CN114685988A - Modified bismaleimide resin and preparation method and application thereof - Google Patents
Modified bismaleimide resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of modified bismaleimide resin, which comprises the following steps: blending bismaleimide monomer containing ether bond and cyanate monomer containing benzene ring, and carrying out primary prepolymerization; mixing the product obtained by the first prepolymerization with a catalyst and a thermoplastic toughening agent with a functional group at the end, and carrying out second prepolymerization; curing the product obtained by the second prepolymerization; wherein the mass ratio of the bismaleimide monomer containing ether bonds to the catalyst is 1 (0.08-0.12). The method not only enhances the toughness and reduces the dielectric constant and the dielectric loss, but also keeps the high temperature resistance and the rigidity of the bismaleimide resin, and the preparation method has the advantages of easily obtained raw materials, simple process and wide popularization and application.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a modified bismaleimide resin and a preparation method and application thereof.
Background
The bismaleimide resin is a resin system derived from a polyimide resin system, is low in price and low in requirements on molding and processing conditions, has good mechanical properties, heat resistance and dielectric properties, is a base resin for a wave-transmitting composite material with good comprehensive properties, and is widely applied to the field of aerospace. The bismaleimide resin has the defects of high brittleness of a cured product due to a three-dimensional cross-linked structure, and the broadband electromagnetic wave transmission performance is not ideal (the dielectric constant of the bismaleimide resin is more than or equal to 2.9, and the dielectric loss tangent is more than or equal to 0.012), and modification is generally needed.
The techniques for improving bismaleimide resins have been widely used to improve the toughness of bismaleimide resins by copolymerizing thermoplastic resins with the bismaleimide resins. The compatibility of the traditional thermoplastic resin toughening agent and bismaleimide is poor, and due to the properties of poor heat resistance and the like of the traditional thermoplastic toughening agent, the toughness of the resin is enhanced after copolymerization, but the high temperature resistance and rigidity of the modified bismaleimide resin are reduced, so that the application of the modified bismaleimide resin is limited.
Disclosure of Invention
Based on the above, the invention provides a preparation method of a modified bismaleimide resin, which can maintain the high temperature resistance and rigidity of the bismaleimide resin while enhancing the toughness and reducing the dielectric constant and dielectric loss.
The invention is realized by the following technical scheme.
A preparation method of modified bismaleimide resin comprises the following steps:
blending bismaleimide monomer containing ether bond and cyanate monomer containing benzene ring, and carrying out primary prepolymerization;
mixing the product obtained by the first prepolymerization with a catalyst and a thermoplastic toughening agent with a functional group at the end, and carrying out second prepolymerization;
curing the product obtained by the second prepolymerization;
wherein the mass ratio of the bismaleimide monomer containing ether bonds to the catalyst is 1 (0.08-0.12).
In one embodiment, the thermoplastic toughening agent with functional groups at the ends is an amino-terminated hyperbranched polymer.
In one embodiment, the catalyst is an allyl-containing compound.
In one embodiment, the bismaleimide monomer containing ether bonds is prepared by mixing a diamine compound and maleic anhydride and reacting; wherein the mass ratio of the diamine compound to the maleic anhydride is 1: 2.5.
In one embodiment, the cyanate ester monomer containing a benzene ring is prepared by mixing cyanogen bromide and a dihydroxy compound containing a benzene ring and reacting; wherein the mass ratio of the cyanogen bromide to the dihydroxy compound containing the benzene ring is 1: 1.
In one embodiment, the ratio of the cyanate ester monomer containing benzene ring, the bismaleimide monomer containing ether bond and the thermoplastic toughening agent with functional groups at the terminal is (0.5-1): 1 (0.1-0.2).
In one embodiment, the conditions for the first prepolymerization are as follows: stirring at the constant temperature of 110-130 ℃ for 30-50 min; the conditions for the second prepolymerization were: stirring at 110-130 deg.c for 30-50 min.
In one embodiment, the curing conditions are: after vacuum defoaming is carried out for 20min to 40min at the temperature of 125 ℃ to 150 ℃, the first-stage curing, the second-stage curing and the third-stage curing are carried out in sequence;
wherein, the conditions of the first stage curing are as follows: keeping the temperature for 1 to 1.5 hours at the temperature of between 155 and 165 ℃;
the conditions for the second stage curing were: keeping the temperature at 180-190 ℃ for 1.5-2.5 h;
the conditions for the third stage curing are: keeping the temperature for 1.5 to 2.5 hours at 235 to 245 ℃.
The invention also provides the modified bismaleimide resin prepared by the preparation method of the modified bismaleimide resin.
The invention also provides application of the modified bismaleimide resin in preparation of wave-transmitting composite materials or antenna window products.
Compared with the prior art, the preparation method of the modified bismaleimide resin has the following beneficial effects:
according to the preparation method of the modified bismaleimide resin, the benzene ring high-heat-stability group is introduced into the chain structure of the cyanate ester, and the ether bond flexible chain segment is introduced into the chain structure of the bismaleimide resin, so that the dielectric property and the mechanical property of the modified resin are maintained, and meanwhile, the high heat resistance is maintained. In addition, a catalyst and a thermoplastic toughening agent with a functional group at the end are added into a blending system of cyanate ester and bismaleimide resin, the content of a bismaleimide monomer containing ether bonds and the catalyst is limited, multiple toughening mechanisms such as an interpenetrating network structure, cross-linking density reduction, interface enhancement and the like are fully utilized to achieve a synergistic toughening effect, the compatibility of the thermoplastic toughening agent with the functional group at the end and the blending system is good, and the toughness, the dielectric constant and the dielectric loss of the finally prepared modified bismaleimide resin are improved on the basis of keeping high temperature resistance.
The preparation method has the advantages of easily available raw materials, simple process and wide popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic flow chart of a preparation method of a modified bismaleimide resin provided by the invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, the present invention provides a method for preparing a modified bismaleimide resin, which comprises the following steps S110 to S130:
step S110: blending bismaleimide monomer containing ether bond and cyanate monomer containing benzene ring, and carrying out primary prepolymerization;
step S120: mixing the product obtained by the first prepolymerization with a catalyst and a thermoplastic toughening agent with a functional group at the end, and carrying out second prepolymerization; wherein the mass ratio of the bismaleimide monomer containing ether bonds to the catalyst is 1 (0.08-0.12).
Step S130: and curing the product obtained by the second prepolymerization.
The researchers of the present invention found that controlling the amount ratio of the bismaleimide monomer containing ether bond and the catalyst can largely affect the crosslinking density of the cyanate ester and the bismaleimide resin, thereby enhancing the product properties, such as toughness, high temperature resistance, rigidity and dielectric constant and dielectric loss reduction.
In step S110, in a specific example, the bismaleimide monomer containing an ether bond is prepared by mixing a diamine compound and maleic anhydride and reacting them.
More specifically, the diamine compound used can be prepared by, but is not limited to, the following steps:
synthesizing a dinitro compound containing a benzene ring by using p-nitrochlorobenzene and a dihydroxy compound according to the mass ratio of (1.8-2.4) to 1;
ethanol is used as a solvent, ferric trichloride is used as a catalyst, and a dinitro compound containing benzene rings and hydrazine hydrate are synthesized into a diamine compound at the temperature of 70-90 ℃ according to the mass ratio of 1 (1.9-2.5).
Preferably, the mass ratio of diamine compound to maleic anhydride is 1: 2.5.
In a specific example, the cyanate ester monomer containing a benzene ring is prepared by mixing cyanogen bromide with a dihydroxy compound containing a benzene ring and reacting.
More specifically, the cyanogen bromide used can be prepared by, but is not limited to, the following steps:
mixing potassium cyanide and liquid bromine according to the mass ratio of (0.8-1.4) to 1, and reacting at 0-5 ℃ to synthesize cyanogen bromide.
More specifically, the mass ratio of cyanogen bromide to the dihydroxy compound containing a benzene ring is 1: 1.
More specifically, the reaction temperature of cyanogen bromide and dihydroxy compound containing benzene ring is-5 ℃ to 5 ℃.
In a specific example, the conditions for the first prepolymerization are: stirring at 110-130 deg.c for 30-50 min. It is understood that, in the present invention, the temperature can be set to, but not limited to, 110 ℃, 115 ℃, 118 ℃, 119 ℃, 120 ℃, 121 ℃, 122 ℃, 125 ℃, 130 ℃; the time period can be set to, but is not limited to, 30min, 35min, 38min, 39min, 40min, 41min, 42min, 45min, 50 min.
In step S120, in one specific example, the particle size of the thermoplastic toughening agent is 10 μm to 50 μm.
In one particular example, the terminally functionalized thermoplastic toughening agent is an amino-terminated hyperbranched polymer.
The amino-terminated hyperbranched polymer can ensure good compatibility with a blending system.
Further, in one particular example, the terminally functional thermoplastic toughening agent is an amino-terminated hyperbranched polysiloxane.
In a specific example, the preparation of the amino-terminated hyperbranched polysiloxane comprises the following steps:
mixing gamma-aminopropyltriethoxysilane, distilled water and ethanol, stirring at room temperature for 10-20 min, heating the solution to 50-60 deg.c, stirring at the temperature for 4-6 hr, and steaming to eliminate ethanol in 55-65 deg.c environment.
In one specific example, the catalyst is selected from compounds containing allyl groups, such as, but not limited to, allylphenol compounds. In a more specific example, the catalyst is allyl bisphenol a.
In a specific example, the ratio of the cyanate ester monomer containing benzene ring, the bismaleimide monomer containing ether bond and the thermoplastic toughening agent with functional groups at the end is (0.5-1): 1 (0.1-0.2).
In one specific example, the conditions for the second prepolymerization are: stirring at 110-130 deg.c for 30-50 min. It is understood that, in the present invention, the temperature can be set to, but not limited to, 110 ℃, 115 ℃, 118 ℃, 119 ℃, 120 ℃, 121 ℃, 122 ℃, 125 ℃, 130 ℃; the time period can be set to, but is not limited to, 30min, 35min, 38min, 39min, 40min, 41min, 42min, 45min, 50 min.
The person skilled in the art finds that the length of time for the second prepolymerization significantly affects the properties of the final product.
In step S130, in a specific example, the curing conditions are: after vacuum defoaming is carried out for 20min to 40min at the temperature of 125 ℃ to 150 ℃, the first stage curing, the second stage curing and the third stage curing are carried out;
wherein, the conditions of the first stage curing are as follows: keeping the temperature for 1 to 1.5 hours at the temperature of between 155 and 165 ℃;
the conditions for the second stage curing were: keeping the temperature at 180-190 ℃ for 1.5-2.5 h;
the conditions for the third stage curing are: keeping the temperature for 1.5 to 2.5 hours at 235 to 245 ℃.
In a more specific example, the method for preparing the modified bismaleimide resin comprises the following steps:
synthesizing a dinitro compound containing a benzene ring by using p-nitrochlorobenzene and a dihydroxy compound according to a mass ratio of (1.8-2.4) to 1; synthesizing a diamine compound by taking ethanol as a solvent and ferric trichloride as a catalyst and taking the mass ratio of a dinitro compound containing benzene rings to hydrazine hydrate at 70-90 ℃ as 1 (1.9-2.5);
mixing a diamine compound and maleic anhydride with the mass ratio of 1:2.5, and reacting to obtain a bismaleimide monomer containing ether bonds;
mixing potassium cyanide and liquid bromine according to the mass ratio of (0.8-1.4) to 1, and reacting at 0-5 ℃ to prepare cyanogen bromide; cyanogen bromide and dihydroxy compounds containing benzene rings are mixed, the mass ratio is 1:1, and the cyanate ester monomer containing the benzene rings is prepared by reaction at the temperature of-5 ℃;
blending bismaleimide monomer containing ether bond and cyanate ester monomer containing benzene ring, and carrying out first prepolymerization under the following conditions: stirring at the constant temperature of 110-130 ℃ for 10-30 min;
mixing the product obtained by the first prepolymerization with an allyl-containing compound and an amino-terminated hyperbranched polymer, and carrying out second prepolymerization; wherein the mass ratio of cyanate ester monomer containing benzene ring, bismaleimide monomer containing ether bond and amino-terminated hyperbranched polymer is (0.5-1): 1, (0.1-0.2), and the mass ratio of bismaleimide monomer containing ether bond and compound containing allyl is 1, (0.08-0.12); the conditions for the second prepolymerization were: stirring at the constant temperature of 110-130 ℃ for 20-40 min;
and (3) curing the product obtained by the second prepolymerization under the following curing conditions: performing vacuum defoaming at 125-150 deg.C for 20-40 min, and performing first stage curing, second stage curing and third stage curing;
wherein, the conditions of the first stage curing are as follows: keeping the temperature for 1 to 1.5 hours at the temperature of between 155 and 165 ℃;
the conditions for the second stage curing were: keeping the temperature at 180-190 ℃ for 1.5-2.5 h;
the conditions for the third stage curing are: keeping the temperature for 1.5 to 2.5 hours at 235 to 245 ℃.
Based on the preparation method, the invention also provides a modified bismaleimide resin. The modified bismaleimide resin has the advantages of strong toughness and rigidity, high temperature resistance, and small dielectric loss and dielectric constant.
Furthermore, the invention also provides an application of the modified bismaleimide resin in preparing a wave-transparent composite material. Specifically, the wave-transparent composite material is a composite material with integrated functions and structures of light, electricity, magnetism, heat and the like, and can be an antenna window material and an antenna cover material, and is not particularly limited herein.
The modified bismaleimide resin material and the preparation method thereof according to the present invention will be described in further detail with reference to the following specific examples. The starting materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
The embodiment provides a preparation method of a modified bismaleimide resin, which comprises the following specific steps:
s1: dropwise adding potassium cyanide and liquid bromine into the liquid bromine at a ratio of 1.1:1, controlling the reaction temperature at 0-5 ℃, and preparing cyanogen bromide; cyanogen bromide and dihydroxy Compound (CH) containing benzene ring2OHC6H4CH2CH2OH) is mixed in a ratio of 1:1, the reaction temperature is controlled at-5 to 5 ℃, and a high-temperature resistant cyanate ester monomer (CH) is synthesized under the action of a catalyst2OHC6H4CH2CH2OCN)；
S2: using p-nitrochlorobenzene and dihydroxy Compound (CH)2OHCH2CH2OH) in a mass ratio of 2.1:1 to form dinitro compounds (NO)2C6H4OCH2CH2CH2OC6H4NO2) (ii) a The ethanol is used as a solvent, and the ethanol,ferric trichloride as catalyst and dinitro compound (NO) containing benzene ring2C6H4CH2OCH2C6H4NO2) Synthesis of diamine Compound (NH) with hydrazine hydrate at 80 ℃ in a mass ratio of 1:2.22C6H4CH2OCH2C6H4NH2) (ii) a Diamine compound (NH) to be synthesized at room temperature2C6H4CH2OCH2C6H4NH2) The THF solution of (a) was added dropwise to a THF solution of maleic anhydride in a ratio of 1:2.5, to prepare a bismaleimide monomer (C) containing an ether bond by the reaction4H2O2NC6H4CH2OCH2C6H4C4H2O2N)；
S3: mixing gamma-aminopropyltriethoxysilane, distilled water and ethanol to form a solution, stirring at room temperature, heating the solution to 55 ℃ after 15min, and stirring for 5h while maintaining the temperature. Then putting the obtained product into a vacuum oven, and steaming at 60 ℃ to remove ethanol to obtain transparent viscous liquid, namely the amino-terminated hyperbranched polysiloxane;
s4: synthesizing high temperature resistant cyanate monomer (CH)2OHC6H4CH2CH2OCN), bismaleimide monomer containing ether bond (C)4H2O2NC6H4CH2OCH2C6H4C4H2O2N) are mixed according to the mass ratio of 1:2, stirred at the constant temperature of 120 ℃ for 20min, and added with amino-terminated hyperbranched polysiloxane and allyl bisphenol A catalyst, wherein the mass ratio of the amino-terminated hyperbranched polysiloxane to the bismaleimide is 0.2 and 0.1 respectively. Stirring at constant temperature of 120 ℃, pre-polymerizing for 0.5h, injecting the resin into a preheated mold, defoaming for 0.5h at 135 ℃, curing according to the process of 160 ℃/1h +185 ℃/2h +240 ℃/2h, and naturally cooling to normal temperature to obtain the cured resin.
Example 2
The embodiment provides a preparation method of a modified bismaleimide resin, which comprises the following specific steps:
s1: dropwise adding potassium cyanide and liquid bromine into the liquid bromine at a ratio of 1.1:1, controlling the reaction temperature at 0-5 ℃, and preparing cyanogen bromide; cyanogen bromide and dihydroxy Compound (CH) containing benzene ring2OHC6H4CH2CH2OH) is mixed in a ratio of 1:1, the reaction temperature is controlled at-5 to 5 ℃, and a high-temperature-resistant cyanate monomer (CH) is synthesized under the action of a catalyst2OHC6H4CH2CH2OCN)；
S2: using p-nitrochlorobenzene and dihydroxy Compound (CH)2OHC6H4CH2CH2OH) in a mass ratio of 2.1:1 to form dinitro compounds (NO)2C6H4OCH2CH2CH2OC6H4NO2) (ii) a Ethanol is used as solvent, ferric trichloride is used as catalyst, and benzene ring-containing dinitro compound (NO) is used2C6H4OCH2CH2CH2OC6H4NO2) Synthesis of diamine Compound (NH) with hydrazine hydrate at 80 ℃ in a mass ratio of 1:2.22C6H4CH2OCH2C6H4NH2) (ii) a Diamine compound (NH) to be synthesized at room temperature2C6H4CH2OCH2C6H4NH2) The THF solution of (a) was added dropwise to a THF solution of maleic anhydride in a ratio of 1:2.5, and a bismaleimide monomer (C) containing an ether bond was prepared by the reaction4H2O2NC6H4CH2OCH2C6H4C4H2O2N)；
S3: mixing gamma-aminopropyltriethoxysilane, distilled water and ethanol to form a solution, stirring at room temperature, heating the solution to 55 ℃ after 15min, and stirring for 5h while keeping the temperature. Then putting the obtained product into a vacuum oven, and steaming to remove ethanol at 60 ℃ to obtain transparent viscous liquid, namely the amino-terminated hyperbranched polysiloxane;
s4: the synthesized high-temperature resistant cyanate monomerBody (CH)2OHC6H4CH2CH2OCN), bismaleimide monomer containing ether bond (C)4H2O2NC6H4CH2OCH2C6H4C4H2O2N) mixing the materials according to the mass ratio of 1:1, stirring the mixture at the constant temperature of 120 ℃ for 20min, and adding the amino-terminated hyperbranched polysiloxane and the allyl bisphenol A catalyst, wherein the mass ratio of the amino-terminated hyperbranched polysiloxane to the bismaleimide is 0.2 and 0.1 respectively. Stirring at constant temperature of 120 ℃, pre-polymerizing for 0.5h, injecting the resin into a preheated mold, defoaming for 0.5h at 135 ℃, curing according to the process of 160 ℃/1h +185 ℃/2h +240 ℃/2h, and naturally cooling to normal temperature to obtain the cured resin.
Example 3
The embodiment provides a preparation method of a modified bismaleimide resin, which comprises the following specific steps:
s1: dropwise adding potassium cyanide and liquid bromine into the liquid bromine at a ratio of 1.1:1, controlling the reaction temperature at 0-5 ℃, and preparing cyanogen bromide; cyanogen bromide and dihydroxy Compound (CH) containing benzene ring2OHC6H4CH2CH2OH) is mixed in a ratio of 1:1, the reaction temperature is controlled at-5 to 5 ℃, and a high-temperature-resistant cyanate monomer (CH) is synthesized under the action of a catalyst2OHC6H4CH2CH2OCN)；
S2: using p-nitrochlorobenzene and dihydroxy Compound (CH)2OHCH2CH2OH) in a mass ratio of 2.1:1 to form dinitro compounds (NO)2C6H4OCH2CH2CH2OC6H4NO2) (ii) a Ethanol is used as solvent, ferric trichloride is used as catalyst, and benzene ring-containing dinitro compound (NO) is used2C6H4CH2OCH2C6H4NO2) Synthesis of diamine Compound (NH) with hydrazine hydrate at 80 ℃ in a mass ratio of 1:2.22C6H4CH2OCH2C6H4NH2) (ii) a Diamine compound (NH) to be synthesized at room temperature2C6H4CH2OCH2C6H4NH2) The THF solution of (a) was added dropwise to a THF solution of maleic anhydride in a ratio of 1:2.5, and a bismaleimide monomer (C) containing an ether bond was prepared by the reaction4H2O2NC6H4CH2OCH2C6H4C4H2O2N)；
S3: mixing gamma-aminopropyltriethoxysilane, distilled water and ethanol to form a solution, stirring at room temperature, heating the solution to 55 ℃ after 15min, and stirring for 5h while keeping the temperature. Then putting the obtained product into a vacuum oven, and steaming to remove ethanol at 60 ℃ to obtain transparent viscous liquid, namely the amino-terminated hyperbranched polysiloxane;
s4: synthesizing high temperature resistant cyanate monomer (CH)2OHC6H4CH2CH2OCN), bismaleimide monomer containing ether bond (C)4H2O2NC6H4CH2OCH2C6H4C4H2O2N) are mixed according to the mass ratio of 1:2, stirred at the constant temperature of 120 ℃ for 20min, and added with amino-terminated hyperbranched polysiloxane and allyl bisphenol A catalyst, wherein the mass ratio of the amino-terminated hyperbranched polysiloxane to the bismaleimide is 0.5 and 0.1 respectively. Stirring at constant temperature of 120 ℃, pre-polymerizing for 0.5h, injecting the resin into a preheated mold, defoaming for 0.5h at 135 ℃, curing according to the process of 160 ℃/1h +185 ℃/2h +240 ℃/2h, and naturally cooling to normal temperature to obtain the cured resin.
Example 4
The embodiment provides a preparation method of a modified bismaleimide resin, which comprises the following specific steps:
s1: dropwise adding potassium cyanide and liquid bromine into the liquid bromine at a ratio of 1.1:1, controlling the reaction temperature at 0-5 ℃, and preparing cyanogen bromide; cyanogen bromide and dihydroxy Compound (CH) containing benzene ring2OHC6H4CH2CH2OH) is mixed in a ratio of 1:1, the reaction temperature is controlled at-5 to 5 ℃, and a high-temperature-resistant cyanate monomer (CH) is synthesized under the action of a catalyst2OHC6H4CH2CH2OCN)；
S2: using p-nitrochlorobenzene and a dihydroxy Compound (CH)2OHCH2CH2OH) in a mass ratio of 2.1:1 to form dinitro compounds (NO)2C6H4OCH2CH2CH2OC6H4NO2) (ii) a Ethanol is used as solvent, ferric trichloride is used as catalyst, and benzene ring-containing dinitro compound (NO) is used2C6H4CH2OCH2C6H4NO2) Synthesis of diamine Compound (NH) with hydrazine hydrate at 80 ℃ in a mass ratio of 1:2.22C6H4CH2OCH2C6H4NH2) (ii) a Diamine compound (NH) to be synthesized at room temperature2C6H4CH2OCH2C6H4NH2) The THF solution of (a) was added dropwise to a THF solution of maleic anhydride in a ratio of 1:2.5, to prepare a bismaleimide monomer (C) containing an ether bond by the reaction4H2O2NC6H4CH2OCH2C6H4C4H2O2N)；
S3: mixing gamma-aminopropyltriethoxysilane, distilled water and ethanol to form a solution, stirring at room temperature, heating the solution to 55 ℃ after 15min, and stirring for 5h while keeping the temperature. Then putting the obtained product into a vacuum oven, and steaming to remove ethanol at 60 ℃ to obtain transparent viscous liquid, namely the amino-terminated hyperbranched polysiloxane;
s4: synthesizing high temperature resistant cyanate monomer (CH)2OHC6H4CH2CH2OCN), bismaleimide monomer containing ether bond (C)4H2O2NC6H4CH2OCH2C6H4C4H2O2N) mixing the materials according to the mass ratio of 0.5:1, stirring the mixture for 20min at the constant temperature of 120 ℃, adding the amino-terminated hyperbranched polysiloxane and the allyl bisphenol A catalyst, wherein the mass ratio of the amino-terminated hyperbranched polysiloxane to the bismaleimide is respectively0.2 and 0.1. Stirring at constant temperature of 120 ℃, prepolymerizing for 10min, injecting the resin into a preheated mold, defoaming in vacuum at 135 ℃ for 0.5h, curing according to the process of 160 ℃/1h +185 ℃/2h +240 ℃/2h, and naturally cooling to normal temperature to obtain the cured resin.
Comparative example 1
This example provides a comparative example of a modified bismaleimide resin as follows:
s1: dropwise adding potassium cyanide and liquid bromine into the liquid bromine at a ratio of 1.1:1, controlling the reaction temperature at 0-5 ℃, and preparing cyanogen bromide; cyanogen bromide and dihydroxy Compound (CH) containing benzene ring2OHC6H4CH2CH2OH) is mixed in a ratio of 1:1, the reaction temperature is controlled at-5 to 5 ℃, and a high-temperature-resistant cyanate monomer (CH) is synthesized under the action of a catalyst2OHC6H4CH2CH2OCN)；
S2: using p-nitrochlorobenzene and dihydroxy Compound (CH)2OHCH2CH2OH) in a mass ratio of 2.1:1 to form dinitro compounds (NO)2C6H4OCH2CH2CH2OC6H4NO2) (ii) a Ethanol is used as solvent, ferric trichloride is used as catalyst, and benzene ring-containing dinitro compound (NO) is used2C6H4CH2OCH2C6H4NO2) Synthesis of diamine Compound (NH) with hydrazine hydrate at 80 ℃ in a mass ratio of 1:2.22C6H4CH2OCH2C6H4NH2) (ii) a Diamine compound (NH) to be synthesized at room temperature2C6H4CH2OCH2C6H4NH2) The THF solution of (a) was added dropwise to a THF solution of maleic anhydride in a ratio of 1:2.5, and a bismaleimide monomer (C) containing an ether bond was prepared by the reaction4H2O2NC6H4CH2OCH2C6H4C4H2O2N)；
S3: synthesizing high temperature resistant cyanate monomer (CH)2OHC6H4CH2CH2OCN), bismaleimide monomer containing ether bond (C)4H2O2NC6H4CH2OCH2C6H4C4H2O2N) are mixed in a mass ratio of 0.5:1, stirred at a constant temperature of 120 ℃ for 20min, and an allyl bisphenol A catalyst is added, wherein the mass ratio of the allyl bisphenol A catalyst to the bismaleimide is 0.1. Stirring at constant temperature of 120 ℃, pre-polymerizing for 30min, injecting the resin into a preheated mold, defoaming for 0.5h at 135 ℃ in vacuum, curing according to the process of 160 ℃/1h +185 ℃/2h +240 ℃/2h, and naturally cooling to normal temperature to obtain the cured resin.
Comparative example 2
This example provides a comparative example of a modified bismaleimide resin as follows:
s1: dropwise adding potassium cyanide and liquid bromine into the liquid bromine at a ratio of 1.1:1, controlling the reaction temperature at 0-5 ℃, and preparing cyanogen bromide; cyanogen bromide and dihydroxy Compound (CH) containing benzene ring2OHC6H4CH2CH2OH) is mixed in a ratio of 1:1, the reaction temperature is controlled at-5 to 5 ℃, and a high-temperature-resistant cyanate monomer (CH) is synthesized under the action of a catalyst2OHC6H4CH2CH2OCN)；
S2: using p-nitrochlorobenzene and dihydroxy Compound (CH)2OHC6H4CH2CH2OH) in a mass ratio of 2.1:1 to form dinitro compounds (NO)2C6H4OCH2CH2CH2OC6H4NO2) (ii) a Ethanol is used as solvent, ferric trichloride is used as catalyst, and benzene ring-containing dinitro compound (NO) is used2C6H4OCH2CH2CH2OC6H4NO2) Synthesis of diamine Compound (NH) with hydrazine hydrate at 80 ℃ in a mass ratio of 1:2.22C6H4CH2OCH2C6H4NH2) (ii) a Diamine compound (NH) to be synthesized at room temperature2C6H4CH2OCH2C6H4NH2) The THF solution of (a) was added dropwise to a THF solution of maleic anhydride in a ratio of 1:2.5, and a bismaleimide monomer (C) containing an ether bond was prepared by the reaction4H2O2NC6H4CH2OCH2C6H4C4H2O2N)；
S3: mixing gamma-aminopropyltriethoxysilane, distilled water and ethanol to form a solution, stirring at room temperature, heating the solution to 55 ℃ after 15min, and stirring for 5h while keeping the temperature. Then putting the obtained product into a vacuum oven, and steaming to remove ethanol at 60 ℃ to obtain transparent viscous liquid, namely the amino-terminated hyperbranched polysiloxane;
s4: the synthesized high-temperature resistant cyanate ester monomer (CH)2OHC6H4CH2CH2OCN), bismaleimide monomer containing ether bond (C)4H2O2NC6H4CH2OCH2C6H4C4H2O2N) mixing the materials according to the mass ratio of 1:1, stirring the mixture at the constant temperature of 120 ℃ for 20min, and adding the amino-terminated hyperbranched polysiloxane and the allyl bisphenol A catalyst, wherein the mass ratio of the amino-terminated hyperbranched polysiloxane to the bismaleimide is 0.2 and 0.05 respectively. Stirring at constant temperature of 120 ℃, pre-polymerizing for 0.5h, injecting the resin into a preheated mold, defoaming for 0.5h at 135 ℃, curing according to the process of 160 ℃/1h +185 ℃/2h +240 ℃/2h, and naturally cooling to normal temperature to obtain the cured resin.
Effect test
The above examples 1 to 4 and comparative examples 1 to 2 were subjected to effect verification experiments including measurement of glass transition temperature, dielectric constant, dielectric loss, tensile strength and impact strength of the cured product.
Glass transition temperature measurement method: consistent with ASTM D7028;
dielectric constant measurement method: in accordance with ASTM D149;
the dielectric loss measuring method comprises the following steps: in accordance with ASTM D149;
tensile strength measurement method: is consistent with GB/T2567-;
the impact strength measurement method comprises the following steps: in accordance with GB/T2567-.
The process parameters and the results of the effect verification experiments of examples 1 to 4 and comparative examples 1 to 2 are shown in table 1.
TABLE 1
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of modified bismaleimide resin is characterized by comprising the following steps:
blending bismaleimide monomer containing ether bond and cyanate monomer containing benzene ring, and carrying out primary prepolymerization;
mixing the product obtained by the first prepolymerization with a catalyst and a thermoplastic toughening agent with a functional group at the end, and carrying out second prepolymerization;
curing the product obtained by the second prepolymerization;
wherein the mass ratio of the bismaleimide monomer containing ether bonds to the catalyst is 1 (0.08-0.12).
2. The method for preparing modified bismaleimide resin according to claim 1 wherein the thermoplastic toughening agent with functional groups at the end is an amino-terminated hyperbranched polymer.
3. The method for preparing a modified bismaleimide resin as claimed in claim 1 wherein the catalyst is an allyl group containing compound.
4. The method for preparing a modified bismaleimide resin according to claim 1, wherein the bismaleimide monomer having an ether bond is prepared by mixing a diamine compound and maleic anhydride and reacting the mixture; wherein the mass ratio of the diamine compound to the maleic anhydride is 1: 2.5.
5. The method for preparing modified bismaleimide resin as claimed in claim 1, wherein the cyanate ester monomer containing benzene ring is prepared by mixing cyanogen bromide with dihydroxy compound containing benzene ring and reacting; wherein the mass ratio of the cyanogen bromide to the dihydroxy compound containing the benzene ring is 1: 1.
6. The method for preparing the modified bismaleimide resin according to any one of claims 1 to 5, wherein the ratio of the cyanate ester monomer containing the benzene ring, the bismaleimide monomer containing the ether bond and the thermoplastic toughening agent with the functional group at the end is (0.5-1): 1 (0.1-0.2).
7. The method for preparing the modified bismaleimide resin according to any one of claims 1 to 5, wherein the first prepolymerization is carried out under the following conditions: stirring at the constant temperature of 110-130 ℃ for 30-50 min; the conditions for the second prepolymerization were: stirring at 110-130 deg.c for 30-50 min.
8. The process for producing a modified bismaleimide resin according to any one of claims 1 to 5 wherein the curing conditions are as follows: after vacuum defoaming is carried out for 20min to 40min at the temperature of 125 ℃ to 150 ℃, the first-stage curing, the second-stage curing and the third-stage curing are carried out in sequence;
wherein, the conditions of the first stage curing are as follows: keeping the temperature for 1 to 1.5 hours at the temperature of between 155 and 165 ℃;
the conditions for the second stage curing were: keeping the temperature at 180-190 ℃ for 1.5-2.5 h;
the conditions for the third stage curing are: keeping the temperature for 1.5 to 2.5 hours at 235 to 245 ℃.
9. A modified bismaleimide resin obtained by the method of any one of claims 1 to 8.
10. Use of the modified bismaleimide resin of claim 9 in the preparation of a wave-transparent composite or an antenna window product.
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