CN107474534B - Preparation method of cyanate foamed plastic - Google Patents

Preparation method of cyanate foamed plastic Download PDF

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CN107474534B
CN107474534B CN201710623576.7A CN201710623576A CN107474534B CN 107474534 B CN107474534 B CN 107474534B CN 201710623576 A CN201710623576 A CN 201710623576A CN 107474534 B CN107474534 B CN 107474534B
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cyanate ester
silazane
cyanate
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linear
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CN107474534A (en
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罗永明
徐彩虹
陈艳杰
李永明
张宗波
曾凡
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Abstract

The invention relates to a preparation method of cyanate ester foam plastic, belongs to the technical field of cyanate ester polymerization reaction, and prepares the cyanate ester foam plastic on the premise of not using a catalyst. Firstly, mixing cyanate ester and silazane, stirring uniformly, heating and preserving heat, carrying out foaming reaction, then raising the temperature of a reaction system, preserving heat, and carrying out crosslinking curing reaction on the cyanate ester foam plastic prepolymer to obtain the cyanate ester foam plastic. The preparation method of the cyanate ester foam plastic provided by the invention can be used for preparing the cyanate ester foam plastic.

Description

Preparation method of cyanate foamed plastic
Technical Field
The invention relates to a cyanate ester polymerization reaction, in particular to a preparation method of cyanate ester foam plastic.
Background
The cyanate foamed plastic is a high polymer material formed by dispersing a large number of gas micropores in cyanate resin, and has the advantages of light weight, heat insulation, sound insulation, low thermal conductivity, high specific strength, impact load absorption and the like. In addition, the cyanate ester resin can form a triazine ring structure after being cured, so that the cyanate ester foam plastic also has the advantages of excellent dimensional stability and thermal stability, excellent mechanical property and adhesive property, high glass transition temperature, low moisture absorption rate, low toxicity, low thermal expansion coefficient, low dielectric constant, small dielectric loss tangent value and the like, and is widely applied to the fields of aerospace, submarines, other light structure materials and the like.
In the prior art, the preparation method of the cyanate ester foam mainly comprises a cenosphere method, a foaming agent method and the like, but in the preparation process, catalysts are used in the preparation methods, and the catalysts are remained in the cyanate ester foam after the preparation is completed, so that the comprehensive properties of the cyanate ester foam in various aspects such as thermal stability, mechanical property, dielectric constant, dielectric loss tangent value and the like are influenced.
In addition, in the existing preparation method of the cyanate ester foam, the curing temperature of the cyanate ester is high (generally above 250 ℃), so that the safety of a reaction system is reduced, and energy is wasted.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a method for preparing cyanate ester foam, which can prepare cyanate ester foam without using a catalyst.
The purpose of the invention is mainly realized by the following technical scheme:
the invention provides a preparation method of cyanate ester foam plastic, which comprises the following steps:
step S1: mixing 100 parts by mass of a raw material cyanate with 5-30 parts by mass of a raw material silazane, and uniformly stirring to obtain a mixture of cyanate and silazane;
step S2: heating a mixture of cyanate and silazane, preserving heat, and carrying out foaming reaction to obtain a cyanate foamed plastic prepolymer;
step S3: and (4) increasing the temperature of the reaction system in the step S2, and preserving the temperature to enable the cyanate ester foam plastic prepolymer to perform a crosslinking curing reaction to obtain the cyanate ester foam plastic.
Further, the step S1 includes the following steps: mixing 100 parts by mass of raw material cyanate with 5-30 parts by mass of raw material silazane at 0-30 ℃, and uniformly stirring to obtain a mixture of cyanate and silazane.
Further, the step S2 includes the following steps: heating the mixture of cyanate and silazane to 50-100 ℃, and carrying out foaming reaction for 5-120 min to obtain cyanate foamed plastic prepolymer;
further, the step S3 includes the following steps: and (4) raising the temperature of the reaction system in the step S2 to 130-200 ℃, and preserving the temperature for 1-4 h to enable the cyanate ester foam plastic prepolymer to perform a crosslinking curing reaction to obtain the cyanate ester foam plastic.
Further, in step S1, the viscosity of the mixture of cyanate ester and silazane is 0.1-200 Pa.s.
Further, the raw material cyanate ester is liquid raw material cyanate ester or an organic solvent solution of the raw material cyanate ester; the silazane is a liquid silazane or an organic solvent solution of the silazane.
Further, the raw material cyanate ester is at least one of aliphatic cyanate ester and cyanate ester with general formulas (I-III); has the general formula (I)
General formula (II) is
Figure BDA0001362254980000032
Formula (III) is
Figure BDA0001362254980000033
In the formula R1～R8Is one of H, C1-C10 straight chain or branched chain alkyl, C3-C8 naphthenic base, C1-C10 alkoxy, halogen, phenyl or phenoxy;
R9is H or one of C1-C10 alkyl, n is an integer, n is more than or equal to 0 and less than or equal to 20;
z is a chemical bond, SO2、CF2、CH2、CHF、CH(CH3) Isopropylidene and hexafluoroIsopropylidene, C1-C10 alkylene, O, N ═ N, C ═ N, C ═ C, COO, C ═ N-N ═ C, alkyleneoxy having C1-C8 alkylene, S, Si (CH)3)2
Figure BDA0001362254980000041
Or one of the above.
Further, the raw material cyanate ester is at least one of phenylene-1, 3-dicyanate, phenylene-1, 4-dicyanate, 2,4, 5-trifluorophenylene-1, 3-dicyanate, 4 ' -bis (phenyl cyanate) methane, dicyclopentadiene type cyanate ester, 4 ' -bis (phenyl cyanate) isopropane, 2-bis (4-cyanate-phenyl) hexafluoropropane, cyclopentadiene type cyanate ester, phenol type cyanate ester, 4 ' -methylenediphenyl dicyanate ester, or general formula (IV);
formula (IV) is N ≡ C-O-R10-O-C≡N
In the formula R10Is C3-C12 aliphatic hydrocarbon group.
Further, the silazane as the raw material is a mixture of one or more of silazane, boron/aluminum silazane, carbosilazane and siloxanane.
Further, the silazanes have the formula
Figure BDA0001362254980000051
The general formula of the boron/aluminum-silicon-nitrogen alkane is
Figure BDA0001362254980000052
The silasiloxane has the general formula
Figure BDA0001362254980000053
Carbosilazanes of the general formula
Figure BDA0001362254980000061
In the formula R10、R11、R11'、R13、R13'、R15And R15'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl and linear or branched alkenylaryl;
R10'is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl and a general formula (V)
Figure BDA0001362254980000062
R12And R12'Is one of alkyl and phenyl of H, C1-C4;
R14and R14'Is one of H, linear or branched alkyl, linear or branched alkenyl and general formula (VI)
Figure BDA0001362254980000063
R16Is an alkylene group of C1 to C10;
m is B or Al;
m, k, p, q, o and s are integers; m is more than or equal to 0 and less than or equal to 2000, k is more than or equal to 0 and less than or equal to 2000, when m is equal to 0, 15k is not equal to 0, and when k is equal to 0, m is not equal to 0; s is more than or equal to 1 and less than or equal to 50; p is more than or equal to 1 and less than or equal to 100; q is more than or equal to 0 and less than or equal to 2000, and o is more than or equal to 1 and less than or equal to 1000.
Compared with the prior art, the invention has the following beneficial effects:
a) according to the preparation method of the cyanate ester foam plastic, the raw material silazane can be subjected to in-situ reaction with the raw material cyanate ester to generate gas for nucleation, aggregation and foaming, and the raw material silazane can be used as a catalyst to catalyze the cyanate ester foam plastic prepolymer to carry out a crosslinking curing reaction, so that the catalyst is not needed in the preparation process, the problem of catalyst residue of the cyanate ester foam plastic is solved, and the comprehensive performance of the cyanate ester foam plastic is improved.
b) The cyanate foamed plastic prepared by the preparation method provided by the invention has the advantages of light weight, heat insulation, sound insulation, low thermal conductivity, high specific strength, impact load absorption, excellent dimensional stability and thermal stability, excellent mechanical property and adhesive property, high glass transition temperature, low moisture absorption rate, low toxicity, low thermal expansion coefficient, low dielectric constant, small dielectric loss tangent value and the like.
c) The preparation method of the cyanate ester foam plastic provided by the invention is simple and convenient to operate, low in curing temperature, high in reaction system safety and more suitable for industrial production.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a diagram showing the results of DSC tests of the reaction process in the preparation method of cyanate ester foam of the present invention.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention.
In a first aspect, the present invention provides a cyanate ester foam, wherein the cyanate ester foam comprises the following raw materials, by mass: 100 parts of cyanate and 5-30 parts of silazane.
Compared with the prior art, the cyanate ester foam plastic provided by the invention can be nucleated, aggregated and foamed by gas generated by the in-situ reaction of the raw material silazane and the raw material cyanate ester, and the raw material silazane can be used as a catalyst to catalyze the cyanate ester foam plastic prepolymer to carry out a crosslinking curing reaction, so that the catalyst is not needed in the preparation process, the problem of catalyst residue of the cyanate ester foam plastic is solved, and the comprehensive performance of the cyanate ester foam plastic is improved. The cyanate foamed plastic has the advantages of light weight, heat insulation, sound insulation, low thermal conductivity, high specific strength, impact load absorption, excellent dimensional stability and thermal stability, excellent mechanical property and adhesive property, high glass transition temperature, low moisture absorption rate, low toxicity, low thermal expansion coefficient, low dielectric constant, small dielectric loss tangent value and the like.
In order to improve the performance of the cyanate ester plastic foam in certain aspects, the cyanate ester plastic foam further comprises the following raw materials in parts by mass: 1 to 30 parts of filler (such as titanium dioxide, iron powder and tin foil) and 1 to 10 parts of fiber.
Illustratively, the mass part of the filler can be 4-6 parts, and the mass part of the fiber can be 10-10 parts.
The structures of the raw cyanate ester and the raw silazane will be described in detail below.
The cyanate ester may be one or more of a mixture of bifunctional or multifunctional cyanate ester monomer, cyanate ester oligomer, cyanate ester polymer, and modified cyanate ester, for example, at least one of aliphatic cyanate ester and cyanate ester of general formulas (I-III).
Has the general formula (I)
Figure BDA0001362254980000091
In the formula R1～R4Is one of H, C1-C10 straight chain or branched chain alkyl, C3-C8 naphthenic base, C1-C10 alkoxy, halogen (such as F, Cl, Br or I), phenyl or phenoxy, wherein, the C1-C10 straight chain or branched chain alkyl, C3-C8 naphthenic base, C1-C10 alkoxy, phenyl and phenoxy can be completely fluorinated or partially fluorinated. In addition, R is1～R4May be the same or different and are not limited herein.
Illustratively, the cyanate ester of the general formula (I) may be phenylene-1, 3-dicyanate, phenylene-1, 4-dicyanate, 2,4, 5-trifluorophenylene-1, 3-dicyanate.
General formula (II) is
Figure BDA0001362254980000092
In the formula R1～R8Is one of H, C1-C10 straight chain or branched chain alkyl, C3-C8 naphthenic base, C1-C10 alkoxy, halogen (such as F, Cl, Br or I), phenyl or phenoxy, wherein, the C1-C10 straight chain or branched chain alkyl, C3-C8 naphthenic base, C1-C10 alkoxy, phenyl and phenoxy can be completely fluorinated or partially fluorinated. In addition, R is1～R8May be the same or different and are not limited herein.
Z is a chemical bond, SO2、CF2、CH2、CHF、CH(CH3) Isopropylidene, hexafluoroisopropylidene, C1-C10 alkylene, O, N ═ N, C ═ N, C ═ C, COO, C ═ N-N ═ C, alkyleneoxy having C1-C8 alkylene, S, Si (CH)3)2
Figure BDA0001362254980000101
Figure BDA0001362254980000102
One kind of (1).
Illustratively, the raw cyanate ester of the general formula (II) may be 4,4 ' -bis (phenyl cyanate) methane, dicyclopentadiene type cyanate ester, 4 ' -bis (phenyl cyanate) isopropane (B10), 2-bis (4-cyanate-phenyl) hexafluoropropane, 4 ' -bis (phenyl cyanate) ethane (L10), or cyclopentadiene type cyanate ester.
Formula (III) is
Figure BDA0001362254980000111
In the formula R9Is one of H or C1-C10 alkyl, n is an integer，0≤n≤20。
Illustratively, the raw cyanate ester of the general formula (III) may be a novolac-type cyanate ester (N10) or 4, 4' -methylene diphenyl dicyanate.
The aliphatic cyanate may be a cyanate of the general formula (IV) which is
N≡C-O-R10-O-C≡N
In the formula R10Is an aliphatic hydrocarbon group, wherein the aliphatic hydrocarbon group may be fully fluorinated or partially fluorinated. Illustratively, the aliphatic hydrocarbon group may be a C3-C12 aliphatic hydrocarbon group.
As the raw material silazane, it may be one or a mixture of more of silazane, boron/aluminum silazane, carbosilazane, siloxanane, modified silicon nitrogen compounds containing a silicon-nitrogen bond.
The silicon nitrogen compound may be a silicon nitrogen oligomer having 2 to 10 silicon atoms in the molecular structure or a silicon nitrogen polymer containing at least 11 silicon atoms in the molecular structure.
Wherein the silazane has the formula
Figure BDA0001362254980000121
Wherein m and k are integers, 0. ltoreq. m.ltoreq.2000, 0. ltoreq. k.ltoreq.2000, when m is 0, k. noteq.0, when k is 0, m. ltoreq.0, for example, 5. ltoreq. m.ltoreq.25, 5. ltoreq. k.ltoreq.25; r10、R11、R11'、R13And R13'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl and linear or branched alkenylaryl; r12And R12'Is one of alkyl and phenyl of H, C1-C4; r10'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl and a general formula (V)
Figure BDA0001362254980000122
In addition, R is10、R10′、R11、R11′、R12、R12′、R13And R13′May be the same or different and are not limited herein.
The general formula of the boron/aluminum-silicon-nitrogen alkane is
Figure BDA0001362254980000124
Wherein m and k are integers, 0. ltoreq. m.ltoreq.2000, 0. ltoreq. k.ltoreq.2000, when m is 0, k. noteq.0, when k is 0, m. ltoreq.0, for example, 5. ltoreq. m.ltoreq.25, 5. ltoreq. k.ltoreq.25; m is B or Al; r10、R11、R11'、R13And R13'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl and linear or branched alkenylaryl; r12'Is one of alkyl and phenyl of H, C1-C4; r10'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl and a general formula (V)
Figure BDA0001362254980000131
R14And R14'Is one of H, linear or branched alkyl, linear or branched alkenyl and general formula (VI)
Figure BDA0001362254980000132
Wherein s is an integer, 1. ltoreq. s.ltoreq.50, for example, 1. ltoreq. s.ltoreq.10.
In addition, R is10、R10'、R11、R11'、R12'、R13And R13'、R14And R14'May be the same or different and are not limited herein.
The silasiloxane has the general formula
Figure BDA0001362254980000141
Wherein m, k, p are integers, 0. ltoreq. m.ltoreq.2000, 0. ltoreq. k.ltoreq.2000, 1. ltoreq. p.ltoreq.100, when m is 0, k.noteq.0, when k is 0, m.ltoreq.0, for example, 5. ltoreq. m.ltoreq.25, 5. ltoreq. k.ltoreq.25, 1. ltoreq. p.ltoreq.20; r10、R11、R11'、R13、R13'、R15And R15'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl and linear or branched alkenylaryl; r12、R12'Is one of alkyl and phenyl of H, C1-C4; r10'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl and a general formula (V)
Figure BDA0001362254980000142
In addition, R is10、R10'、R11、R11'、R12、R12'、R13And R13'、R14、R14'、R15And R15'May be the same or different and are not limited herein.
Carbosilazanes of the general formula
Figure BDA0001362254980000143
Wherein q and o are integers, 0. ltoreq. q.ltoreq.2000, 1. ltoreq. o.ltoreq.1000, for example, 5. ltoreq. q.ltoreq.25, 5. ltoreq. o.ltoreq.30; r10、R11、R11'、R13And R13'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl and linear or branched alkenylaryl; r12、R12'Alkyl of H, C1-C4One of phenyl and phenyl; r16Alkylene group having C1 to C10 (for example, ethylene group); r10'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl and a general formula (V)
Figure BDA0001362254980000151
In addition, R is10、R10'、R11、R11'、R12、R12'、R13And R13'May be the same or different and are not limited herein.
On the other hand, the invention also provides a preparation method of the cyanate ester foam plastic, which comprises the following steps:
step S1: mixing 100 parts by mass of a raw material cyanate with 5-30 parts by mass of a raw material silazane, and uniformly stirring to obtain a mixture of cyanate and silazane;
step S2: heating a mixture of cyanate and silazane, preserving heat, and carrying out foaming reaction to obtain a cyanate foamed plastic prepolymer;
step S3: and (4) increasing the temperature of the reaction system in the step S2, and preserving the temperature to enable the cyanate ester foam plastic prepolymer to perform a crosslinking curing reaction to obtain the cyanate ester foam plastic.
Compared with the prior art, the preparation method of the cyanate ester foam plastic provided by the invention can carry out nucleation, aggregation and foaming through gas generated by in-situ reaction of the raw material silazane and the raw material cyanate ester, and the raw material silazane can be used as a catalyst to catalyze the cyanate ester foam plastic prepolymer to carry out crosslinking curing reaction, so that the catalyst is not needed in the preparation process, the problem of catalyst residue of the cyanate ester foam plastic is solved, and the comprehensive performance of the cyanate ester foam plastic is improved. The cyanate ester foam plastic prepared by the preparation method has the advantages of light weight, heat insulation, sound insulation, low thermal conductivity, high specific strength, impact load absorption, excellent dimensional stability and thermal stability, excellent mechanical property and adhesive property, high glass transition temperature, low moisture absorption rate, low toxicity, low thermal expansion coefficient, low dielectric constant, small dielectric loss tangent value and the like. In addition, the preparation method of the cyanate ester foam plastic is simple and convenient to operate, low in curing temperature, high in reaction system safety and more suitable for industrial production.
The differential scanning thermal analysis (DSC) is used to test the reaction process of the above preparation method, and the DSC test result is shown in fig. 1, and as can be seen from fig. 1, the DSC curve includes two exothermic peaks, where the exothermic peak at about 50-100 ℃ is the exothermic peak of the foaming reaction of the raw material cyanate ester and the raw material silazane, and the exothermic peak at about 130-200 ℃ is the exothermic peak of the crosslinking curing reaction of the cyanate ester foam prepolymer, which indicates that the foaming reaction and the crosslinking curing reaction of the raw material cyanate ester and the raw material silazane can occur by using the above preparation method.
In order to ensure that the cyanate ester and the silazane can be sufficiently reacted, in step S1, the viscosity of the mixture of cyanate ester and silazane is 0.1 to 200 pa.s. The cyanate may be a liquid cyanate or an organic solvent solution of cyanate, and the silazane may be a liquid silazane or an organic solvent solution of silazane.
Specifically, the preparation method of the cyanate ester foam comprises the following steps:
step S11: mixing 100 parts by mass of raw material cyanate with 5-30 parts by mass of raw material silazane at 0-30 ℃, and uniformly stirring to obtain a mixture of cyanate and silazane;
step S12: heating the mixture of cyanate and silazane to 50-100 ℃, and carrying out foaming reaction for 5-120 min to obtain cyanate foamed plastic prepolymer;
step S13: and (4) raising the temperature of the reaction system in the step S2 to 130-200 ℃, and preserving the temperature for 1-4 h to enable the cyanate ester foam plastic prepolymer to perform a crosslinking curing reaction to obtain the cyanate ester foam plastic.
In step S13, the length of the incubation time is related to the temperature of the reaction system, that is, the temperature of the reaction system is high, the incubation time is short, the temperature of the reaction system is low, and the incubation time is long, which is not limited herein.
Example 1
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 5 parts by mass of silazane (silazane) with the structural formula (a), uniformly stirring and mixing the silazane by using magnetic force at the water bath temperature of 10 ℃, then putting the mixture into an oven, keeping the temperature at 60 ℃ for 60min, heating to 150 ℃, keeping the temperature for 2 hours, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
The cyanate ester foam of example 1 had a density of 0.52g/cm as determined by testing3The porosity was 52.7%.
Example 2
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 10 parts by mass of silazane, wherein the structural formula of the silazane is (a), uniformly stirring and mixing the silazane by magnetic force at the water bath temperature of 10 ℃, then putting the mixture into an oven, keeping the temperature at 60 ℃ for 60min, heating to 150 ℃, keeping the temperature for 2 hours, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000172
The cyanate ester foam of example 2 had a density of 0.48g/cm as determined by testing3The porosity was 56.4%.
Example 3
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 15 parts by mass of silazane (silazane) with the structural formula (a), uniformly stirring and mixing the silazane by using magnetic force at the water bath temperature of 10 ℃, then putting the mixture into an oven, keeping the temperature at 60 ℃ for 60min, heating to 150 ℃, keeping the temperature for 2 hours, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000181
The cyanate ester foam of example 3 had a density of 0.42g/cm as determined by testing3The porosity was 61.8%.
Example 4
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of silazane (silazane) with the structural formula (a), uniformly stirring and mixing the silazane by using magnetic force at the water bath temperature of 10 ℃, then putting the mixture into an oven, keeping the temperature at 60 ℃ for 60min, heating to 150 ℃, keeping the temperature for 2 hours, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000182
The cyanate ester foam of example 4 had a density of 0.30g/cm as determined by testing3The porosity was 72.7%.
Example 5
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 25 parts by mass of silazane (silazane) with the structural formula (a), uniformly stirring and mixing the silazane by using magnetic force at the water bath temperature of 10 ℃, then putting the mixture into an oven, keeping the temperature at 60 ℃ for 60min, heating to 150 ℃, keeping the temperature for 2 hours, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000191
The cyanate ester foam of example 5 had a density of 0.36g/cm as determined by testing3The porosity was 67.3%.
Example 6
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 30 parts by mass of silazane (silazane) with the structural formula (a), uniformly stirring and mixing the silazane by using magnetic force at the water bath temperature of 10 ℃, then putting the mixture into an oven, keeping the temperature at 60 ℃ for 60min, heating to 150 ℃, keeping the temperature for 2 hours, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000192
The cyanate ester foam of example 6 had a density of 0.41g/cm as determined by testing3The porosity was 62.7%.
Example 7
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of silazane (structural formula (b)), uniformly stirring and mixing the silazane by using magnetic force in an ice water bath (0 ℃), then putting the mixture into an oven, preserving heat at 70 ℃ for 30min, heating to 170 ℃, preserving heat for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000201
The cyanate ester foam of example 7 had a density of 0.33g/cm as determined by testing3The porosity was 70%.
Example 8
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of silazane (structural formula (c)), uniformly stirring and mixing the silazane by using magnetic force in an ice water bath (0 ℃), then putting the mixture into an oven, preserving the temperature at 70 ℃ for 30min, heating to 170 ℃, preserving the temperature for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000202
The cyanate ester foam of example 8 had a density of 0.32g/cm as determined by testing3The porosity was 70.9%.
Example 9
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of silazane (structural formula (d)), uniformly stirring and mixing the silazane by using magnetic force in an ice water bath (0 ℃), then putting the mixture into an oven, preserving the temperature at 70 ℃ for 30min, heating to 170 ℃, preserving the temperature for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000211
The cyanate ester foam of example 9 had a density of 0.39g/cm as determined by testing3The porosity was 64.5%.
Example 10
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of silazane, wherein the silazane has the structural formula (c) and the structural formula (d), and the mass ratio of the silazane with the structural formula (c) to the silazane with the structural formula (d) is 1: 1, uniformly stirring and mixing the materials by using magnetic force in an ice-water bath (0 ℃), then putting the materials into an oven, preserving the heat for 30min at 70 ℃, heating the materials to 170 ℃, preserving the heat for 2 hours, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000221
The cyanate ester foam of example 10 had a density of 0.34g/cm as determined by testing3The porosity was 69.1%.
Example 11
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of silazane (structural formula (d)), uniformly stirring and mixing the silazane by using magnetic force at the water bath temperature of 25 ℃, then putting the mixture into an oven, keeping the temperature at 90 ℃ for 20min, heating to 200 ℃, keeping the temperature for 1 hour, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000222
The cyanate ester foam of example 11 had a density of 0.28g/cm as determined by testing3The porosity was 74.5%.
Example 12
Mixing 100 parts by mass of a mixture of 4,4 '-methylene diphenyl dicyanate and 4, 4' -bis (phenyl cyanate) ethane with 20 parts by mass of silazane, wherein the mass ratio of the 4,4 '-methylene diphenyl dicyanate to the 4, 4' -bis (phenyl cyanate) ethane is 2: and (3) silazane with the structural formula (d) is uniformly stirred and mixed by magnetic force in an ice water bath (0 ℃), then the mixture is put into an oven, the temperature is kept for 30min at 70 ℃, the temperature is raised to 170 ℃, the temperature is kept for 2 hours, and crosslinking curing reaction is carried out to obtain the cyanate ester foamed plastic.
Figure BDA0001362254980000231
The cyanate ester foam of example 12 had a density of 0.36g/cm as determined by testing3The porosity was 67.3%.
Example 13
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of borosilazane, wherein the structural formula of the borosilazane is (e), uniformly stirring and mixing the mixture by using magnetic force in an ice water bath (0 ℃), then putting the mixture into an oven, preserving the heat for 30min at 70 ℃, heating to 170 ℃, preserving the heat for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000232
The cyanate ester foam of example 13 had a density of 0.34g/cm as determined by testing3The porosity was 69.1%.
Example 14
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of siloxazane, wherein the structural formula of the siloxazane is (f), uniformly stirring and mixing the mixture by using magnetic force in an ice water bath (0 ℃), then putting the mixture into an oven, preserving heat for 30min at 70 ℃, heating to 170 ℃, preserving heat for 2 hours, and carrying out crosslinking curing reaction to obtain the cyanate foamed plastic.
It can be seen from the tests that the density of the cyanate ester foam of example 14 is 0.40g/cm3The porosity was 63.6%.
Example 15
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of carbosilazane, wherein the structural formula of the carbosilazane is shown as (g), stirring and mixing uniformly by magnetic force in an ice-water bath (0 ℃), then putting the mixture into an oven, keeping the temperature at 70 ℃ for 30min, heating to 170 ℃, keeping the temperature for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000242
It can be seen from the tests that the density of the cyanate ester foam of example 15 is 0.38g/cm3The porosity was 65.4%.
Example 16
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of carbosilazane, wherein the structural formula of the carbosilazane is shown as (g), stirring and mixing uniformly by magnetic force at the water bath temperature of 30 ℃, then putting the mixture into an oven, keeping the temperature at 50 ℃ for 120min, heating to 130 ℃, keeping the temperature for 4 hours, and carrying out cross-linking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000251
It can be seen from the tests that the density of the cyanate ester foam of example 16 is 0.39g/cm3The porosity was 65.1%.
Example 17
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of carbosilazane, wherein the structural formula of the carbosilazane is shown as (g), stirring and mixing uniformly by magnetic force at the water bath temperature of 30 ℃, then putting the mixture into an oven, keeping the temperature at 100 ℃ for 5min, heating to 200 ℃, keeping the temperature for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000252
It can be seen from the tests that the density of the cyanate ester foam of example 17 is 0.41g/cm3The porosity was 63.1%.
Example 18
100 parts of cyanate ester and 20 parts of carbosilazane are mixed by mass, the structural formula of the cyanate ester is (h), the structural formula of the carbosilazane is (a), the mixture is stirred and mixed uniformly by magnetic force under the condition that the water bath temperature is 30 ℃, then the mixture is put into an oven, the temperature is kept for 5min at 100 ℃, the temperature is raised to 200 ℃, the temperature is kept for 2 hours, and the crosslinking curing reaction is carried out, so that the cyanate ester foamed plastic is obtained.
(h)
Figure BDA0001362254980000261
The cyanate ester foam of example 17 had a density of 0.38g/cm as determined by testing3The porosity was 66.5%.
Example 19
Mixing 100 parts of cyanate ester with 20 parts of silazane, wherein the structural formula of the cyanate ester is (I) and the structural formula of the silazane is (a), uniformly stirring and mixing the cyanate ester and the silazane by magnetic force at the water bath temperature of 15 ℃, then putting the mixture into an oven, keeping the temperature at 80 ℃ for 40min, heating to 170 ℃, keeping the temperature for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate ester foamed plastic.
Figure BDA0001362254980000262
It can be seen from the tests that the density of the cyanate ester foam of example 19 is 0.40g/cm3The porosity was 65.2%.
Example 20
Mixing 100 parts of cyanate ester and 20 parts of silazane, wherein the structural formula of the cyanate ester is (J) and the structural formula of the silazane is (f), stirring and mixing uniformly by magnetic force at the water bath temperature of 30 ℃, then placing the mixture into an oven, keeping the temperature at 100 ℃ for 20min, heating to 200 ℃, keeping the temperature for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate ester foam plastic.
Figure BDA0001362254980000271
It can be seen from the tests that the density of the cyanate ester foam of example 20 is 0.42g/cm3The porosity was 63.6%.
Example 21
Mixing 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane and 20 parts by mass of borosilazane, wherein the structural formula of the aluminosilazane is (k), uniformly stirring and mixing the mixture by using magnetic force in an ice water bath (0 ℃), then putting the mixture into an oven, preserving the heat for 30min at 70 ℃, heating to 170 ℃, preserving the heat for 2 hours, and carrying out cross-linking curing reaction to obtain the cyanate foamed plastic.
Figure BDA0001362254980000281
It can be seen from the tests that the density of the cyanate ester foam of example 21 is 0.35g/cm3The porosity was 68.1%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (5)

1. A preparation method of cyanate ester foam plastic is characterized in that gas is generated through in-situ reaction of raw material silazane and raw material cyanate ester for nucleation, aggregation and foaming, the raw material silazane is used as a catalyst to catalyze cyanate ester foam plastic prepolymer to carry out crosslinking curing reaction, and the preparation method comprises the following steps:
step S1: mixing 100 parts by mass of a raw material cyanate and 5-30 parts by mass of a raw material silazane at 0-30 ℃, and uniformly stirring to obtain a mixture of cyanate and silazane;
step S2: heating the mixture of cyanate and silazane to 50-100 ℃, preserving heat, and carrying out foaming reaction for 5-120 min to obtain cyanate foamed plastic prepolymer;
step S3: raising the temperature of the reaction system in the step S2 to 130-200 ℃, and preserving the temperature for 1-4 h to ensure that the cyanate ester foam plastic prepolymer generates a crosslinking curing reaction to obtain cyanate ester foam plastic;
the silazane as the raw material is one or a mixture of more of silazane, boron/aluminum silazane, carbon silazane and silicon oxynitrilane;
the silazane has the formula
Figure FDA0002281091580000011
The general formula of the boron/aluminum-silicon-nitrogen alkane is shown in the specification
Figure FDA0002281091580000012
The silasiloxane has the general formula
Figure FDA0002281091580000021
The carbosilazane has the general formula
Figure FDA0002281091580000022
In the formula R10、R11、R11'、R13、R13'、R15And R15'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl and linear or branched alkenylaryl;
R10'is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl and a general formula (V)
Figure FDA0002281091580000023
R12And R12'Is one of alkyl and phenyl of H, C1-C4;
R14and R14'Is one of H, linear or branched alkyl, linear or branched alkenyl and general formula (VI)
Figure FDA0002281091580000031
R16Is an alkylene group of C1 to C10;
m is B or Al;
m, k, p, q, o and s are integers; m is more than or equal to 0 and less than or equal to 2000, k is more than or equal to 0 and less than or equal to 2000, when m is equal to 0, k is not equal to 0, and when k is equal to 0, m is not equal to 0; s is more than or equal to 1 and less than or equal to 50; p is more than or equal to 1 and less than or equal to 100; q is more than or equal to 0 and less than or equal to 2000, and o is more than or equal to 1 and less than or equal to 1000.
2. The method for preparing cyanate ester foam according to claim 1, wherein in step S1, the viscosity of the mixture of cyanate ester and silazane is 0.1 to 200 pa.s.
3. The method for preparing cyanate ester foam according to claim 1, wherein the raw cyanate ester is a liquid raw cyanate ester or an organic solvent solution of the raw cyanate ester;
the raw material silazane is liquid raw material silazane or an organic solvent solution of the raw material silazane.
4. The method for preparing cyanate ester foam according to claim 1, wherein the raw material cyanate ester is at least one of aliphatic cyanate ester and cyanate ester of general formulas (I to III);
has the general formula (I)
Figure FDA0002281091580000032
General formula (II) is
Figure FDA0002281091580000041
Formula (III) is
In the formula R1～R8Is one of H, C1-C10 straight chain or branched chain alkyl, C3-C8 naphthenic base, C1-C10 alkoxy, halogen, phenyl or phenoxy;
R9is H or one of C1-C10 alkyl, n is an integer, n is more than or equal to 0 and less than or equal to 20;
z is a chemical bond, SO2、CF2CHF, hexafluoroisopropylidene, C1-C10 alkylene, O, N ═ N, C ═ N, C ═ C, COO, C ═ N — N ═ C, alkyleneoxy having C1-C8 alkylene, S, Si (CH)3)2
Or N-R9
Or
Figure FDA0002281091580000051
Or
Figure FDA0002281091580000052
Figure FDA0002281091580000053
Or one of the above.
5. The method for producing a cyanate ester foam according to claim 4, wherein said raw material cyanate ester is at least one of phenylene-1, 3-dicyanate, phenylene-1, 4-dicyanate, 2,4, 5-trifluorophenylene-1, 3-dicyanate, 4 ' -bis (phenylcyanate) methane, 4 ' -bis (phenylcyanate) isopropane, 2-bis (4-cyanate-phenyl) hexafluoropropane, 4 ' -methylenediphenyl dicyanate, or general formula (IV);
general formula (IV) is
Figure FDA0002281091580000054
In the formula R10Is C3-C12 aliphatic hydrocarbon group.
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