CN106046783A - Boride ceramic in-situ filling cyanate ester resin base composite material and preparation method thereof - Google Patents
Boride ceramic in-situ filling cyanate ester resin base composite material and preparation method thereof Download PDFInfo
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- CN106046783A CN106046783A CN201610611960.0A CN201610611960A CN106046783A CN 106046783 A CN106046783 A CN 106046783A CN 201610611960 A CN201610611960 A CN 201610611960A CN 106046783 A CN106046783 A CN 106046783A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention belongs to the technical field of an advanced composite material science, and particularly relates to a boride ceramic in-situ filling cyanate ester resin base composite material and a preparation method thereof. By an in-situ polymerization method, firstly, bisphenol A is dissolved in a benzene or alkane type organic solvent; a certain amount of cyanogen halide is added; mechanical stirring is performed in an environment being -10 to 0 DEG C to obtain a mixed solution; under the strong stirring, metal boride ceramic powder is added into the mixed solution; the stirring is continuously performed; at -10 to 0 DEG C, triethylamine is dropwise added into the system; the system takes polymerization; after the organic solvent is removed through distillation, metal boride powder in-situ filling cyanate ester resin is obtaine; then, a catalyst is added for stirring; after vacuum degassing treatment, curing formation is performed at a high temperature. The prepared metal boride in-situ filling cyanate ester resin base composite material has the structure performance characteristics of uniform material tissue, heat resistance and excellent heat conduction performance, and can be used as a base board material, an encapsulating material and the like of a printed circuit board in electronic equipment for space navigation industry and aerospace industry.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of boride ceramics filling in situ cyanate resin base multiple
Condensation material and preparation method thereof.
Background technology
Along with high power, the highly integrated and development of miniaturization of modern microelectronics devices, in commercial Application electronic equipment
Heat radiation and the stability in time of baseplate material, encapsulating material etc. seem most important.Cyanate (Cyanate Ester, CE)
Resin is as a kind of important high-performance thermosetting resin, owing to it has good thermostability, relatively low dielectric constant and Jie
The combination properties such as electrical loss and good weatherability, at high performance print circuit board, aerospace structure member, stealth material, radar
The advanced technology such as antenna house and artificial satellite field has broad application prospects.Cyanate ester monomer is after solidification crosslinking, and it is tied
There is the 1,3,5-triazines ring structure of high structural stability, low polarity in structure, even compact structure makes cyanate ester resin solid
After change, fragility is big, heat conductivility is poor, produces violent temperature rise because not dispelling the heat in time and then causes material under high loading conditions
Structure and performance failure, it is difficult to meet the structure actual requirement to material property under hot environment so that it is application is by certain
Limit.To cyanate resin modifier, as utilize thermosetting resin, thermoplastic resin, rubber elastomer, containing unsaturated double-bond chemical combination
Thing and inorganic filler etc. have been carried out substantial amounts of research work, and research focuses mostly on to toughening modification of cyanate ester resin.Wherein
Utilize inorganic ceramic filling modifier cyanate organic resin hot property, particularly improve the mechanical property under its high temperature, lead
Hot property is a kind of more effective method.Research shows, inorganic ceramic filling modifier organic resin has merged inorganic pottery
Heat conduction heat resistance and the high flexibility of organic resin, machinability that porcelain is excellent can significantly improve organic resin material and bear at height
Heat conductivility under lotus.From the point of view of previous research, the inorganic filler for filling-modified cyanate ester resin is concentrated mainly on carbon
Nanotube, Graphene, SiO2、TiO2With BN etc., material preparation mainly uses the method that physical mechanical is blended, and for profit
Then it is rarely reported with the research of boride ceramics particularly metal boride ceramic filler modified cyanic acid ester, especially by situ
Polymerization is prepared the research of the filling-modified cyanate ester resin composite material of high-thermal conductive metal boride ceramics and is the most not yet seen
Report.
List of references:
[1] Caifei Han, Aijuan Gu, Guozheng Liang, Li Yuan. Carbon nanotubes/
cyanate ester composites with low percolation threshold, high dielectric
constant and outstanding thermal property[J].Composites: Part A, 2010,41:
1321-1328
[2] Qilang Lin, Lijuan Qu, Qiufeng lu. Preparation and properties of
graphene oxide nanosheets/cyanate ester resin composites[J]. Polymer Testing,
2013, 32: 330-337
[3] Tim J. Wooster, Simmi Abrol, Jeffrey M. Hey, Douglas R. MacFarlane.
The effect of particle matrix adhesion on the mechanical properties of silica
filled cyanate ester composites[J]. Macromol. Mater. Eng. 2004, 289:872-879
[4] Jingwen Li, Zhixiong Wu, Chuanjun Huang, etc.Mechanical properties of
cyanate ester/epoxy nanocomposites modified with plasma functionalized MWCNTs
[J]. Composites Science and Technology, 2014,90:166-173
[5] John N. Suman, John Kathi, Shekharam Tammishetti.Thermoplastic
modification of monomeric and partially polymerized bisphenol A dicyanate
ester[J]. European Polymer Journal, 2005, 41:2963-2972。
Summary of the invention
It is an object of the invention to provide a kind of high metal boride ceramic filler cyanate ester resin heat-resisting, high heat conduction multiple
Condensation material and preparation method thereof, to meet the field of engineering technology such as aerospace industry, aerospace structure part to exotic material
Actual demand.
The metal boride Situ of Ceramics that the present invention provides fills cyanate ester resin composite material, is by cyanate resin
Fat adds high performance metal boride ceramic packing, improves cyanate ester resin high-temperature heat-conductive heat resistance, specifically by metal
Boride one-component ceramic powder body, cyanate ester resin and catalyst composition；According to the mass fraction, the consumption of each component is as follows:
Cyanate ester resin: 85 ~ 95；
Metal boride ceramic powder: 5 ~ 15；
Catalyst: 0.01 ~ 0.05.
In the present invention, described metal boride ceramic powder is titanium diboride, zirconium diboride, niobium dioxide or two boronations
Tantalum powder body, mean diameter is 1 μm ~ 50 μm, and wherein, zirconium diboride and titanium diboride are optimal.
In the present invention, described cyanate ester resin is bisphenol A cyanate ester resin, average molecular mass is 500 ~
2000；This resin is by bisphenol-A in organic solvent, react with cyanogen halides and obtain under conditions of organic base exists.Wherein, bis-phenol
A: cyanogen halides: organic base: the quality proportioning of organic solvent is (1 ~ 1.1): (1.1 ~ 1.2): (0.9 ~ 1.1): (5 ~ 10).
Wherein, described organic solvent is alkane, benzene class or acetone, ethanol etc..
Described organic base is the organic base tertiary amine that can accept Bronsted acid, preferably triethylamine.
Described cyanogen halides is cyanogen chloride, Bromine cyanide. or cyanogen iodide.Preferably Bromine cyanide..
In the present invention, described catalyst is major catalyst/synergistic catalyst, and major catalyst is organo-metallic compound
The carboxylate of Cu, Co, Zn or Mn, synergistic catalyst is compatible reaction reagent, wherein, preferably Zn/nonyl phenol, Co/nonyl phenol.
The preparation method of cyanate resin base composite material filled by the boride ceramics that the present invention provides, and uses in-situ polymerization
Method, concretely comprises the following steps:
(1) preparation bisphenol-A, cyanogen halides organic solution, by quality proportioning, is placed in-10 ~ 0 DEG C bisphenol-A, cyanogen halides, organic solvent
In environment, mechanical agitation；It is subsequently adding metal boride ceramic powder, controls stir speed (S.S.) at 800 ~ 1500r/min；
(2) at-10 ~ 0 DEG C, dropping organic base (such as triethylamine), strong agitation, rate of addition is 0.1 ~ 0.5/s, 2.5 ~
Dropping in 3.5 hours is complete.Insulated and stirred 1 ~ 3 hour, obtains suspension.It is washed to neutrality, by floccular hydrogen bromination with distilled water
Amine salt separates, and isolated hydrogen bromination amine salt acetone soak leaches the cyanate ester resin of residual.Finally revolve steaming, remove organic molten
Agent, obtains metal boride ceramic powder filling in situ cyanate ester resin；
(3) add catalyst, high-speed stirred 5 ~ 10min, Fruit storage, inject rapidly mould, be warming up to 120 DEG C ~ 200
DEG C, solidify 5 ~ 7 hours, the demoulding, obtain metal boride Situ of Ceramics and fill cyanate ester resin composite material.
The metal boride Situ of Ceramics that the present invention provides fills cyanate ester resin composite material, adds in cyanate ester resin
Add boride ceramics to improve the research of cyanate ester resin performance, yet there are no report.Compared with existing similar research, utilize
In-situ polymerization has more uniform tissue signature than the filled composite materials that mechanical-physical blend method is obtained, thus
Material prepared by guarantee has more excellent performance；It addition, boride ceramics has high fusing point, splendid energy against corrosion
Power and thermal shock resistance and the high capacity of heat transmission, therefore, utilize the cyanate ester resin of high-performance boride ceramics filling in situ
Composite will have the performances such as higher heat conduction is heat-resisting, have a extensive future in high-temperature-resistant structure and functor application.
Detailed description of the invention
Embodiment 1
In 1000ml there-necked flask, add 100g bisphenol-A, Bromine cyanide. 105g and 400ml acetone soln, and there-necked flask is placed in ice
In water or ice salt bath, under 1000r/min mechanical agitation, add 6g zirconium diboride (ZrB2), in whole building-up process, temperature
Degree should control at 0 DEG C or less.Being dripped under 1200r/min stirs by separatory funnel by 90g triethylamine, rate of addition is 0.5
Dripping/s, dropping in about 3.5 hours is complete, continues stirring 1h, obtains suspension.Then with distilled water washing suspension to neutral, separate
The hydrogen bromination amine salt acetone soak gone out leaches the cyanate ester resin of residual and refunds former suspension.After hydrogen bromination amine salt being separated
Suspension system rotation steam, remove acetone solvent, obtain zirconium diboride powder body filling in situ cyanate ester resin, then to being set
Resin system adds 0.014gZn/nonyl phenol catalyst, high-speed stirred 6min, Fruit storage, injects rapidly mould, press
Carry out solidifying and post processing according to 120 DEG C/1h+150 DEG C/1h+180 DEG C/1h+200 DEG C/4h.The demoulding obtains zirconium diboride and fills out in situ
Fill cyanate ester resin composite material about 127g.Test result shows, the glass transition temperature Tg of this composite is 310.8 DEG C
(under identical experiment condition, the cyanate ester resin glass transition temperature Tg of synthesis is 278.5 DEG C, and general ceramic powder is such as
SiO2、Al2O3The glass transition temperature Tg filling cyanate ester resin composite material is 294 ~ 302 DEG C)；At ambient temperature, should
The thermal conductivity of composite be 0.38W/m K (under the conditions of same test, the cyanate ester resin of synthesis is 0.22 W/m K,
General ceramic powder such as SiO2、Al2O3The thermal conductivity filling cyanate ester resin composite material is 0.28 ~ 0.32 W/m K).
Embodiment 2
In 500ml there-necked flask, add 50g bisphenol-A, Bromine cyanide. 52.5g and 200ml acetone soln, and there-necked flask is placed in ice
In water or ice salt bath, under 800r/min mechanical agitation, add 3g titanium diboride (TiB2), in whole building-up process, temperature
Degree should control at 0 DEG C or less.Being dripped under 1000r/min stirs by separatory funnel by 45g triethylamine, rate of addition is 0.3
Dripping/s, dropping in about 3.0 hours is complete, continues stirring 1h, obtains suspension.Then with distilled water washing suspension to neutral, separate
The hydrogen bromination amine salt acetone soak gone out leaches the cyanate ester resin of residual and refunds former suspension.After hydrogen bromination amine salt being separated
Suspension system rotation steam, remove acetone solvent, obtain titanium diboride powder body filling in situ cyanate ester resin, then to being set
Resin system adds 0.01gZn/nonyl phenol catalyst, high-speed stirred 5min, Fruit storage, injects rapidly mould, according to
120 DEG C/1h+150 DEG C/1h+180 DEG C/1h+200 DEG C/4h carries out solidifying and post processing.The demoulding obtains titanium diboride filling in situ
Cyanate ester resin composite material about 65g.Test result shows, the glass transition temperature Tg of this composite is 308.8 DEG C；?
Under room temperature condition, the thermal conductivity of this composite is 0.378W/m K.
Embodiment 3
In 250ml there-necked flask, add 25g bisphenol-A, Bromine cyanide. 26.25g and 100ml acetone soln, and there-necked flask is placed in ice
In water or ice salt bath, under 800r/min mechanical agitation, add 3.05g zirconium diboride (ZrB2), in whole building-up process,
Temperature should control at 0 DEG C or less.Being dripped under 900r/min stirs by separatory funnel by 22.5g triethylamine, rate of addition is
0.1/s, dropping in about 3.0 hours is complete, continues stirring 1h, obtains suspension.Then with distilled water washing suspension to neutral, point
The hydrogen bromination amine salt acetone soak separated out leaches the cyanate ester resin of residual and refunds former suspension.Hydrogen bromination amine salt will be separated
After suspension system rotation steam, remove acetone solvent, obtain zirconium diboride powder body filling in situ cyanate ester resin, then to obtaining
Resin system adds 0.01gZn/nonyl phenol catalyst, high-speed stirred 5min, Fruit storage, injects rapidly mould, press
Carry out solidifying and post processing according to 120 DEG C/1h+150 DEG C/1h+180 DEG C/1h+200 DEG C/4h.The demoulding obtains zirconium diboride and fills out in situ
Fill cyanate ester resin composite material about 33.5g.Test result shows, the glass transition temperature Tg of this composite is 312.4
℃；At ambient temperature, the thermal conductivity of this composite is 0.43W/m K.
Embodiment 4
In 500ml there-necked flask, add 50g bisphenol-A, Bromine cyanide. 55g and 250ml acetone soln, and there-necked flask is placed in frozen water
Or in ice salt bath, under 800r/min mechanical agitation, add 7.315g zirconium diboride (ZrB2), in whole building-up process,
Temperature should control at 0 DEG C or less.Being dripped under 1000r/min stirs by separatory funnel by 50g triethylamine, rate of addition is
0.3/s, dropping in about 3.0 hours is complete, continues stirring 1h, obtains suspension.Then with distilled water washing suspension to neutral, point
The hydrogen bromination amine salt acetone soak separated out leaches the cyanate ester resin of residual and refunds former suspension.Hydrogen bromination amine salt will be separated
After suspension system rotation steam, remove acetone solvent, obtain zirconium diboride powder body filling in situ cyanate ester resin, then to obtaining
Resin system adds 0.01gCo/nonyl phenol catalyst, high-speed stirred 8min, Fruit storage, injects rapidly mould, press
Carry out solidifying and post processing according to 120 DEG C/1h+150 DEG C/1h+180 DEG C/1h+200 DEG C/4h.The demoulding obtains zirconium diboride and fills out in situ
Fill cyanate ester resin composite material about 68g.Test result shows, the glass transition temperature Tg of this composite is 314.2 DEG C；
At ambient temperature, the thermal conductivity of this composite is 0.48W/m K.
Embodiment 5
In 500ml there-necked flask, add 50g bisphenol-A, Bromine cyanide. 55g and 250ml acetone soln, and there-necked flask is placed in frozen water
Or in ice salt bath, under 800r/min mechanical agitation, add 7.315g titanium diboride (TiB2), in whole building-up process,
Temperature should control at 0 DEG C or less.Being dripped under 1000r/min stirs by separatory funnel by 50g triethylamine, rate of addition is
0.3/s, dropping in about 3.0 hours is complete, continues stirring 1h, obtains suspension.Then with distilled water washing suspension to neutral, point
The hydrogen bromination amine salt acetone soak separated out leaches the cyanate ester resin of residual and refunds former suspension.Hydrogen bromination amine salt will be separated
After suspension system rotation steam, remove acetone solvent, obtain titanium diboride powder body filling in situ cyanate ester resin, then to obtaining
Resin system adds 0.01gCo/nonyl phenol catalyst, high-speed stirred 8min, Fruit storage, injects rapidly mould, press
Carry out solidifying and post processing according to 120 DEG C/1h+150 DEG C/1h+180 DEG C/1h+200 DEG C/4h.The demoulding obtains titanium diboride and fills out in situ
Fill cyanate ester resin composite material about 68g.Test result shows, the glass transition temperature Tg of this composite is 311.2 DEG C；
At ambient temperature, the thermal conductivity of this composite is 0.436W/m K.
Embodiment 6
In 1000ml there-necked flask, add 100g bisphenol-A, Bromine cyanide. 105g and 500ml acetone soln, and there-necked flask is placed in ice
In water or ice salt bath, under 1000r/min mechanical agitation, add 19.51g zirconium diboride (ZrB2), in whole building-up process
In, temperature should control at 0 DEG C or less.100g triethylamine is dripped under 1200r/min stirs by separatory funnel, rate of addition
Being 0.5/s, dropping in about 3.5 hours is complete, continues stirring 1h, obtains suspension.Then with distilled water washing suspension to neutral,
Isolated hydrogen bromination amine salt acetone soak leaches the cyanate ester resin of residual and refunds former suspension.Hydrogen amine bromide will be separated
Suspension system rotation after salt is steamed, and removes acetone solvent, obtains zirconium diboride powder body filling in situ cyanate ester resin, then to obtaining
In resin system, add 0.064gCo/nonyl phenol catalyst, high-speed stirred 10min, Fruit storage, inject rapidly mould
Tool, carries out solidifying and post processing according to 120 DEG C/1h+150 DEG C/1h+180 DEG C/1h+200 DEG C/4h.The demoulding obtains zirconium diboride
Filling in situ cyanate ester resin composite material about 141.4g.Test result shows, the glass transition temperature Tg of this composite
It it is 315.7 DEG C；At ambient temperature, the thermal conductivity of this composite is 0.56W/m K.
Embodiment 7
In 500ml there-necked flask, add 50g bisphenol-A, Bromine cyanide. 52.5g and 250ml acetone soln, and there-necked flask is placed in ice
In water or ice salt bath, under 800r/min mechanical agitation, add 9.755g titanium diboride (TiB2), in whole building-up process
In, temperature should control at 0 DEG C or less.50g triethylamine is dripped under 1000r/min stirs by separatory funnel, rate of addition
Being 0.3/s, dropping in about 3.0 hours is complete, continues stirring 1h, obtains suspension.Then with distilled water washing suspension to neutral,
Isolated hydrogen bromination amine salt acetone soak leaches the cyanate ester resin of residual and refunds former suspension.Hydrogen amine bromide will be separated
Suspension system rotation after salt is steamed, and removes acetone solvent, obtains titanium diboride powder body filling in situ cyanate ester resin, then to obtaining
In resin system, add 0.01gZn/nonyl phenol catalyst, high-speed stirred 5min, Fruit storage, inject rapidly mould,
Carry out solidifying and post processing according to 120 DEG C/1h+150 DEG C/1h+180 DEG C/1h+200 DEG C/4h.The demoulding obtains titanium diboride in situ
Fill cyanate ester resin composite material about 72g.Test result shows, the glass transition temperature Tg of this composite is 312.8
℃；At ambient temperature, the thermal conductivity of this composite is 0.512W/m K.
Claims (8)
1. a metal boride Situ of Ceramics fills cyanate ester resin composite material, it is characterised in that this composite be by
Metal boride one-component ceramic powder body, cyanate ester resin and catalyst composition；According to the mass fraction, the consumption of each component is as follows:
Cyanate ester resin: 85 ~ 95；
Metal boride ceramic powder: 5 ~ 15；
Catalyst: 0.01 ~ 0.05.
Metal boride Situ of Ceramics the most according to claim 1 fills cyanate ester resin composite material, it is characterised in that
Described metal boride ceramic powder is titanium diboride, zirconium diboride, niobium dioxide or tantalum diboride powder body, and mean diameter is 1 μ
m~50μm。
Metal boride Situ of Ceramics the most according to claim 1 and 2 fills cyanate ester resin composite material, and its feature exists
In, described cyanate ester resin is bisphenol A cyanate ester resin, and average molecular mass is 500 ~ 2000；This resin is by bisphenol-A
In organic solvent, react with cyanogen halides under conditions of organic base exists and obtain；Wherein, bisphenol-A: cyanogen halides: organic base: have
The quality proportioning of machine solvent is (1 ~ 1.1): (1.1 ~ 1.2): (0.9 ~ 1.1): (5 ~ 10).
Metal boride Situ of Ceramics the most according to claim 3 fills cyanate ester resin composite material, it is characterised in that
Described organic solvent is alkane, benzene class or acetone, or ethanol.
Metal boride Situ of Ceramics the most according to claim 3 fills cyanate ester resin composite material, it is characterised in that
Described organic base is the organic base tertiary amine that can accept Bronsted acid.
Metal boride Situ of Ceramics the most according to claim 3 fills cyanate ester resin composite material, it is characterised in that
Described cyanogen halides is cyanogen chloride, Bromine cyanide. or cyanogen iodide.
7. fill cyanate ester resin composite wood according to the metal boride Situ of Ceramics one of claim 1,2,4,5,6 Suo Shu
Material, it is characterised in that described catalyst is major catalyst/synergistic catalyst, and wherein, major catalyst is organo-metallic compound
The carboxylate of Cu, Co, Zn or Mn, synergistic catalyst is compatible reaction reagent.
8. the preparation side of the boride ceramics filling cyanate resin base composite material as described in one of claim 1-7
Method, uses situ aggregation method, it is characterised in that concretely comprise the following steps:
(1) preparation bisphenol-A, cyanogen halides organic solution, by quality proportioning, is placed in-10 ~ 0 DEG C bisphenol-A, cyanogen halides, organic solvent
In environment, mechanical agitation；It is subsequently adding metal boride ceramic powder, controls stir speed (S.S.) at 800 ~ 1500r/min；
(2) at-10 ~ 0 DEG C, dripping organic base, stirring, rate of addition is 0.1 ~ 0.5/s, and dropping in 2.5 ~ 3.5 hours is complete；
Insulated and stirred 1 ~ 3 hour, obtains suspension；It is washed to neutrality with distilled water, floccular hydrogen amine bromide salt is separated, isolated
Hydrogen bromination amine salt acetone soak leaches the cyanate ester resin of residual；Finally revolve steaming, remove organic solvent, obtain metal boride
Ceramic powder filling in situ cyanate ester resin；
(3) add catalyst, high-speed stirred 5 ~ 10min, Fruit storage, inject rapidly mould, be warming up to 120 DEG C ~ 200
DEG C, solidify 5 ~ 7 hours, the demoulding, obtain metal boride Situ of Ceramics and fill cyanate ester resin composite material.
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| CN114806084A (en) * | 2021-01-29 | 2022-07-29 | 北大方正集团有限公司 | Composite material, preparation method and circuit board |
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| CN114806084A (en) * | 2021-01-29 | 2022-07-29 | 北大方正集团有限公司 | Composite material, preparation method and circuit board |
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