CN106046783B - A kind of boride ceramics filling in situ cyanate resin base composite material and preparation method thereof - Google Patents
A kind of boride ceramics filling in situ cyanate resin base composite material and preparation method thereof Download PDFInfo
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- CN106046783B CN106046783B CN201610611960.0A CN201610611960A CN106046783B CN 106046783 B CN106046783 B CN 106046783B CN 201610611960 A CN201610611960 A CN 201610611960A CN 106046783 B CN106046783 B CN 106046783B
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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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- 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
- C08G73/065—Preparatory processes
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention belongs to advanced compound materials science domain, specially a kind of boride ceramics filling in situ cyanate resin base composite material and preparation method thereof.Bisphenol-A is first dissolved in benzene class or alkanes organic solvent by situ aggregation method, a certain amount of cyanogen halides is added, mechanical stirring obtains mixed solution in -10 ~ 0 DEG C of environment by the present invention；Under strong stirring, metal boride ceramic powder is added into mixed solution, continues to stir；At -10 ~ 0 DEG C, triethylamine is added dropwise in Xiang Shangshu system, system polymerize, and obtains metal diboride powder filling in situ cyanate ester resin after distillation removes organic solvent；Then catalyst stirring is added, curing molding at high temperature after Fruit storage.Metal boride filling in situ cyanate ester resin composite material produced by the present invention has material structure uniform, heat-resisting, excellent thermal conductivity structural behaviour feature, can be used as aerospace industry, aerospace industry electronic equipment in printed circuit board baseplate material, encapsulating material etc..
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of boride ceramics filling in situ cyanate resin base is multiple
Condensation material and preparation method thereof.
Background technique
With the high power of modern microelectronics devices, highly integrated and micromation development, in industrial application electronic equipment
The timely heat dissipation of baseplate material, encapsulating material etc. and stability seem most important.Cyanate (Cyanate Ester, CE)
Resin is as a kind of important high-performance thermosetting resin, since it is with good heat resistance, lower dielectric constant and Jie
The comprehensive performances such as electrical loss and good weatherability, in high performance print circuit board, aerospace structure member, stealth material, radar
The advanced technologies such as antenna house and artificial satellite field has broad application prospects.Cyanate ester monomer is after solidification crosslinking, knot
There is high structural stability, low polar 1,3,5-triazines ring structure in structure, even compact structure makes cyanate ester resin solid
Brittleness is big after change, heating conduction is poor, generates violent temperature rise because that cannot radiate in time under high loading conditions and then leads to material
Structure and performance failure, it is difficult to meet hot environment flowering structure to the actual requirement of material property, make its application by certain
Limitation.To cyanate resin modifier, thermosetting resin, thermoplastic resin, rubber elastomer, chemical combination containing unsaturated double-bond are such as utilized
Object and inorganic filler etc. have been carried out a large amount of research work, and research focuses mostly on to toughening modification of cyanate ester resin.Wherein
Using inorganic ceramic filling modifier cyanate organic resin hot property, especially improves the mechanical property under its high temperature, leads
Hot property is a kind of more effective method.Studies have shown that inorganic ceramic filling modifier organic resin has merged inorganic pottery
It is negative in height that the excellent thermally conductive heat resistance of porcelain and high flexibility, the machinability of organic resin can significantly improve organic resin material
Heating conduction 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., the method that material preparation is mainly blended using physical mechanical, and for benefit
It is then rarely reported with the research of boride ceramics especially metal boride ceramic filler modified cyanic acid ester, especially by original position
The research that polymerization prepares the filling-modified cyanate ester resin composite material of high-thermal conductive metal boride ceramics is not yet shown in so far
Report.
Bibliography:
[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 multiple that the purpose of the present invention is to provide the metal boride ceramic filler cyanate ester resins of a kind of high heat resistance, high thermal conductivity
Condensation material and preparation method thereof, to meet the field of engineering technology such as aerospace industry, aerospace structure part to heat-resisting material
Actual demand.
Metal boride Situ of Ceramics provided by the invention fills cyanate ester resin composite material, is by cyanate resin
High performance metal boride ceramic packing is added in rouge, cyanate ester resin high-temperature heat-conductive heat resistance is improved, specifically by metal
Boride one-component ceramic powder, cyanate ester resin and catalyst composition；According to the mass fraction, the dosage 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, the metal boride ceramic powder is titanium diboride, zirconium diboride, niobium dioxide or two boronations
Tantalum powder body, average grain diameter are 1 μm ~ 50 μm, wherein zirconium diboride and titanium diboride are best.
In the present invention, the cyanate ester resin be bisphenol A cyanate ester resin, average molecular mass be 500 ~
2000；The resin as bisphenol-A in organic solvent, existing for the organic base under the conditions of react and obtain with cyanogen halides.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, the organic solvent is alkane, benzene class or acetone, ethyl alcohol etc..
The organic base is the organic base tertiary amine that can receive Bronsted acid, preferably triethylamine.
The cyanogen halides is cyanogen chloride, cyanogen bromide or cyanogen iodide.It is preferred that cyanogen bromide.
In the present invention, the catalyst is major catalyst/synergistic catalyst, and major catalyst is organo-metallic compound
The carboxylate of Cu, Co, Zn or Mn, synergistic catalyst are compatible reaction reagent, wherein preferred Zn/nonyl phenol, Co/nonyl phenol.
The preparation method of boride ceramics filling cyanate resin base composite material provided by the invention, using in-situ polymerization
Method, specific steps are as follows:
(1) bisphenol-A, cyanogen halides organic solution are prepared and bisphenol-A, cyanogen halides, organic solvent is placed in -10 by quality proportioning
In ~ 0 DEG C of environment, mechanical stirring；Then metal boride ceramic powder is added, controls stirring rate in 800 ~ 1500r/min；
(2) it at -10 ~ 0 DEG C, is added dropwise organic base (such as triethylamine), strong to stir, rate of addition is 0.1 ~ 0.5 drop/s,
It is added dropwise within 2.5 ~ 3.5 hours.Insulated and stirred 1 ~ 3 hour, obtain suspension.It is washed to neutrality with distilled water, by the hydrogen of flocculence
The separation of amine bromide salt, the hydrogen bromination amine salt isolated filter out remaining cyanate ester resin with acetone soak.It finally rotates, removing has
Solvent obtains metal boride ceramic powder filling in situ cyanate ester resin；
(3) catalyst is added, 5 ~ 10min of high-speed stirred, Fruit storage injects rapidly mold, be warming up to 120 DEG C ~
200 DEG C, solidify 5 ~ 7 hours, demoulding fills cyanate ester resin composite material to get metal boride Situ of Ceramics.
Metal boride Situ of Ceramics provided by the invention fills cyanate ester resin composite material, adds into 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 filled composite materials more obtained than mechanical-physical blend method have more uniform tissue signature, thus
Guarantee that prepared material has more excellent performance；In addition, boride ceramics has high fusing point, splendid energy against corrosion
Therefore power and thermal shock resistance and the high capacity of heat transmission utilize the cyanate ester resin of high-performance boride ceramics filling in situ
Composite material will have the higher thermally conductive performances such as heat-resisting, have a extensive future in high-temperature-resistant structure and functor application field.
Specific embodiment
Embodiment 1
100g bisphenol-A, cyanogen bromide 105g and 400ml acetone soln are added in 1000ml there-necked flask, and there-necked flask is set
In ice water or ice salt bath, under 1000r/min mechanical stirring, 6g zirconium diboride (ZrB is added2), in entire synthesis process
In, temperature should be controlled at 0 DEG C or less.90g triethylamine is added dropwise under 1200r/min stirring by separatory funnel, rate of addition
It for 0.5 drop/s, is added dropwise within about 3.5 hours, continues to stir 1h, obtain suspension.Then suspension is washed to neutrality with distilled water,
The hydrogen bromination amine salt isolated filters out remaining cyanate ester resin with acetone soak and refunds former suspension.Hydrogen amine bromide will be separated
After salt suspension system revolving, remove acetone solvent, obtain zirconium diboride powder filling in situ cyanate ester resin, then to
0.014gZn/nonyl phenol catalyst, high-speed stirred 6min are added into resin system, Fruit storage injects rapidly mould
Tool, is solidified and is post-processed according to+180 DEG C/1h+200 DEG C/4h of+150 DEG C/1h of 120 DEG C/1h.Demould to obtain zirconium diboride
Filling in situ cyanate ester resin composite material about 127g.Test result shows that the glass transition temperature Tg of the composite material is
310.8 DEG C (under identical experiment condition, the cyanate ester resin glass transition temperature Tg of synthesis is 278.5 DEG C, general ceramics
Powder such as SiO2、Al2O3The glass transition temperature Tg for filling cyanate ester resin composite material is 294 ~ 302 DEG C)；In room temperature item
Under part, the thermal conductivity of the composite material is that (under the same test conditions, the cyanate ester resin of synthesis is 0.22 to 0.38W/mK
W/mK, general ceramic powder such as SiO2、Al2O3The thermal conductivity for filling cyanate ester resin composite material is 0.28 ~ 0.32 W/m
K)。
Embodiment 2
50g bisphenol-A, cyanogen bromide 52.5g and 200ml acetone soln are added in 500ml there-necked flask, and there-necked flask is set
In ice water or ice salt bath, under 800r/min mechanical stirring, 3g titanium diboride (TiB is added2), in entire synthesis process
In, temperature should be controlled at 0 DEG C or less.45g triethylamine is added dropwise under 1000r/min stirring by separatory funnel, rate of addition
It for 0.3 drop/s, is added dropwise within about 3.0 hours, continues to stir 1h, obtain suspension.Then suspension is washed to neutrality with distilled water,
The hydrogen bromination amine salt isolated filters out remaining cyanate ester resin with acetone soak and refunds former suspension.Hydrogen amine bromide will be separated
After salt suspension system revolving, remove acetone solvent, obtain titanium diboride powder filling in situ cyanate ester resin, then to
0.01gZn/nonyl phenol catalyst, high-speed stirred 5min are added into resin system, Fruit storage injects rapidly mold,
Solidified and post-processed according to+180 DEG C/1h+200 DEG C/4h of+150 DEG C/1h of 120 DEG C/1h.Demould to obtain titanium diboride original position
Fill cyanate ester resin composite material about 65g.Test result shows that the glass transition temperature Tg of the composite material is 308.8
℃；At room temperature, the thermal conductivity of the composite material is 0.378W/mK.
Embodiment 3
25g bisphenol-A, cyanogen bromide 26.25g and 100ml acetone soln are added in 250ml there-necked flask, and there-necked flask is set
In ice water or ice salt bath, under 800r/min mechanical stirring, 3.05g zirconium diboride (ZrB is added2), it was synthesized entirely
Cheng Zhong, temperature should be controlled at 0 DEG C or less.22.5g triethylamine is added dropwise under 900r/min stirring by separatory funnel, speed is added dropwise
Degree is 0.1 drop/s, is added dropwise within about 3.0 hours, continues to stir 1h, obtains suspension.Then with distilled water washing suspension into
Property, the hydrogen bromination amine salt isolated filters out remaining cyanate ester resin with acetone soak and refunds former suspension.Hydrogen bromine will be separated
Suspension system revolving after changing amine salt, removes acetone solvent, obtains zirconium diboride powder filling in situ cyanate ester resin, then
To addition 0.01gZn/nonyl phenol catalyst in resin system, high-speed stirred 5min is obtained, Fruit storage injects rapidly
Mold is solidified and is post-processed according to+180 DEG C/1h+200 DEG C/4h of+150 DEG C/1h of 120 DEG C/1h.Demould to obtain two boronations
Zirconium filling in situ cyanate ester resin composite material about 33.5g.Test result shows the glass transition temperature Tg of the composite material
It is 312.4 DEG C；At room temperature, the thermal conductivity of the composite material is 0.43W/mK.
Embodiment 4
50g bisphenol-A, cyanogen bromide 55g and 250ml acetone soln are added in 500ml there-necked flask, and there-necked flask is placed in
In ice water or ice salt bath, under 800r/min mechanical stirring, 7.315g zirconium diboride (ZrB is added2), in entire synthesis process
In, temperature should be controlled at 0 DEG C or less.50g triethylamine is added dropwise under 1000r/min stirring by separatory funnel, rate of addition
It for 0.3 drop/s, is added dropwise within about 3.0 hours, continues to stir 1h, obtain suspension.Then suspension is washed to neutrality with distilled water,
The hydrogen bromination amine salt isolated filters out remaining cyanate ester resin with acetone soak and refunds former suspension.Hydrogen amine bromide will be separated
After salt suspension system revolving, remove acetone solvent, obtain zirconium diboride powder filling in situ cyanate ester resin, then to
0.01gCo/nonyl phenol catalyst, high-speed stirred 8min are added into resin system, Fruit storage injects rapidly mold,
Solidified and post-processed according to+180 DEG C/1h+200 DEG C/4h of+150 DEG C/1h of 120 DEG C/1h.Demould to obtain zirconium diboride original position
Fill cyanate ester resin composite material about 68g.Test result shows that the glass transition temperature Tg of the composite material is 314.2
℃；At room temperature, the thermal conductivity of the composite material is 0.48W/mK.
Embodiment 5
50g bisphenol-A, cyanogen bromide 55g and 250ml acetone soln are added in 500ml there-necked flask, and there-necked flask is placed in
In ice water or ice salt bath, under 800r/min mechanical stirring, 7.315g titanium diboride (TiB is added2), in entire synthesis process
In, temperature should be controlled at 0 DEG C or less.50g triethylamine is added dropwise under 1000r/min stirring by separatory funnel, rate of addition
It for 0.3 drop/s, is added dropwise within about 3.0 hours, continues to stir 1h, obtain suspension.Then suspension is washed to neutrality with distilled water,
The hydrogen bromination amine salt isolated filters out remaining cyanate ester resin with acetone soak and refunds former suspension.Hydrogen amine bromide will be separated
After salt suspension system revolving, remove acetone solvent, obtain titanium diboride powder filling in situ cyanate ester resin, then to
0.01gCo/nonyl phenol catalyst, high-speed stirred 8min are added into resin system, Fruit storage injects rapidly mold,
Solidified and post-processed according to+180 DEG C/1h+200 DEG C/4h of+150 DEG C/1h of 120 DEG C/1h.Demould to obtain titanium diboride original position
Fill cyanate ester resin composite material about 68g.Test result shows that the glass transition temperature Tg of the composite material is 311.2
℃；At room temperature, the thermal conductivity of the composite material is 0.436W/mK.
Embodiment 6
100g bisphenol-A, cyanogen bromide 105g and 500ml acetone soln are added in 1000ml there-necked flask, and there-necked flask is set
In ice water or ice salt bath, under 1000r/min mechanical stirring, 19.51g zirconium diboride (ZrB is added2), entirely synthesizing
In the process, temperature should be controlled at 0 DEG C or less.100g triethylamine is added dropwise under 1200r/min stirring by separatory funnel, is added dropwise
Speed is 0.5 drop/s, is added dropwise within about 3.5 hours, continues to stir 1h, obtains suspension.Then extremely with distilled water washing suspension
Neutrality, the hydrogen bromination amine salt isolated filter out remaining cyanate ester resin with acetone soak and refund former suspension.Hydrogen will be separated
Suspension system revolving after bromination amine salt, removes acetone solvent, obtains zirconium diboride powder filling in situ cyanate ester resin, so
It obtains adding 0.064gCo/nonyl phenol catalyst in resin system backward, high-speed stirred 10min, Fruit storage, rapidly
Mold is injected, is solidified and is post-processed according to+180 DEG C/1h+200 DEG C/4h of+150 DEG C/1h of 120 DEG C/1h.Demould two
Zirconium boride in-situ fills cyanate ester resin composite material about 141.4g.Test result shows the glass transition of the composite material
Temperature Tg is 315.7 DEG C；At room temperature, the thermal conductivity of the composite material is 0.56W/mK.
Embodiment 7
50g bisphenol-A, cyanogen bromide 52.5g and 250ml acetone soln are added in 500ml there-necked flask, and there-necked flask is set
In ice water or ice salt bath, under 800r/min mechanical stirring, 9.755g titanium diboride (TiB is added2), it was synthesized entirely
Cheng Zhong, temperature should be controlled at 0 DEG C or less.50g triethylamine is added dropwise under 1000r/min stirring by separatory funnel, speed is added dropwise
Degree is 0.3 drop/s, is added dropwise within about 3.0 hours, continues to stir 1h, obtains suspension.Then with distilled water washing suspension into
Property, the hydrogen bromination amine salt isolated filters out remaining cyanate ester resin with acetone soak and refunds former suspension.Hydrogen bromine will be separated
Suspension system revolving after changing amine salt, removes acetone solvent, obtains titanium diboride powder filling in situ cyanate ester resin, then
To addition 0.01gZn/nonyl phenol catalyst in resin system, high-speed stirred 5min is obtained, Fruit storage injects rapidly
Mold is solidified and is post-processed according to+180 DEG C/1h+200 DEG C/4h of+150 DEG C/1h of 120 DEG C/1h.Demould to obtain two boronations
Titanium filling in situ cyanate ester resin composite material about 72g.Test result shows that the glass transition temperature Tg of the composite material is
312.8℃；At room temperature, the thermal conductivity of the composite material is 0.512W/mK.
Claims (8)
1. a kind of metal boride Situ of Ceramics fills cyanate ester resin composite material, which is characterized in that the composite material be by
Metal boride one-component ceramic powder, cyanate ester resin and catalyst composition；According to the mass fraction, the dosage of each component is as follows:
Cyanate ester resin: 85 ~ 95；
Metal boride ceramic powder: 5 ~ 15；
Catalyst: 0.01 ~ 0.05.
2. metal boride Situ of Ceramics according to claim 1 fills cyanate ester resin composite material, which is characterized in that
The metal boride ceramic powder is titanium diboride, zirconium diboride, niobium dioxide or tantalum diboride powder, and average grain diameter is 1 μ
m~50μm。
3. metal boride Situ of Ceramics according to claim 1 or 2 fills cyanate ester resin composite material, feature exists
In the cyanate ester resin is bisphenol A cyanate ester resin, and average molecular mass is 500 ~ 2000；The resin is by bisphenol-A
In organic solvent, it reacts and obtains with cyanogen halides under the conditions of existing for the organic base；Wherein, bisphenol-A: cyanogen halides: organic base: have
The quality proportioning of solvent is (1 ~ 1.1): (1.1 ~ 1.2): (0.9 ~ 1.1): (5 ~ 10).
4. metal boride Situ of Ceramics according to claim 3 fills cyanate ester resin composite material, which is characterized in that
The organic solvent is alkane, benzene class or acetone or ethyl alcohol.
5. metal boride Situ of Ceramics according to claim 3 fills cyanate ester resin composite material, which is characterized in that
The organic base is the organic base tertiary amine that can receive Bronsted acid.
6. metal boride Situ of Ceramics according to claim 3 fills cyanate ester resin composite material, which is characterized in that
The cyanogen halides is cyanogen chloride, cyanogen bromide or cyanogen iodide.
7. according to claim 1, metal boride Situ of Ceramics described in one of 2,4,5,6 fills cyanate ester resin composite wood
Material, which is characterized in that the catalyst is major catalyst/synergistic catalyst, wherein major catalyst is organo-metallic compound
The carboxylate of Cu, Co, Zn or Mn, synergistic catalyst are necleophilic reaction reagent.
8. a kind of system of the metal boride Situ of Ceramics filling cyanate ester resin composite material as described in one of claim 1-7
Preparation Method, using situ aggregation method, which is characterized in that specific steps are as follows:
(1) bisphenol-A, cyanogen halides organic solution are prepared and bisphenol-A, cyanogen halides, organic solvent is placed in -10 ~ 0 DEG C by quality proportioning
In environment, mechanical stirring；Then metal boride ceramic powder is added, controls stirring rate in 800 ~ 1500r/min；
(2) at -10 ~ 0 DEG C, organic base, stirring is added dropwise, rate of addition is 0.1 ~ 0.5 drop/s, is added dropwise within 2.5 ~ 3.5 hours；
Insulated and stirred 1 ~ 3 hour, obtain suspension；It is washed to neutrality with distilled water, the hydrogen amine bromide salt of flocculence is separated, is isolated
Hydrogen bromination amine salt filters out remaining cyanate ester resin with acetone soak；It finally rotates, removes organic solvent, obtain metal boride
Ceramic powder filling in situ cyanate ester resin；
(3) catalyst, 5 ~ 10min of high-speed stirred is added, Fruit storage injects rapidly mold, is warming up to 120 DEG C ~ 200
DEG C, solidify 5 ~ 7 hours, demoulding fills cyanate ester resin composite material to get metal boride Situ of Ceramics.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719097A (en) * | 2012-07-06 | 2012-10-10 | 苏州大学 | Titanium diboride oxide/thermosetting resin composite material and preparation method thereof |
| CN104231624A (en) * | 2014-08-22 | 2014-12-24 | 南京信息职业技术学院 | Modified cyanate resin heat-conducting composite material and preparation method thereof |
| CN104961652A (en) * | 2015-05-30 | 2015-10-07 | 扬州天启新材料股份有限公司 | Bisphenol A type cyanate resin monomer preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719097A (en) * | 2012-07-06 | 2012-10-10 | 苏州大学 | Titanium diboride oxide/thermosetting resin composite material and preparation method thereof |
| CN104231624A (en) * | 2014-08-22 | 2014-12-24 | 南京信息职业技术学院 | Modified cyanate resin heat-conducting composite material and preparation method thereof |
| CN104961652A (en) * | 2015-05-30 | 2015-10-07 | 扬州天启新材料股份有限公司 | Bisphenol A type cyanate resin monomer preparation method |
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