Polymaleimide-triazine resin and preparation method thereof

Abstract

The invention provides polymaleimide-triazine resin and a preparation method thereof, and belongs to the technical field of resin. The polymaleimide-triazine resin provided by the invention is prepared from the following raw materials in percentage by mass: 60 to 80 percent of prepolymer A and 20 to 40 percent of prepolymer B, the prepolymer A is prepared from the following raw materials in percentage by mass: 30 to 60 percent of phenolic polymaleimide resin and 40 to 70 percent of cyanate ester composition; the prepolymer B is prepared from the following raw materials in percentage by mass: 15 to 43 percent of unsaturated group terminated polyphenyl ether, 14 to 30 percent of a cross-linking agent, 0.2 to 1.5 percent of an initiator and 26 to 70 percent of a good solvent. The phenolic aldehyde type maleimide resin contains a rigid structure, and the cyanate ester composition contains a naphthalene ring structure, so that the dimensional stability and the heat resistance are ensured; and the dielectric property is improved by adopting the unsaturated terminated polyphenyl ether.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of resin, and particularly relates to a multi-maleimide-triazine resin and a preparation method thereof. BACKGROUND

[0002] With the wide application of 5G basic network architecture equipment and the continuous progress of the semiconductor integrated circuit industry, the requirements for packaging materials such as BT resin are also getting higher and higher. Integrated circuits are rapidly developing in the direction of large-scale, super-high integration, micro-wiring, high power, high precision, multi-function, etc., and the BT resin needs to have lower dielectric constant and dielectric loss and better dimensional stability.

[0003] The dielectric properties and dimensional stability of the traditional BT resin still cannot meet the packaging requirements, which seriously limits its application in the fields of high-precision space vehicles, radar radomes, precision instruments and composite material molds. Therefore, how to modify the BT resin to have excellent dielectric properties and dimensional stability has become a technical problem to be solved in the field. SUMMARY

[0004] The application aims to provide a multi-maleimide-triazine resin and a preparation method thereof. The multi-maleimide-triazine resin provided by the application has good dielectric properties, heat resistance, processing properties, dimensional stability and low thermal expansion coefficient, can achieve a homogeneous system, and meets the development needs of the fields of aerospace and electronic packaging materials.

[0005] In order to achieve the above application purposes, the application provides the following technical solutions: The application provides a multi-maleimide-triazine resin, which is prepared from raw materials including 60-80% of a prepolymer A and 20-40% of a prepolymer B. The prepolymer A is prepared from raw materials including 30-60% of a phenolic type multi-maleimide resin and 40-70% of a cyanate ester composition. The prepolymer B is prepared from raw materials including 15-43% of an unsaturated group terminated polyphenyl ether, 14-30% of a crosslinking agent, 0.2-1.5% of an initiator and 26-70% of a good solvent.

[0006] Preferably, the cyanate ester composition is a bisphenol A type cyanate ester and a naphthalene cyanate ester.

[0007] Preferably, the naphthalene cyanate is one or a combination of two or more of the following: 1,3-naphthalene dicyanate, 1,4-naphthalene dicyanate, 1,5-naphthalene dicyanate, 1,6-naphthalene dicyanate, 1,7-naphthalene dicyanate, 2,3-naphthalene dicyanate, 2,6-naphthalene dicyanate, 2,7-naphthalene dicyanate, 1,3,5-naphthalene tricyanate, 1,3,6-naphthalene tricyanate, and 1,3,7-naphthalene tricyanate.

[0008] Preferably, the mass ratio of the naphthalene cyanate to the bisphenol A cyanate is (0.05~2):1.

[0009] Preferably, the phenolic polymaleimide resin has the structural formula shown in Formula I: Formula I; In Formula I, MI represents a maleimide group, and n is 1 to 10.

[0010] Preferably, the unsaturated groups of the polyphenylene ether with unsaturated groups at the end are one or more combinations of acrylic acid, benzyl vinyl, vinyl, allyl and propargyl.

[0011] Preferably, the crosslinking agent is one or a combination of two or more of divinylbenzene, divinylnaphthalene, divinylbiphenyl, diallyl bisphenol A, triallyl isocyanurate, and triallyl cyanurate.

[0012] The present invention also provides a method for preparing the polymaleimide-triazine resin described in the above technical solution, comprising the following steps: (1) A phenolic polymaleimide resin and a cyanate ester composition are mixed and subjected to a first polymerization reaction to obtain prepolymer A; (2) Mix polyphenylene ether, crosslinking agent, initiator and good solvent, and carry out a second polymerization reaction to obtain prepolymer B; (3) The prepolymer A obtained in step (1) and the prepolymer B obtained in step (2) are mixed and subjected to a third polymerization reaction to obtain polymaleimide-triazine resin; The steps (1) and (2) are not in any particular order.

[0013] Preferably, the temperature of the first polymerization reaction in step (1) is 120~140℃, and the time of the first polymerization reaction is 3~5h.

[0014] Preferably, the temperature of the third polymerization reaction in step (3) is 80~120℃, and the time of the third polymerization reaction is 1~3h.

[0015] This invention provides a polymaleimide-triazine resin prepared from raw materials comprising the following mass percentages: 60-80% prepolymer A and 20-40% prepolymer B; said prepolymer A is prepared from raw materials comprising the following mass percentages: 30-60% phenolic polymaleimide resin and 40-70% cyanate ester composition; said prepolymer B is prepared from raw materials comprising the following mass percentages: 15-43% unsaturated group-terminated polyphenylene ether, 14-30% crosslinking agent, 0.2-1.5% initiator and 26-70% good solvent. This invention uses phenolic polymaleimide resin to prepare polymaleimide-triazine resin, which contains a rigid structure (benzene ring, naphthalene ring, and maleimide groups) and provides more reaction sites (naphthalene cyanate, containing more maleimide groups). It can form a dense cured product through cross-linking, which improves the heat resistance and mechanical properties of polymaleimide-triazine resin, effectively reduces its coefficient of thermal expansion, and thus ensures its dimensional stability. The invention uses polyphenylene ether with unsaturated end caps, whose unsaturated groups can react with the maleimide groups in prepolymer A, thereby improving the compatibility between resins, reducing the brittleness of the material, increasing the flexural strength, and effectively improving the dielectric properties of polymaleimide-triazine resin. The results of the examples show that the thermal expansion coefficient of the polymaleimide-triazine resin provided by the present invention is 53~58ppm, the relative permittivity (1MHz) is 2.60~2.95, the dielectric loss tangent (1MHz) is 0.003~0.007, the flexural strength is 120~129MPa, and the flexural modulus is 3.57~3.84GPa. Attached Figure Description

[0016] Fig. 1 The relative permittivity curves of the polymaleimide-triazine resins prepared in Examples 1-3 are shown. Fig. 2 The dielectric loss tangent curves of the polymaleimide-triazine resins prepared in Examples 1-3 are shown. Fig. 3 The diagram shows the dimensional stability of the polymaleimide-triazine resins prepared in Examples 1-3. Fig. 4 The diagram shows the flexural strength and flexural modulus of the polymaleimide-triazine resins prepared in Examples 1-3. Detailed Implementation

[0017] The present invention provides a polymaleimide-triazine resin, which is prepared from raw materials comprising the following mass percentages: 60-80% prepolymer A and 20-40% prepolymer B; The prepolymer A is prepared from raw materials comprising the following mass percentages: 30-60% phenolic polymaleimide resin and 40-70% cyanate ester composition. The prepolymer B is prepared from raw materials comprising the following mass percentages: 15-43% unsaturated group-terminated polyphenylene ether, 14-30% crosslinking agent, 0.2-1.5% initiator, and 26-70% good solvent.

[0018] This invention does not impose any special restrictions on the source of the raw materials; commercially available products or well-known preparation methods familiar to those skilled in the art can be used for preparation.

[0019] The raw materials for preparing the polymaleimide-triazine resin of the present invention comprise 60-80% prepolymer A by mass percentage. As one embodiment, the mass percentage of prepolymer A can be 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 71.2%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, or 79%. Limiting the mass percentage of prepolymer A within the above range further improves dielectric properties and dimensional stability.

[0020] The raw materials for preparing the prepolymer A of the present invention comprise 40-70% by mass percentage of a cyanate ester composition. As one embodiment, the mass percentage of the cyanate ester composition can be 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 48.2%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 58.2%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, or 69%. Limiting the mass percentage of the cyanate ester composition within the above range further improves the dielectric properties and dimensional stability of the present invention.

[0021] In this invention, the cyanate composition is preferably bisphenol A cyanate and naphthalene cyanate; the naphthalene cyanate is preferably one or a combination of two or more of 1,3-naphthalene dicyanate, 1,4-naphthalene dicyanate, 1,5-naphthalene dicyanate, 1,6-naphthalene dicyanate, 1,7-naphthalene dicyanate, 2,3-naphthalene dicyanate, 2,6-naphthalene dicyanate, 2,7-naphthalene dicyanate, 1,3,5-naphthalene tricyanate, 1,3,6-naphthalene tricyanate and 1,3,7-naphthalene tricyanate; the mass ratio of the naphthalene cyanate to the bisphenol A cyanate is preferably (0.05~2):1. In one embodiment, the mass ratio of naphthalene cyanate to bisphenol A cyanate can be 0.05:1, 0.10:1, 0.20:1, 0.30:1, 0.40:1, 0.50:1, 0.60:1, 0.70:1, 0.80:1, 0.90:1, 1:1, 1.50:1, or 2:1. Limiting the mass ratio of naphthalene cyanate to bisphenol A cyanate within the above ranges further improves dielectric properties, heat resistance, and dimensional stability.

[0022] In this invention, the naphthalene cyanate is preferably one or a combination of two or more of the following structural formulas: , , , , , , , , , , .

[0023] The raw materials for preparing prepolymer A of the present invention, by weight percentage, comprise 30-60% phenolic polymaleimide resin. As one embodiment, the weight percentage of the phenolic polymaleimide resin can be 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 41.8%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 51.8%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, or 59%. Limiting the weight percentage of the phenolic polymaleimide resin within the above range further improves dimensional stability.

[0024] In this invention, the preferred structural formula of the phenolic polymaleimide resin is shown in Formula I: Formula I; In Formula I, MI represents a maleimide group, and n is 1 to 10. The phenolic polymaleimide resin of the present invention with the above-mentioned structure has a longer flexible chain segment and more maleimide groups than bismaleimide, which can form more physical crosslinking points between molecules. The crosslinking density of the cured product is moderate, which can improve the toughness and impact resistance of the material while maintaining a certain strength and heat resistance. At the same time, it has a lower melting point and better solubility, and is more uniform in processing and curing, reducing the formation of internal defects, thereby improving the mechanical properties of the material.

[0025] This invention does not have a specific limitation on the source of the phenolic polymaleimide resin; any commercially available phenolic polymaleimide resin can achieve the technical effects of this invention. As one embodiment, the phenolic polymaleimide resin can be purchased from Reina Electronic Materials (Shanghai) Co., Ltd.

[0026] The raw materials for preparing the polymaleimide-triazine resin of the present invention comprise 20-40% prepolymer B by weight percentage. As one embodiment, the weight percentage of prepolymer B can be 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 28.8%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, or 39%. Limiting the weight percentage of prepolymer B within the above range further improves dielectric properties and dimensional stability.

[0027] The raw materials for preparing the prepolymer B of this invention, by mass percentage, comprise 15-43% of polyphenylene ether with unsaturated groups at the end of its structure. As one embodiment, the mass percentage of the polyphenylene ether with unsaturated groups at the end of its structure can be 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 30.6%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 38.5%, 39%, 40%, 41%, 42%, or 43%. Limiting the mass percentage of the polyphenylene ether with unsaturated groups at the end of its structure within the above range further improves resin compatibility, reduces material brittleness, increases flexural strength, and effectively improves the dielectric properties of polymaleimide-triazine resin.

[0028] In this invention, the unsaturated groups of the polyphenylene ether with unsaturated groups at the end are preferably one or a combination of two or more of acrylic acid, benzyl vinyl, vinyl, allyl and propargyl.

[0029] In this invention, the weight-average molecular weight of the polyphenylene ether is preferably 2000-4000; the particle size of the polyphenylene ether is preferably 5-100 μm. As one embodiment, the weight-average molecular weight of the polyphenylene ether can be 2500, 3000, or 3500; the particle size of the polyphenylene ether can be 10 μm, 40 μm, 60 μm, or 80 μm.

[0030] The raw materials for preparing the prepolymer B of the present invention comprise 14-30% crosslinking agent by mass percentage. As one embodiment, the mass percentage of the crosslinking agent can be 14.7%, 15%, 15.3%, 15.8%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, or 29%.

[0031] In this invention, the crosslinking agent is preferably one or a combination of two or more of divinylbenzene, divinylnaphthalene, divinylbiphenyl, diallyl bisphenol A, triallyl isocyanurate, and triallyl cyanurate.

[0032] The raw materials for preparing the prepolymer B of the present invention, by mass percentage, include 0.2-1.5% of an initiator; the initiator is preferably at least one selected from dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile. As one embodiment, the mass percentage of the initiator can be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, or 1.4%.

[0033] The raw materials for preparing the prepolymer B of this invention, by mass percentage, include 26-70% of a good solvent; the good solvent is preferably one or a mixture of two or more of cyclohexanone, butanone, dichloromethane, toluene, and xylene. As one embodiment, the mass percentage of the good solvent can be 26%, 30%, 35%, 40%, 44.9%, 45%, 50%, 53.5%, 55%, 60%, 65%, or 70%. This invention uses a good solvent that enables the dissolution of all raw materials.

[0034] This invention uses phenolic polymaleimide resin to prepare polymaleimide-triazine resin, which contains a rigid structure (benzene ring, naphthalene ring, and maleimide groups) and provides more reaction sites (naphthalene cyanate, containing more maleimide groups). It can form a dense cured product through cross-linking, which improves the heat resistance and mechanical properties of polymaleimide-triazine resin, effectively reduces its coefficient of thermal expansion, and thus ensures its dimensional stability. The invention uses polyphenylene ether with unsaturated end caps, whose unsaturated groups can react with the maleimide groups in prepolymer A, thereby improving the compatibility between resins, reducing the brittleness of the material, increasing the flexural strength, and effectively improving the dielectric properties of polymaleimide-triazine resin.

[0035] This invention employs a copolymerization reaction of phenolic polymaleimide resin and cyanate ester composition, and further modifies it by introducing polyphenylene ether with unsaturated end groups. The aim is to improve the dielectric properties and dimensional stability of the polymaleimide-triazine resin while ensuring the cured product reaches a homogeneous system, and simultaneously reduce its coefficient of thermal expansion. The polymaleimide-triazine resin prepared by this invention contains numerous active sites, effectively enhancing its solubility and processing performance. It can be used to prepare resin-based composite materials with low dielectric properties and high dimensional stability. Furthermore, its cured product exhibits advantages such as high strength, high heat resistance, low dielectric properties, and high dimensional stability, making it suitable for applications in aerospace and electronic information fields.

[0036] The present invention also provides a method for preparing the polymaleimide-triazine resin described in the above technical solution, comprising the following steps: (1) A phenolic polymaleimide resin and a cyanate ester composition are mixed and subjected to a first polymerization reaction to obtain prepolymer A; (2) Mix polyphenylene ether, crosslinking agent, initiator and good solvent, and carry out a second polymerization reaction to obtain prepolymer B; (3) The prepolymer A obtained in step (1) and the prepolymer B obtained in step (2) are mixed and subjected to a third polymerization reaction to obtain polymaleimide-triazine resin; The steps (1) and (2) are not in any particular order.

[0037] In this invention, a phenolic polymaleimide resin and a cyanate ester composition are mixed and subjected to a first polymerization reaction to obtain prepolymer A.

[0038] The present invention does not have any special limitations on the operation of mixing the phenolic polymaleimide resin and cyanate ester composition, and any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0039] In this invention, the temperature of the first polymerization reaction is preferably 120-140°C; the time of the first polymerization reaction is preferably 3-5 hours. As one embodiment, the temperature of the first polymerization reaction can be 125°C, 130°C, or 135°C; the time of the first polymerization reaction can be 4 hours. By limiting the process parameters of the first polymerization reaction to the above ranges, this invention ensures the extent of the polymerization reaction.

[0040] In this invention, polyphenylene ether, crosslinking agent, initiator and good solvent are mixed to carry out a second polymerization reaction to obtain prepolymer B.

[0041] The present invention does not have any special limitations on the operation of mixing the polyphenylene ether, crosslinking agent, initiator and good solvent, and any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0042] In this invention, the preferred temperature for the second polymerization reaction is 70-110°C; the preferred time for the second polymerization reaction is 1-5 hours. As one embodiment, the temperature for the second polymerization reaction can be 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, or 105°C; the preferred time for the second polymerization reaction can be 2 hours, 3 hours, or 4 hours. By limiting the process parameters of the second polymerization reaction to the above ranges, this invention ensures the degree of polymerization.

[0043] In this invention, the second polymerization reaction is preferably carried out under stirring conditions; the stirring rate is preferably 30-200 rpm. As one embodiment, the stirring rate can be 60 rpm.

[0044] After obtaining prepolymer A and prepolymer B, the present invention mixes prepolymer A and prepolymer B and carries out a third polymerization reaction to obtain polymaleimide-triazine resin.

[0045] The present invention does not have any special limitations on the operation of mixing prepolymer A and prepolymer B, and any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0046] In this invention, the temperature of the third polymerization reaction is preferably 80-120°C; the time of the third polymerization reaction is preferably 1-3 hours. As one embodiment, the temperature of the third polymerization reaction can be 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, or 115°C; the time of the third polymerization reaction can be 2 hours. By limiting the process parameters of the third polymerization reaction to the above ranges, this invention ensures the degree of polymerization.

[0047] In this invention, the third polymerization reaction is preferably carried out under stirring conditions; the stirring rate is preferably 30-200 rpm. As one embodiment, the stirring rate can be 60 rpm.

[0048] This invention provides a homogeneous polymaleimide-triazine resin obtained through melt polymerization and solution polymerization processes without a catalyst. The polymaleimide-triazine resin of this invention exhibits low dielectric constant and dielectric loss, along with excellent dimensional stability and mechanical properties, meeting the needs of the aerospace and electronic packaging fields. Furthermore, the preparation method is simple and suitable for large-scale production, possessing significant practical application value.

[0049] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0050] Example 1 The polymaleimide-triazine resin was prepared from the following raw materials in the indicated weight percentages: 75% prepolymer A and 25% prepolymer B; The prepolymer A was prepared from the following raw materials in the indicated mass percentages: 41.8% phenolic polymaleimide resin and 58.2% cyanate ester composition. The cyanate composition is bisphenol A cyanate and 2,7-naphthalene dicyanate, with a mass ratio of 2,7-naphthalene dicyanate to bisphenol A cyanate of 0.5:1; The prepolymer B is prepared from the following raw materials in the indicated mass percentages: 15% acrylic acid-terminated polyphenylene ether, 14.7% crosslinking agent triallyl isocyanurate, 0.3% initiator dicumyl peroxide, and 70% toluene. The preparation method of the polymaleimide-triazine resin is as follows: (1) Bisphenol A cyanate was added to a 250 mL three-necked flask equipped with a condenser, stirrer and thermometer, heated to 110 °C and mechanically stirred at constant temperature until the monomer melted. The system was a clear and transparent liquid. Then phenolic polymaleimide (purchased from Reina Electronic Materials (Shanghai) Co., Ltd.) was added. The system gradually turned pale yellow. Then 2,7-naphthalene dicyanate was added. After the addition was completed, the temperature was raised to 120 °C for the first polymerization reaction for 4 h to obtain amber prepolymer A. (2) Add acrylic acid-terminated polyphenylene ether (SA9000, GE) to a three-necked flask equipped with a condenser, stirrer and thermometer, then add toluene to prepare a solution, gradually raise the temperature to 100°C, and then gradually add triallyl isocyanurate and initiator dicumyl peroxide and stir at a constant temperature of 60 rpm for 3 hours to obtain prepolymer B; (3) Add the prepolymer A obtained in step (1) and the prepolymer B obtained in step (2) into a 250mL three-necked flask equipped with a condenser, a stirrer and a thermometer, heat to 100℃, stir at a constant temperature and a stirring rate of 60 rpm, and carry out the third polymerization reaction for 3 hours to obtain polymaleimide-triazine resin.

[0051] Example 2 The domaleimide-triazine resin was prepared from the following raw materials in the indicated weight percentages: 71.2% prepolymer A and 28.8% prepolymer B; The prepolymer A is prepared from the following raw materials in the following mass percentages: 51.8% phenolic polymaleimide resin and 48.2% cyanate ester composition; the cyanate ester composition is bisphenol A cyanate and 1,5-naphthalene dicyanate, and the mass ratio of bisphenol A cyanate and 1,5-naphthalene dicyanate is 1:1. The prepolymer B is prepared from the following raw materials in the indicated mass percentages: 30.6% acrylic acid-terminated polyphenylene ether, 15.3% crosslinking agent triallyl isocyanurate, 0.6% initiator dicumyl peroxide, and 53.5% toluene; The preparation method of the polymaleimide-triazine resin is as follows: (1) Bisphenol A cyanate was added to a 250 mL three-necked flask equipped with a condenser, stirrer and thermometer, heated to 110 °C and mechanically stirred at constant temperature until the monomer melted. The system was a clear and transparent liquid. Then phenolic polymaleimide (purchased from Reina Electronic Materials (Shanghai) Co., Ltd.) was added. The system gradually turned pale yellow. Then 1,5-naphthalene dicyanate was added. After the addition was completed, the temperature was raised to 120 °C for the first polymerization reaction for 4 h to obtain amber prepolymer A. (2) Acrylic acid-terminated polyphenylene ether (SA9000, GE) and toluene were added to a three-necked flask equipped with a condenser, stirrer and thermometer to prepare a solution. The temperature was gradually raised to 100°C, and then triallyl isocyanurate and dicumyl peroxide were added dropwise. The second polymerization reaction was carried out at a constant temperature and stirred for 3 hours at a stirring rate of 60 rpm to obtain prepolymer B. (3) Add the prepolymer A obtained in step (1) and the prepolymer B obtained in step (2) into a 250mL three-necked flask equipped with a condenser, a stirrer and a thermometer, heat to 110°C, stir at a constant temperature of 60 rpm, and carry out the third polymerization reaction for 2 hours to obtain polymaleimide-triazine resin.

[0052] Example 3 The domaleimide-triazine resin was prepared from the following raw materials in the indicated weight percentages: 72% prepolymer A and 28% prepolymer B; The prepolymer A is prepared from the following raw materials in the following mass percentages: 41.8% phenolic polymaleimide resin and 58.2% cyanate ester composition; the cyanate ester composition is bisphenol A cyanate and 3,6-naphthalene dicyanate, and the mass ratio of 3,6-naphthalene dicyanate to bisphenol A cyanate is 2:1; The prepolymer B is prepared from the following raw materials in the indicated mass percentages: 38.5% acrylic acid-terminated polyphenylene ether, 15.8% crosslinking agent triallyl isocyanurate, 0.8% initiator dicumyl peroxide, and 44.9% toluene; The preparation method of the polymaleimide-triazine resin is as follows: (1) Bisphenol A cyanate was added to a 250 mL three-necked flask equipped with a condenser, stirrer and thermometer, heated to 110 °C and mechanically stirred at constant temperature until the monomer melted. The system was a clear and transparent liquid. Then phenolic polymaleimide (purchased from Reina Electronic Materials (Shanghai) Co., Ltd.) was added. The system gradually turned pale yellow. Then 3,6-naphthalene dicyanate was added. After the addition was completed, the temperature was raised to 120 °C for the first polymerization reaction for 4 h to obtain amber prepolymer A. (2) Acrylic acid-terminated polyphenylene ether (SA9000, GE) and toluene were added to a three-necked flask equipped with a condenser, stirrer and thermometer to prepare a solution. The temperature was gradually raised to 100°C, and then triallyl isocyanurate and initiator dicumyl peroxide were gradually added. The mixture was stirred at a constant temperature for 3 hours to carry out the second polymerization reaction. The stirring speed was 60 rpm to obtain prepolymer B. (3) Add the prepolymer A obtained in step (1) and the prepolymer B obtained in step (2) into a 250mL three-necked flask equipped with a condenser, a stirrer and a thermometer, heat to 100℃, and carry out the third polymerization reaction by constant temperature mechanical stirring for 3h. The stirring rate is 60 rpm to obtain polymaleimide-triazine resin.

[0053] Comparative Example 1 The preparation method of bismaleimide-triazine resin is as follows: (1) 33.33 g of bisphenol A cyanate was added to a 250 mL three-necked flask equipped with a condenser, stirrer and thermometer. The mixture was heated to 100 °C and mechanically stirred at a constant temperature until the monomer melted. The system was a clear and transparent liquid. Then 35.84 g of diphenylmethane bismaleimide (purchased from Reina Electronic Materials (Shanghai) Co., Ltd.) was added. The system gradually turned pale yellow. After the addition was completed, the temperature was raised to 120 °C until the mixture was uniform. The reaction was continued for 4 h to obtain amber-colored bismaleimide-triazine resin.

[0054] The polymaleimide-triazine resins prepared in Examples 1-3 and the bismaleimide-triazine resins prepared in Comparative Example 1 were subjected to vacuum distillation to remove the solvent. The resins were then poured into molds coated with a silicone release agent for testing. The molds were degassed in a vacuum oven at 90°C for 30 minutes, followed by curing in a forced-air drying oven at 120°C for 2 hours, 140°C for 2 hours, 160°C for 2 hours, 180°C for 2 hours, 210°C for 2 hours, 230°C for 2 hours, and 250°C for 4 hours. After natural cooling, the cast specimens were obtained. These specimens were then polished, and their dielectric properties, coefficient of thermal expansion, thermogravimetric analysis, glass transition temperature, and flexural properties were tested. The methods are as follows, and the data are shown in Table 1 and... Figs. 1-4 As shown: (1) Thermal decomposition temperature (T) d5 ) and pyrolysis residue (Yc): Thermogravimetric analysis (TGA) was used for testing. The heating rate was 10℃ / min. The temperature at which 5% thermal decomposition weight loss was measured was T. d5 The mass residue rate at 800℃ is Yc, and the test atmosphere is air.

[0055] (2) Glass transition temperature (Tg): The glass transition temperature (Tg) was tested using the Dynamic Thermomechanical Analyzer (DMA) method. The sample size was 60×12×4mm. The three-point bending method was used. The test temperature range was room temperature to 350℃, the heating rate was 10℃ / min, and the test atmosphere was air.

[0056] (3) Coefficient of thermal expansion: The test was conducted using a coefficient of thermal expansion tester. The sample size was 25×5×5mm, the heating rate was 5℃ / min, the test temperature range was from room temperature to 300℃, and the test atmosphere was a nitrogen atmosphere.

[0057] (4) Relative permittivity (ε) and dielectric loss tangent (tanδ): A broadband dielectric impedance meter was used, with a sample diameter of 30 mm and a thickness of 1 mm for cured resin discs, and the test frequency was 1 Hz to 1 MHz.

[0058] (5) Bending strength and bending modulus: The bending strength and bending modulus were tested using a universal electronic tensile testing machine. The sample size was 80×10×4mm. The three-point bending method was used, with the span being 16 times the thickness, and the loading speed was 2mm / min.

[0059] Table 1. Performance data of the polymaleimide-triazine resins prepared in Examples 1-3 and the bismaleimide-triazine resin prepared in Comparative Example 1.

[0060] From Table 1 and Figs. 1-4 It can be seen that the polymaleimide-triazine resin provided by the present invention has superior heat resistance, high dimensional stability coefficient, low dielectric constant, low dielectric loss and good mechanical properties compared with pure BT resin.

[0061] As can be seen from the examples and comparative examples, the polymaleimide-triazine resin provided by the present invention has good dielectric properties, heat resistance, processing performance, dimensional stability and low coefficient of thermal expansion. The cured product reaches a homogeneous system, which can meet the development needs of aerospace and electronic packaging materials.

[0062] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A polymaleimide-triazine resin, characterized in that, It is prepared from raw materials comprising the following mass percentages: 60-80% prepolymer A and 20-40% prepolymer B; The prepolymer A is prepared from raw materials comprising the following mass percentages: 30-60% phenolic polymaleimide resin and 40-70% cyanate ester composition. The prepolymer B is prepared from raw materials comprising the following mass percentages: 15-43% unsaturated group-terminated polyphenylene ether, 14-30% crosslinking agent, 0.2-1.5% initiator, and 26-70% good solvent.

2. The polymaleimide-triazine resin according to claim 1, characterized in that, The cyanate composition is bisphenol A cyanate and naphthalene cyanate.

3. The polymaleimide-triazine resin according to claim 2, characterized in that, The naphthalene cyanate is one or a combination of two or more of the following: 1,3-naphthalene dicyanate, 1,4-naphthalene dicyanate, 1,5-naphthalene dicyanate, 1,6-naphthalene dicyanate, 1,7-naphthalene dicyanate, 2,3-naphthalene dicyanate, 2,6-naphthalene dicyanate, 2,7-naphthalene dicyanate, 1,3,5-naphthalene tricyanate, 1,3,6-naphthalene tricyanate, and 1,3,7-naphthalene tricyanate.

4. The polymaleimide-triazine resin according to claim 2, characterized in that, The mass ratio of the naphthalene cyanate to the bisphenol A cyanate is (0.05~2):

1.

5. The polymaleimide-triazine resin according to claim 1, characterized in that, The structural formula of the phenolic polymaleimide resin is shown in Formula I: Formula I; In Formula I, MI represents a maleimide group, and n is 1 to 10.

6. The polymaleimide-triazine resin according to claim 1, characterized in that, The unsaturated groups of the polyphenylene ether end-capped with unsaturated groups are one or more combinations of acrylic acid, benzyl vinyl, vinyl, allyl and propargyl.

7. The polymaleimide-triazine resin according to claim 1, characterized in that, The crosslinking agent is one or a combination of two or more of divinylbenzene, divinylnaphthalene, divinylbiphenyl, diallyl bisphenol A, triallyl isocyanurate, and triallyl cyanurate.

8. A method for preparing the polymaleimide-triazine resin according to any one of claims 1 to 7, characterized in that, Includes the following steps: (1) A phenolic polymaleimide resin and a cyanate ester composition are mixed and subjected to a first polymerization reaction to obtain prepolymer A; (2) Mix polyphenylene ether, crosslinking agent, initiator and good solvent, and carry out a second polymerization reaction to obtain prepolymer B; (3) The prepolymer A obtained in step (1) and the prepolymer B obtained in step (2) are mixed and subjected to a third polymerization reaction to obtain polymaleimide-triazine resin; The steps (1) and (2) are not in any particular order.

9. The preparation method according to claim 8, characterized in that, The temperature of the first polymerization reaction in step (1) is 120~140℃, and the time of the first polymerization reaction is 3~5h.

10. The preparation method according to claim 8, characterized in that, The temperature of the third polymerization reaction in step (3) is 80~120℃, and the time of the third polymerization reaction is 1~3h.

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