified bismaleimide resin:
blending according to the molar ratio of maleimide group to allyl double bond of 1:0.8, melting and uniformly mixing 134.4g of N, N ' -4,4' -diphenylmethane Bismaleimide (BMI) and 92.48g of 2,2' -Diallyl Bisphenol A (DBA) at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition. The storage modulus-temperature curve, the loss factor-temperature curve, the residual mass-temperature curve, the limiting oxygen index and the bending strength are shown in attached figures 4, 5, 6, 7 and 8 respectively.
Example 3
(1) Preparation of modifier 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene
The same as in example 1.
(2) Bismaleimide resin composition and preparation of cured product thereof
Blending according to the molar ratio of maleimide group to allyl double bond of 1:0.6, melting and mixing 134.4g of N, N '-4,4' -diphenylmethane bismaleimide BMI and 52.2g of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for defoaming for 30min, pouring the prepolymer into a preheated mold, and defoaming for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition. The storage modulus-temperature curve, the loss factor-temperature curve, the residual mass-temperature curve, the limiting oxygen index and the bending strength are shown in attached figures 4, 5, 6, 7 and 8 respectively.
Comparative example 3 preparation of 2,2' -diallylbisphenol a modified bismaleimide resin:
blending according to the molar ratio of maleimide group to allyl double bond of 1:0.6, melting and mixing 134.4g of N, N ' -4,4' -diphenylmethane Bismaleimide (BMI) and 69.36g of 2,2' -Diallyl Bisphenol A (DBA) uniformly at 140 ℃, placing in a vacuum drying oven at 120 ℃ for defoaming for 30min, pouring the prepolymer into a preheated mold, and defoaming for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition. The storage modulus-temperature curve, the loss factor-temperature curve, the residual mass-temperature curve, the limiting oxygen index and the bending strength are shown in attached figures 4, 5, 6, 7 and 8 respectively.
Example analysis of results:
FIG. 4 is a graph showing the comparison of the storage modulus-temperature curves of the modified bismaleimide resins prepared in examples 1 to 3 and comparative examples 1 to 3 of the present invention. It can be seen from the figure that the storage modulus of the modified bismaleimide resin cured products based on the bio-based resveratrol provided in examples 1 to 3 of the present invention is significantly improved compared to the storage modulus (at 300 ℃) of the 2,2' -diallyl bisphenol a modified bismaleimide resin cured products prepared in comparative examples 1 to 3, the storage modulus of examples 1 to 3 is 2296.7MPa or more, and is improved by at least 880.5MPa compared to comparative examples 1 to 3, because 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene has three crosslinking reaction sites, and the network crosslinking density of the cured products formed is higher, and the cured products have higher rigidity.
FIG. 5 is a graph showing the results of comparing the loss factor-temperature curves of the modified bismaleimide resins prepared in examples 1 to 3 and comparative examples 1 to 3 of the present invention. It can be seen from the figure that the glass transition temperatures of the cured bismaleimide resins modified by the resveratrol modifier provided in examples 1 to 3 of the present invention are significantly higher than those of the 2,2' -diallylbisphenol a modified bismaleimide resins prepared in comparative examples 1 to 3, wherein the glass transition temperatures of examples 1 to 3 are all as high as 378.7 ℃, and are at least 44.5 ℃ higher than those of the bismaleimide resins prepared in comparative examples 1 to 3, because 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene has three crosslinking reaction sites, which results in high rigidity and crosslinking density of the cured products and difficulty in transferring polymer segments. And the glass transition temperature of example 3 is presumed to be higher than 400 c in fig. 5.
FIG. 6 is a graph showing the comparative results of the residual mass-temperature curves of the modified bismaleimide resins provided in examples 1 to 3 of the present invention and comparative examples 1 to 3. As can be seen from the graphs, the initial decomposition temperature (T) of the cured bismaleimide resin modified by the resveratrol modifier provided in examples 1 to 3 of the present inventiond5％) Equivalent to the bismaleimide resin prepared in comparative examples 1-3; however, the bismaleimide resins prepared in examples 1 to 3 had a residual carbon ratio (. gamma.) at 800 ℃800℃) The total content of the bismaleimide resin is up to 48.4%, which is at least 13.7% higher than that of the bismaleimide resin prepared in comparative examples 1-3, because the stilbene structure in the 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene enables two benzene rings to be in a large conjugated system, the structure is difficult to damage, and the carbon residue rate is improved.
Meanwhile, as shown in fig. 7, the numerical values of the limiting oxygen indexes of the cured bismaleimide resins based on resveratrol modification provided in examples 1 to 3 of the present invention are improved compared with those of the bismaleimide resins prepared in comparative examples 1 to 3, wherein the limiting oxygen indexes of examples 1 to 3 are as high as 36%, and are improved by at least 8% compared with those of comparative examples 1 to 3. The limit oxygen index is generally in a positive correlation with the carbon residue rate, and the increase of the carbon residue rate also indicates that the cured bismaleimide resin modified based on the resveratrol modifier provided by the embodiment has better flame retardance.
FIG. 8 is a graph showing the results of comparison of the flexural strength of the modified bismaleimide resins of examples 1 to 3 of the present invention and comparative examples 1 to 3. As can be seen from the figure, the cured bismaleimide resin modified by the resveratrol modifier provided in examples 1-3 of the invention has improved bending strength compared to the bismaleimide resin prepared in comparative examples 1-3, wherein the bending strength of examples 1-3 is improved compared to the bending strength of comparative examples 1-3, and is improved by at least 15.1 MPa. The reason is that the crosslinking density of the cured bismaleimide resin modified by the resveratrol modifier is higher, so that the strength is greatly improved.
The analysis shows that the bismaleimide resin modified by the resveratrol modifier has high glass transition temperature, good flame retardant property and mechanical property. The high-temperature-resistant adhesive can be widely applied to the fields of aerospace, composite materials, high-temperature-resistant adhesives, copper-clad plates, third-generation semiconductor packaging materials and the like, and has wide application prospects.
Example 4
(1) Preparation of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene
The same as in example 1.
(2) Bismaleimide resin composition and preparation of cured product thereof
Blending according to the molar ratio of maleimide group to allyl double bond of 1:0.4, melting and mixing 134.4g of N, N '-4,4' -diphenylmethane bismaleimide BMI and 69.75g of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for defoaming for 30min, pouring the prepolymer into a preheated mold, and defoaming for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition.
Comparative example 4 preparation of diallyl bisphenol a modified bismaleimide resin:
blending according to the molar ratio of maleimide group to allyl double bond of 1:0.4, melting and mixing 134.4g of N, N ' -4,4' -diphenylmethane Bismaleimide (BMI) and 92.48g of 2,2' -Diallyl Bisphenol A (DBA) uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the diallyl bisphenol A modified bismaleimide resin.
Example 5
(1) Preparation of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene
The same as in example 1.
(2) Bismaleimide resin composition and preparation of cured product thereof
Blending according to the molar ratio of maleimide group to allyl double bond of 1:1, melting and mixing 165.9g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70 and 87.08g of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for defoaming for 30min, pouring the prepolymer into a preheated mold, and defoaming for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition.
Comparative example 5 preparation of diallyl bisphenol a modified bismaleimide resin:
blending according to the molar ratio of maleimide groups to allyl double bonds of 1:1, melting and uniformly mixing 132.7g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70 and 92.48g of 2,2' -Diallyl Bisphenol A (DBA) at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the diallyl bisphenol A modified bismaleimide resin.
Example 6
(1) Preparation of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene
The same as in example 1.
(2) Bismaleimide resin composition and preparation of cured product thereof
Blending according to the molar ratio of maleimide group to allyl double bond of 1:0.8, melting and mixing 165.9g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70 and 69.67g of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition.
Comparative example 6 preparation of diallyl bisphenol a modified bismaleimide resin:
blending according to the molar ratio of maleimide group to allyl double bond of 1:0.8, melting and uniformly mixing 132.7g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70 and 73.98g of 2,2' -Diallyl Bisphenol A (DBA) at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the diallyl bisphenol A modified bismaleimide resin.
Example 7
(1) Preparation of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene
The same as in example 1.
(2) Bismaleimide resin composition and preparation of cured product thereof
Blending according to the molar ratio of maleimide group to allyl double bond of 1:0.6, melting and mixing 165.9g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70 and 52.24g of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition.
Comparative example 7 preparation of diallyl bisphenol a modified bismaleimide resin:
blending according to the molar ratio of maleimide group to allyl double bond of 1:0.6, melting and uniformly mixing 132.7g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70 and 55.49g of 2,2' -Diallyl Bisphenol A (DBA) at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the diallyl bisphenol A modified bismaleimide resin.
Example 8
(1) Preparation of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene
The same as in example 1.
(2) Bismaleimide resin composition and preparation of cured product thereof
Blending according to the molar ratio of maleimide group to allyl double bond of 1:0.4, melting and mixing 165.9g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70 and 34.83g of 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene ARE uniformly at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the bismaleimide resin composition.
Comparative example 8 preparation of diallyl bisphenol a modified bismaleimide resin:
blending according to the molar ratio of maleimide group to allyl double bond of 1:0.4, melting and uniformly mixing 132.7g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70 and 36.99g of 2,2' -Diallyl Bisphenol A (DBA) at 140 ℃, placing the mixture in a vacuum drying oven at 120 ℃ for deaeration for 30min, pouring the prepolymer into a preheated mold, and deaerating for 30 min. Curing according to the curing and post-curing procedures of 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h and 240 ℃/4h to obtain the cured product of the diallyl bisphenol A modified bismaleimide resin.
Examples 4-8 analysis of results:
example 4 and comparative example 4 the same results as in examples 1 to 3 and comparative examples 1 to 3 were obtained, namely that bismaleimide resins modified based on a resveratrol modifier had higher glass transition temperatures, good flame retardant properties and mechanical properties compared to the use of 2,2' -diallyl bisphenol a (dba) as modifier.
Examples 5 to 8 and comparative examples 5 to 8 are experimental modes in which, in addition to examples 1 to 3 and comparative examples 1 to 3, N '-4,4' -diphenylmethane bismaleimide BMI was replaced with bis (3-ethyl-5-methyl-4-maleimidophenyl) methane BMI-70, in order to verify the applicability of the modifier to which the present invention is applied to the modification action of different bismaleimide resins. The results show that examples 5-8 and comparative examples 5-8 also obtained the same results as examples 1-3 and comparative examples 1-3, namely that the bismaleimide resin modified based on the resveratrol modifier has higher glass transition temperature, good flame retardant property and mechanical property compared with the bismaleimide resin modified by 2,2' -Diallyl Bisphenol A (DBA) as the modifier.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (10)

1. A bismaleimide resin composition comprising a bismaleimide resin and a modifier, wherein the modifier is a resveratrol derivative 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene and has a structure represented by the following formula (1):
Figure DEST_PATH_IMAGE001
（1）。
2. the bismaleimide resin composition of claim 1 wherein the bismaleimide resin contains at least two maleimide groups and the bismaleimide resin comprises one of the chemical structures shown in formulas (2) and (3):
Figure DEST_PATH_IMAGE002
（2）
in the formula (2), R1 is an organic group having 1-30 carbon atoms and containing an aromatic ring structure;
Figure DEST_PATH_IMAGE003
（3）
in the formula (3), R2 is any one of hydrogen atom, alkyl containing 1-4 carbon atoms or halogen atom independently, and n is an integer of 0-5.
3. The bismaleimide resin composition of claim 1 wherein the molar ratio of maleimide groups of the bismaleimide resin to allylic double bonds of the modifier is 1:0.2 to 1: 1.
4. A process for producing the bismaleimide resin composition as claimed in any one of claims 1 to 3, comprising the steps of:
(1) preparation of the modifier: under the protection of inert gas, taking resveratrol and an acid-binding agent, stirring and mixing in an organic solvent, then dropwise adding allyl halohydrocarbon, and performing nucleophilic substitution reaction on the allyl halohydrocarbon and the resveratrol to prepare 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene;
(2) preparation of the composition: and (2) mixing the bismaleimide resin and the 1, 3-bis (allyloxy) -5- (4- (allyloxy) styryl) benzene obtained in the step (1) to obtain the bismaleimide resin composition.
5. The method of preparing bismaleimide resin composition as claimed in claim 4, wherein the acid binding agent in step (1) comprises one of triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate, sodium hydroxide, calcium hydroxide, potassium hydroxide, iron hydroxide, calcium carbonate, cesium carbonate, sodium phosphate, sodium acetate or any combination thereof.
6. The method for preparing bismaleimide resin composition as claimed in claim 4 wherein the allyl halide hydrocarbon in step (1) comprises one or any combination of allyl iodide, allyl chloride, allyl bromide and allyl fluoride.
7. The method for preparing bismaleimide resin composition as claimed in claim 4, wherein the organic solvent in step (1) comprises one of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, ethanol, propanol, acetone, 2-butanone or any combination thereof.
8. The method for preparing bismaleimide resin composition as claimed in claim 4, wherein the molar ratio of resveratrol, acid-binding agent and allyl halogenated hydrocarbon in step (1) is 1:3 to 6; the temperature of the nucleophilic substitution reaction is 40-200 ℃, and the reaction time is 4-48 h.
9. A cured product obtained by curing the composition according to any one of claims 1 to 3.
10. The cured product of claim 9, wherein the cured product is used in the fields of aerospace, composite materials, high temperature adhesives, copper clad laminates, and third generation semiconductor packaging materials.
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