CN106497512A - Superhigh temperature resistant adhesive based on liquid poly carbon silane ceramics presoma and preparation method thereof - Google Patents
Superhigh temperature resistant adhesive based on liquid poly carbon silane ceramics presoma and preparation method thereof Download PDFInfo
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- CN106497512A CN106497512A CN201611030593.1A CN201611030593A CN106497512A CN 106497512 A CN106497512 A CN 106497512A CN 201611030593 A CN201611030593 A CN 201611030593A CN 106497512 A CN106497512 A CN 106497512A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/16—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K3/34—Silicon-containing compounds
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention discloses superhigh temperature resistant adhesive based on liquid poly carbon silane ceramics presoma and preparation method thereof.In terms of parts by weight, the adhesive is grouped into by following groups：Liquid poly carbon silane ceramics presoma or its polymer-modified 100 parts, 0.5～5 part of firming agent, 0～300 part of solid packing, 0～10 part of chopped strand.The present invention has heat resistance high based on the superhigh temperature resistant adhesive of liquid poly carbon silane ceramics presoma, still there is higher shear strength at 1000 DEG C～1700 DEG C, can be used for the bonding between ceramic composite materials, C-base composte material, and can be used to aoxidizing, under inert atmosphere.Invention adhesive has preferable heat stability, mechanical property and adhesive property, and its temperature tolerance is better than phenolic resin；Compared with inorganic adhesive, with good toughness.
Description
Technical field
The present invention relates to adhesive and preparation method thereof, more particularly to based on the resistance to super of liquid poly carbon silane ceramics presoma
High temperature adhesive and preparation method thereof.
Background technology
With the high-tech development such as Aeronautics and Astronautics, for example：The development of heavy rocket, high-speed aircraft etc., to being related to
Material temperature tolerance propose higher and higher requirement, adhesive as important functional material, equally to its temperature classification
Also it is correspondingly improved.At present, superhigh temperature resistant adhesive includes inorganic adhesive, silicones, modified phenolic etc..Inorganic adhesive master
Silicate to be included, phosphate and aluminosilicate etc., this kind of adhesive resistance to elevated temperatures are extremely excellent, can be at 180～2900 DEG C
In the range of widely use, but its fragility is bigger, poor thermal shock resistance, and produces certain corrosion to material.Modified phenolic
Class adhesive has many excellent performances, is widely used in fields such as Aeronautics and Astronautics, but the carbon-based adhesive of phenolic
Non-oxidizability is poor, it is difficult to meet the use requirement under high temperature aerobic environment.The molecular backbone structure of organic siliconresin by bond energy very
High siliconoxygen bond is constituted, more much higher than the molecular structure thermostability of carbochain, is the main constituent of good Heat-Resisting Adhesive, but silicon tree
Under lipid adhesive high temperature, adhesive property is poor.
Content of the invention
It is an object of the invention to provide the superhigh temperature resistant adhesive and its preparation based on liquid poly carbon silane ceramics presoma
Method, the superhigh temperature resistant adhesive have preferable heat stability, mechanical property and adhesive property, can be used for pottery and its are combined
Bonding between material, C-base composte material.
A kind of adhesive that the present invention is provided, in terms of parts by weight, the adhesive is grouped into by following groups：The poly- carbon of liquid
Silane ceramics presoma or its polymer-modified 100 parts, 0.5～5 part of firming agent, 0～300 part of solid packing, chopped strand 0～
10 parts.
Specifically, in terms of parts by weight, the adhesive is by following 1) -10) any one of group be grouped into：
1) 100 parts of liquid poly carbon silane ceramics presoma, 0.5～5 part of firming agent, 40～198 parts of solid packing, be chopped fibre
0～15 part of dimension；
2) 100 parts of liquid poly carbon silane ceramics presoma, 0.5 part of firming agent, 155 parts of solid packing, 3 parts of chopped strand；
3) 100 parts of liquid poly carbon silane ceramics presoma, 2 parts of firming agent, 55 parts of solid packing, 15 parts of chopped strand；
4) 100 parts of liquid poly carbon silane ceramics presoma, 5 parts of firming agent, 40 parts of solid packing, 10 parts of chopped strand；
5) 100 parts of liquid poly carbon silane ceramics presoma, 3 parts of firming agent, 198 parts of solid packing, 1 part of chopped strand；
6) 100 parts of liquid poly carbon silane ceramics presoma, 1.5 parts of firming agent, 73 parts of solid packing, 0 part of chopped strand；
7) 100 parts of liquid poly carbon silane ceramics presoma, 5 parts of firming agent, 97 parts of solid packing, 2 parts of chopped strand；
8) 100 parts of liquid poly carbon silane ceramics presoma, 4 parts of firming agent, 129 parts of solid packing, 0 part of chopped strand.
In above-mentioned adhesive, so liquid poly carbon silane ceramics presoma includes two structure lists of following mol ratio
Unit：
Wherein, it is the group containing C=C, C ≡ C or cyclopropyl independently of one another that R is, x=0.7～0.9.Preferably, R
It is CH independently of one another2=CH-, CH2=CHCH2-, CH2=C (CH3)-, CH3CH=CH-, HC ≡ C-, HC ≡ C-CH2- or
(CH2)2CH-；It is highly preferred that R is CH2=CH-.X concretely 0.7～0.8,0.8～0.9,0.7,0.8 or 0.9.
25 DEG C of viscosity of the liquid poly carbon silane ceramics presoma can be 100～10000mPa.s, concretely 500～
5000mPa.s, 500～3000mPa.s, 1000～4000mPa.s, 3000～5000mPa.s, 500mPa.s, 1000mPa.s,
3000mPa.s, 4000mPa.s or 5000mPa.s.
The firming agent can be peroxide firming agent or azo-initiator.The peroxide firming agent can be organic
Peroxide firming agent；The organic peroxide curing agent is included but is not limited to：Cumyl peroxide (DCP), peroxidating
Butanone (MEKP), perbenzoic acid (BPO), 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes (DBPH)；Described
Azo-initiator can be azodiisobutyronitrile (AIBN).
The solid packing can be carborundum (SiC), zirconium carbide (ZrC), titanium carbide (TiC), hafnium carbide (HfC), carbonization
Boron (B4C), aluminium carbide (Al4C3), silicon nitride (Si3N4), aluminium nitride (AlN), zirconium boride (ZrB2), titanium boride (TiB2), boronation
Silicon (SiB6), titanium disilicide (TiSi2), yittrium oxide (Y2O3), aluminium oxide (Al2O3) and silicon oxide (SiO2) at least one.
The particle diameter of the solid packing can be 0.2～50 micron, such as 0.5～5 micron.
The chopped strand can be mullite fiber, alumina fibre, silicon dioxide fibre, carbon fiber, silicon carbide fibre
In at least one.The length of the chopped strand can be 1～10 millimeter, such as 1～5 millimeter.
Invention further provides the preparation method of above-mentioned adhesive, comprises the steps：The adhesive will be prepared
Each component according to deaerating the adhesive that obtain after parts by weight mixing.Following steps specifically may include：To first remove
Component mixing beyond the firming agent, then adds the firming agent, and deaerates after mixing the resistance to superelevation that be obtained
Warm adhesive.
Present invention also offers above-mentioned superhigh temperature resistant adhesive in pottery or ceramic matric composite, carbon-based or which is compound
Application in the bonding of storeroom.The bonding can be carried out under any one atmosphere in oxidation, reduction, inertia and vacuum.
The present invention has the advantages that：
The present invention has heat resistance high based on the superhigh temperature resistant adhesive of liquid poly carbon silane ceramics presoma, 1000
DEG C～1700 DEG C still have higher shear strength, can be used for the bonding between ceramic composite materials, C-base composte material,
And can be used to aoxidizing, under inert atmosphere.Invention adhesive has preferable heat stability, mechanical property and adhesive property,
Its temperature tolerance is better than phenolic resin；Compared with inorganic adhesive, with good toughness.
Specific embodiment
Experimental technique used in following embodiments if no special instructions, is conventional method.Compression shear strength
Method of testing is carried out according to GB GB/T 17517-1998.
In following embodiments, material used, reagent etc., if no special instructions, commercially obtain.
Liquid poly carbon silane ceramics presoma of the present invention can according to Publication No. CN104177621A, entitled " one
The preparation method of the new liquid Polycarbosilane disclosed in kind new liquid Polycarbosilane and preparation method and application " is carried out
Synthesis, specifically may include following steps：
(1) magnesium chips or magnesium powder are added in dry ether solvent, thereto a small amount of chloromethyl alkoxy silane of Deca
Or chloromethyl alkoxy silane and chloromethyl dimethoxysilane, one methoxy silane of chloromethyl and ether solvent, reaction initiation
Afterwards, lower Deca chloromethyl alkoxy silane or chloromethyl alkoxy silane and chloromethyl dimethoxysilane, chloromethyl one are stirred
Methoxy silane and the mixed solution of ether solvent, 0～80 DEG C of 1～12h of reaction；
(2) stir Grignard reagent of the lower Deca containing reactive group or can with magnesium be formed in situ Grignard reagent containing reactivity
The halogenated hydrocarbons of group or chloromethyl silane compound, 0～80 DEG C of 1～36h of reaction；
(3) lower addition reducing agent, 0～80 DEG C of 1～36h of reaction are stirred；
(4) it is sufficiently stirred for down, adds deionized water, concentrated hydrochloric acid and low boiling alkane, -20～30 DEG C of 0.5～5h of reaction is quiet
.5～5h is set to 0, upper organic phase drying after split-phase, is isolated, distillation obtains product.
Described ether solvent is selected from ether, tetrahydrofuran, 2- methyltetrahydrofurans, glycol dimethyl ether, ethylene glycol bisthioglycolate
One kind in butyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, methyl tertiary butyl ether(MTBE), cyclopentyl methyl ether etc. or its two kinds
Above mixture, preferably tetrahydrofuran and 2- methyltetrahydrofurans.Low boiling alkane selected from pentane, Pentamethylene., hexane and
One kind or its two or more mixture, preferably hexane and Pentamethylene. in petroleum ether (30-60 DEG C) etc..
Described chloromethyl alkoxy silane is chloromethyl trimethoxy silane, chloromethyl triethoxysilane or chloromethane
Three isopropoxy silane of base, preferably chloromethyl triethoxysilane.
In described mixture, the molar content of chloromethyl trialkoxy silane is more than 50%.
The volume ratio of described chloromethyl alkoxy silane monomer and described ether solvent is 1:1～1:5.
The Grignard reagent is the unsaturated alkyl magnesium halide containing vinyl or alkynyl, selected from following any one：
CH2=CH-MgBr, CH2=CH-MgCl, CH2=CHCH2- MgBr, CH2=C (CH3)-MgBr, CH3CH=CH-MgBr, CH2=
CHCH2- MgCl, CH3CH=CH-MgCl, HC ≡ C-MgBr, HC ≡ C-CH2MgBr, preferably CH2=CH-MgBr；Containing reactivity
The halogenated hydrocarbons of group include：CH2=CHCH2Cl, CH2=CHBr, HC ≡ C-CH2Br, (CH2)2CHBr；Described chloromethyl silane
Compound includes：ClCH2SiMeH2,ClCH2SiH2(CH=CH2).
Described reducing agent is lithium aluminium hydride reduction, lithium hydride, magnesium hydride, sodium hydride or calcium hydride, preferably lithium aluminium hydride reduction.
The volume ratio of the deionized water, the concentrated hydrochloric acid and the low boiling alkane is 2:1:0.5～11:1:5.
The preparation and application of embodiment 1, adhesive
First, formula
In terms of parts by weight, the present embodiment adhesive is grouped into by following groups：
Wherein, liquid poly carbon silane ceramics presoma includes two construction units of following mol ratio：
2nd, preparation method
(1) liquid poly carbon silane ceramics presoma shown in formula 1
Liquid poly carbon silane ceramics presoma shown in formula 1 in accordance with the following steps：
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
Triethoxysilane and the mixed solution of 2mL tetrahydrofurans, are slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 60mL ethylene is added by constant pressure funnel
The methyltetrahydrofuran solution of base magnesium bromide (1.6mol/L), 30 DEG C of insulation reaction 6h.After reaction terminates, 7.45g hydrogenations are added
Aluminum lithium, continues to react 10h at 30 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes is added, at 0～5 DEG C, reacts 0.5～2h, stood and divide
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, and separation is organic
Phase, adds 15g anhydrous magnesium sulfates to dry, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
73%, the product is-CH=CH corresponding to the R in formula (1)2, x=0.3, its molecular weight Mw=1162, Mn=584.
(2) adhesive is prepared
According to the proportioning of each component in above-mentioned formula, in beaker add formula 1 shown in liquid poly carbon silane ceramics presoma,
SiC、ZrB2、Y2O3And SiO2Chopped strand, adds BPO after uniform mixing, mixes well, resistance to surpassing is obtained after the 5-7 minutes that deaerate
High temperature adhesive.
3rd, apply
The above-mentioned adhesive for preparing is used for viscous between graphite, C-base composte material and ceramic composite materials
Connect, solidify 2～5 hours at 180 DEG C～260 DEG C, after solidification, determine adhesive property.
Table 1 provides the adhesive to graphite, the room temperature adhesion strength of carbon-based, ceramic and composite, and table 2 provides adhesive
For shear strength of the graphite material under room temperature and high temperature nitrogen atmosphere that bond.
Table 1, adhesive is to graphite, the adhesion strength of carbon-based, ceramic and composite
The mechanical property that table 2, adhesive is tested in room temperature and different temperatures
The preparation and application of embodiment 2, adhesive
First, formula
In terms of parts by weight, the present embodiment adhesive is grouped into by following groups：
Wherein, liquid poly carbon silane ceramics presoma includes two construction units of following mol ratio：
2nd, preparation method
(1) liquid poly carbon silane ceramics presoma shown in formula 2
Liquid poly carbon silane ceramics presoma shown in formula 2 in accordance with the following steps：
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
Triethoxysilane and the mixed solution of 2mL tetrahydrofurans, are slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 60mL allyls are added by constant pressure funnel
The methyltetrahydrofuran solution of base magnesium bromide (1.6mol/L), 30 DEG C of insulation reaction 6h.After reaction terminates, 7.45g hydrogenations are added
Aluminum lithium, continues to react 10h at 30 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes is added, at 0～5 DEG C, reacts 0.5～2h, stood and divide
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, and separation is organic
Phase, adds 15g anhydrous magnesium sulfates to dry, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane (this presoma
Structure is more complicated, is in most cases line-ring mixed structure), yield is 72%, the product corresponding to the R in formula (1) for-
CH2- CH=CH2, x=0.3, its molecular weight Mw=1340, Mn=620.
(2) resistance to adhesive is prepared
According to the proportioning of each component in above-mentioned formula, in beaker add formula 2 shown in liquid poly carbon silane ceramics presoma,
SiC、B4C、ZrB2、TiSi2With carborundum chopped strand, DCP is added after uniform mixing, mix well, deaerate 5 minutes, you can obtain
Adhesive.
3rd, apply
Using the above-mentioned adhesive for preparing as the adhesive of graphite substrate material, solidify 2 hours at 260 DEG C, make 5
Group bonding piece, determines room temperature, high-temperature behavior respectively, and measurement atmosphere is air, as a result as shown in table 3.
The shear strength of table 3, superhigh temperature resistant adhesive at room temperature and 1000 DEG C
The preparation and application of embodiment 3, adhesive
First, formula
In terms of parts by weight, the present embodiment adhesive is grouped into by following groups：
Wherein, liquid poly carbon silane ceramics presoma includes two construction units of following mol ratio：
2nd, preparation method
(1) liquid poly carbon silane ceramics presoma shown in formula 3
Liquid poly carbon silane ceramics presoma shown in formula 3 in accordance with the following steps：
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
Triethoxysilane and the mixed solution of 2mL tetrahydrofurans, are slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 20mL ethylene is added by constant pressure funnel
The methyltetrahydrofuran solution of base magnesium bromide (1.6mol/L), 30 DEG C of insulation reaction 6h.After reaction terminates, 7.45g hydrogenations are added
Aluminum lithium, continues to react 10h at 30 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes is added, at 0～5 DEG C, reacts 0.5～2h, stood and divide
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, and separation is organic
Phase, adds 15g anhydrous magnesium sulfates to dry, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
70%, the product is-CH=CH corresponding to the R in formula (1)2, x=0.1, its molecular weight Mw=1472, Mn=654.
(2) adhesive is prepared
According to the proportioning of each component in above-mentioned formula, in beaker add formula 3 shown in liquid poly carbon silane ceramics presoma,
HfC、TiB2、SiC、B4C and mullite chopped strand, add AIBN after uniform mixing, mix well, deaerate 6 minutes, you can obtain
Resistance to adhesive.
3rd, apply
Using the above-mentioned adhesive for preparing as CfThe adhesive of/C composite, 180 DEG C solidify 5 hours, make 5 groups
Bonding piece, determines its room temperature and high-temperature behavior, and measurement atmosphere is nitrogen.As a result as shown in table 4.
Shear strength of the table 4, adhesive at room temperature and 1000 DEG C
The preparation and application of embodiment 4, adhesive
First, formula
In terms of parts by weight, the present embodiment adhesive is grouped into by following groups：
Wherein, liquid poly carbon silane ceramics presoma includes two construction units of following mol ratio：
2nd, preparation method
(1) liquid poly carbon silane ceramics presoma shown in formula 4
Liquid poly carbon silane ceramics presoma shown in formula 4 in accordance with the following steps：
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
Triethoxysilane and the mixed solution of 2mL tetrahydrofurans, are slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 40mL ethylene is added by constant pressure funnel
The methyltetrahydrofuran solution of base magnesium bromide (1.6mol/L), 30 DEG C of insulation reaction 6h.After reaction terminates, 7.45g hydrogenations are added
Aluminum lithium, continues to react 10h at 30 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes is added, at 0～5 DEG C, reacts 0.5～2h, stood and divide
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, and separation is organic
Phase, adds 15g anhydrous magnesium sulfates to dry, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
75%, the product is-CH=CH corresponding to the R in formula (1)2, x=0.2, its molecular weight Mw=1381, Mn=610.
(2) adhesive is prepared
According to the proportioning of each component in above-mentioned formula, in beaker add formula 4 shown in liquid poly carbon silane ceramics presoma,
SiC、B4C、SiO2、Al2O3、Y2O3With carborundum chopped strand, uniform mix after add MEKP, mix well, deaerate 7 minutes after i.e.
Adhesive is obtained.
3rd, apply
Using the above-mentioned adhesive for preparing as CfThe adhesive of/C composite, solidifies 3 hours at 220 DEG C, makes 5
Group bonding piece, determines its room temperature and high-temperature behavior, and measurement atmosphere is nitrogen, as a result as shown in table 5.
Shear strength of the table 5, adhesive at room temperature and 1400 DEG C
The preparation and application of embodiment 5, adhesive
First, formula
In terms of parts by weight, the present embodiment adhesive is grouped into by following groups：
Wherein, liquid poly carbon silane ceramics presoma includes two construction units of following mol ratio：
2nd, preparation method
(1) liquid poly carbon silane ceramics presoma shown in formula 5
Liquid poly carbon silane ceramics presoma shown in formula 5 in accordance with the following steps：
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
Triethoxysilane and the mixed solution of 2mL tetrahydrofurans, are slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 40mL ethylene is added by constant pressure funnel
The methyltetrahydrofuran solution of base magnesium bromide (1.6mol/L), 30 DEG C of insulation reaction 6h.After reaction terminates, 7.45g hydrogenations are added
Aluminum lithium, continues to react 10h at 30 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes is added, at 0～5 DEG C, reacts 0.5～2h, stood and divide
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, and separation is organic
Phase, adds 15g anhydrous magnesium sulfates to dry, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
75%, the product is-CH=CH corresponding to the R in formula (1)2, x=0.2, its molecular weight Mw=1381, Mn=610.
(2) resistance to adhesive is prepared
According to the proportioning of each component in above-mentioned formula, in beaker add formula 5 shown in liquid poly carbon silane ceramics presoma,
SiC、ZrB2, TiC and Al2O3, uniform mix after add BPO, mix well, deaerate 5 minutes after adhesive is obtained.
3rd, apply
Using the above-mentioned adhesive for preparing as CfThe adhesive of/SiC ceramic matrix composite material, solidifies 3 hours at 230 DEG C, system
Into 5 groups of bonding pieces, its room temperature and high-temperature behavior is determined, measurement atmosphere is nitrogen.As a result as shown in table 6.
Shear strength of the table 6, adhesive at room temperature and 1400 DEG C
The preparation and application of embodiment 6, adhesive
First, formula
In terms of parts by weight, the present embodiment adhesive is grouped into by following groups：
Wherein, liquid poly carbon silane ceramics presoma includes two construction units of following mol ratio：
2nd, preparation method
(1) liquid poly carbon silane ceramics presoma shown in formula 6
Liquid poly carbon silane ceramics presoma shown in formula 6 in accordance with the following steps：
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
Triethoxysilane and the mixed solution of 2mL tetrahydrofurans, are slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 40mL propylene is added by constant pressure funnel
The methyltetrahydrofuran solution of base magnesium bromide (1.6mol/L), is warming up to 40 DEG C and insulation reaction 6h.After reaction terminates, add
7.45g lithium aluminium hydride reductions, continue to react 10h at 40 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes is added, at 0～5 DEG C, reacts 0.5～2h, stood and divide
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, and separation is organic
Phase, adds 15g anhydrous magnesium sulfates to dry, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
70%, the product is CH corresponding to the R in formula (1)3- CH=CH-, x=0.2, its molecular weight Mw=1334, Mn=622.
(2) adhesive is prepared
According to the proportioning of each component in above-mentioned formula, in beaker add formula 6 shown in liquid poly carbon silane ceramics presoma,
Si3N4、Y2O3、Al2O3、SiO2And chopped carbon fiber, uniform mix after add DCP, mix well, deaerating 6 minutes is obtained glue
Stick.
3rd, apply
Using the above-mentioned adhesive for preparing as silicon nitride matrix material adhesive, then 180 DEG C solidify 3 hours, system
Into 5 groups of bonding pieces, its room temperature and high-temperature behavior is determined, measurement atmosphere is air.As a result as shown in table 7.
Shear strength of the table 7, adhesive at room temperature and 1000 DEG C
The preparation and application of embodiment 7, adhesive
First, formula
In terms of parts by weight, the present embodiment adhesive is grouped into by following groups：
Wherein, liquid poly carbon silane ceramics presoma includes two construction units of following mol ratio：
2nd, preparation method
(1) liquid poly carbon silane ceramics presoma shown in formula 7
Liquid poly carbon silane ceramics presoma shown in formula 7 in accordance with the following steps：
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
Triethoxysilane and the mixed solution of 2mL tetrahydrofurans, are slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 40mL isopropyls are added by constant pressure funnel
The methyltetrahydrofuran solution of thiazolinyl magnesium bromide (1.6mol/L), is warming up to 50 DEG C and insulation reaction 6h.After reaction terminates, add
7.45g lithium aluminium hydride reductions, continue to react 10h at 50 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes is added, at 0～5 DEG C, reacts 0.5～2h, stood and divide
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, and separation is organic
Phase, adds 15g anhydrous magnesium sulfates to dry, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
70%, the product is CH corresponding to the R in formula (1)3-CH(CH2)-, x=0.2, its molecular weight Mw=1307, Mn=589.
(2) adhesive is prepared
According to the proportioning of each component in above-mentioned formula, in beaker add formula 7 shown in liquid poly carbon silane ceramics presoma,
SiC、Y2O3、ZrB2And Al2O3, uniform mix after add AIBN, mix well, deaerate 6 minutes after adhesive is obtained.
3rd, apply
Using the above-mentioned adhesive for preparing as the adhesive of silicon carbide ceramics, solidify 2 hours at 260 DEG C, make 5 groups
Bonding piece, determines its room temperature and high-temperature behavior, and measurement atmosphere is air.As a result as shown in table 8.
Shear strength of the table 8, adhesive at room temperature and 1000 DEG C
The preparation and application of embodiment 8, adhesive
First, formula
In terms of parts by weight, the present embodiment adhesive is grouped into by following groups：
Wherein, liquid poly carbon silane ceramics presoma includes two construction units of following mol ratio：
2nd, preparation method
(1) liquid poly carbon silane ceramics presoma shown in formula 8
Liquid poly carbon silane ceramics presoma shown in formula 8 in accordance with the following steps：
One dry 1L three neck round bottom flask, connects mechanical agitator, reflux condensing tube, constant pressure funnel and inducing QI
Device, then evacuation displacement nitrogen three times, while heat gun baking is except the steam of attachment removal.In a nitrogen atmosphere, to reaction
5.0g magnesium chips is added in bottle, 4mL tetrahydrofurans is added, is heated to 30 DEG C.2.97g chloromethyls are added in constant pressure funnel
Triethoxysilane and the mixed solution of 2mL tetrahydrofurans, are slowly dropped in reaction bulb to cause grignard reaction.Drip to constant pressure
The mixed solution of 59.17g chloromethyls triethoxysilane and 150mL tetrahydrofurans is added in liquid funnel, with appropriate under stirring
Speed is added drop-wise in above reaction system, insulation reaction 4h at 30 DEG C.Then 40mL acetylene is added by constant pressure funnel
The methyltetrahydrofuran solution of base magnesium bromide (1.6mol/L), is warmed up to 60 DEG C and insulation reaction 6h.After reaction terminates, add
7.45g lithium aluminium hydride reductions, continue to react 10h at 60 DEG C.
368mL deionized waters, 130mL concentrated hydrochloric acid and 150mL hexanes is added, at 0～5 DEG C, reacts 0.5～2h, stood and divide
Layer, water are mutually extracted with 150mL hexanes, are merged organic faciess, and are washed with the dilute hydrochloric acid of 260mL, 1.7mol/L three times, and separation is organic
Phase, adds 15g anhydrous magnesium sulfates to dry, and filters revolving and obtains final product, is light yellow liquid Polycarbosilane, and yield is
70%, the product is CH corresponding to the R in formula (1)3-CH(CH2)-, x=0.2, its molecular weight Mw=1307, Mn=589.
(2) adhesive is prepared
According to the proportioning of each component in above-mentioned formula, in beaker add formula 8 shown in liquid poly carbon silane ceramics presoma,
SiC、Y2O3、ZrB2And Al2O3, uniform mix after add DBPH, mix well, deaerate 7 minutes after adhesive is obtained.
3rd, apply
Using the above-mentioned adhesive for preparing as the adhesive of silicon carbide ceramics, solidify 6 hours at 180 DEG C, make 5 groups
Bonding piece, determines its room temperature and high-temperature behavior, and measurement atmosphere is air.As a result as shown in table 9.
Shear strength of the table 9, adhesive at room temperature and 1000 DEG C
In sum, the invention provides a kind of based on liquid poly carbon silane ceramics presoma or which is polymer-modified resistance to
Superhigh temperature adhesive and preparation method thereof.The above, the only present invention preferably specific embodiment, but the protection of the present invention
Scope is not limited thereto, any those familiar with the art the invention discloses technical scope in, can be easily
The change or replacement that expects, should all be included within the scope of the present invention.
Claims (10)
1. a kind of adhesive, it is characterised in that：In terms of parts by weight, the adhesive is grouped into by following groups：The poly- carbon silicon of liquid
Alkane ceramic forerunner or its polymer-modified 100 parts, 0.5～5 part of firming agent, 0～300 part of solid packing, chopped strand 0～10
Part.
2. adhesive according to claim 1, it is characterised in that：The liquid poly carbon silane ceramics presoma includes as follows
Two construction units of mol ratio：
In formula, it is the group containing C=C, C ≡ C or cyclopropyl independently of one another that R is, x=0.7～0.9.
3. adhesive according to claim 1 and 2, it is characterised in that：The 25 of the liquid poly carbon silane ceramics presoma
DEG C viscosity is 100～10000mPa.s.
4. the adhesive according to any one of claim 1-3, it is characterised in that：The firming agent is peroxide cure
Agent or azo-initiator.
5. adhesive according to claim 4, it is characterised in that：The peroxide firming agent can be organic peroxide
Firming agent；The organic peroxide curing agent is included but is not limited to：Cumyl peroxide, methyl ethyl ketone peroxide, peroxidating
Benzoic acid, 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes；
The azo-initiator can be azodiisobutyronitrile.
6. the adhesive according to any one of claim 1-5, it is characterised in that：The solid packing is carborundum, carbon
Change zirconium, titanium carbide, hafnium carbide, boron carbide, aluminium carbide, silicon nitride, aluminium nitride, zirconium boride, titanium boride, silicon boride, titanium disilicide,
At least one in yittrium oxide, aluminium oxide and silicon oxide；And/or,
The particle diameter of the solid packing is 0.2～50 micron.
7. the preparation method according to any one of claim 1-6, it is characterised in that：The chopped strand is that mullite is fine
At least one in dimension, alumina fibre, silicon dioxide fibre, carbon fiber, silicon carbide fibre；And/or,
The length of the chopped strand is 1～10 millimeter.
8. the preparation method of the adhesive any one of claim 1-7, comprises the steps：The adhesive will be prepared
Each component according to deaerating the adhesive that obtain after parts by weight mixing.
9. the adhesive any one of claim 1-8 is in pottery or ceramic matric composite, carbon-based or its composite
Between bonding in application.
10. application according to claim 9, it is characterised in that：Described it is bonded in oxidation, reduction, inertia and vacuum
Any one atmosphere under carry out.
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| CN108250984A (en) * | 2018-01-22 | 2018-07-06 | 黑龙江省科学院石油化学研究院 | A kind of heat-resisting 3300 DEG C of superhigh temperature resistant adhesive |
| CN108794042A (en) * | 2018-07-13 | 2018-11-13 | 航天材料及工艺研究所 | A kind of binder for porous ceramics and preparation method thereof and application method |
| CN109970452A (en) * | 2019-04-30 | 2019-07-05 | 巩义市泛锐熠辉复合材料有限公司 | A kind of pressureless sintering preparation method of ceramic evaporation boat composite material |
| CN112300748A (en) * | 2020-09-25 | 2021-02-02 | 航天材料及工艺研究所 | Adhesive filler for splicing light porous composite material and preparation method thereof |
| CN113174206A (en) * | 2021-06-04 | 2021-07-27 | 成都工业学院 | High-temperature-resistant high-strength ceramic high-temperature glue, and preparation method and application thereof |
| CN115160572A (en) * | 2022-06-30 | 2022-10-11 | 航天材料及工艺研究所 | SiC ceramic precursor capable of being cured by ultraviolet light, preparation method and ceramic coating repairing method |
| CN115678019A (en) * | 2021-07-26 | 2023-02-03 | 中国科学院化学研究所 | Liquid polycarbosilane and preparation method and application thereof |
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| CN108250984A (en) * | 2018-01-22 | 2018-07-06 | 黑龙江省科学院石油化学研究院 | A kind of heat-resisting 3300 DEG C of superhigh temperature resistant adhesive |
| CN108250984B (en) * | 2018-01-22 | 2020-06-09 | 黑龙江省科学院石油化学研究院 | Heat-resistant 3300 ℃ ultrahigh temperature-resistant adhesive |
| CN108794042A (en) * | 2018-07-13 | 2018-11-13 | 航天材料及工艺研究所 | A kind of binder for porous ceramics and preparation method thereof and application method |
| CN108794042B (en) * | 2018-07-13 | 2020-11-10 | 航天材料及工艺研究所 | Binder for porous ceramic and preparation method and use method thereof |
| CN109970452A (en) * | 2019-04-30 | 2019-07-05 | 巩义市泛锐熠辉复合材料有限公司 | A kind of pressureless sintering preparation method of ceramic evaporation boat composite material |
| CN109970452B (en) * | 2019-04-30 | 2021-07-09 | 巩义市泛锐熠辉复合材料有限公司 | Pressureless sintering preparation method of composite material for ceramic evaporation boat |
| CN112300748A (en) * | 2020-09-25 | 2021-02-02 | 航天材料及工艺研究所 | Adhesive filler for splicing light porous composite material and preparation method thereof |
| CN112300748B (en) * | 2020-09-25 | 2023-05-12 | 航天材料及工艺研究所 | Adhesive filler for splicing light porous composite materials and preparation method thereof |
| CN113174206A (en) * | 2021-06-04 | 2021-07-27 | 成都工业学院 | High-temperature-resistant high-strength ceramic high-temperature glue, and preparation method and application thereof |
| CN115678019A (en) * | 2021-07-26 | 2023-02-03 | 中国科学院化学研究所 | Liquid polycarbosilane and preparation method and application thereof |
| CN115160572A (en) * | 2022-06-30 | 2022-10-11 | 航天材料及工艺研究所 | SiC ceramic precursor capable of being cured by ultraviolet light, preparation method and ceramic coating repairing method |
| CN115160572B (en) * | 2022-06-30 | 2024-02-09 | 航天材料及工艺研究所 | Ultraviolet-curable SiC ceramic precursor, preparation method and ceramic coating repair method |
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