CN114716970B - Silicon-boron-carbon-nitrogen composite adhesive and preparation and use methods thereof - Google Patents
Silicon-boron-carbon-nitrogen composite adhesive and preparation and use methods thereof Download PDFInfo
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- CN114716970B CN114716970B CN202210404932.7A CN202210404932A CN114716970B CN 114716970 B CN114716970 B CN 114716970B CN 202210404932 A CN202210404932 A CN 202210404932A CN 114716970 B CN114716970 B CN 114716970B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- ZQOBAJVOKBJPEE-UHFFFAOYSA-N [B].[C].[N].[Si] Chemical compound [B].[C].[N].[Si] ZQOBAJVOKBJPEE-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 16
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 21
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 methyl vinyl phenyl Chemical group 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052582 BN Inorganic materials 0.000 claims abstract description 10
- 239000012530 fluid Substances 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 22
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 13
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 11
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 9
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 9
- 239000005049 silicon tetrachloride Substances 0.000 claims description 9
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims 1
- 239000002861 polymer material Substances 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000002679 ablation Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09J183/04—Polysiloxanes
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- 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
-
- 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
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The silicon-boron-carbon-nitrogen composite adhesive comprises the following raw materials in parts by weight: 30-50 parts of methyl vinyl phenyl silazane melamine, 5-15 parts of hexagonal boron nitride, 40-50 parts of tackifier and 5-10 parts of epoxy T-shaped structural multifunctional silane, during preparation, the raw materials are uniformly mixed according to a required proportion, then the mixture is placed in a yarn mill modifier to react at 200-300 ℃ under the condition of more than or equal to 2MPa to form a fluid silicon boron carbon nitrogen composite adhesive, and when the adhesive is used, the adhesive is mixed with a solvent and sprayed on the surface of a substrate to form a film. The design not only has excellent high temperature resistance, but also has simple preparation process and convenient use.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a silicon-boron-carbon-nitrogen composite adhesive and a preparation method and a use method thereof.
Background
Along with the continuous development of technology, the high-temperature resistant materials are increasingly widely applied in the fields of machinery, chemical industry, electronics and the like. Among the high temperature resistant materials, silicon, boron, carbon and nitrogen are taken as novel quaternary structural ceramics, and the unique tissue structure and excellent high temperature performance of the quaternary structural ceramics are widely paid attention to domestic and foreign students. The silicon-boron-carbon-nitrogen ceramic can keep an amorphous state below 1500 ℃, and meanwhile, the silicon-boron-carbon-nitrogen fiber hardly loses weight at about 2000 ℃, and has excellent high-temperature stability.
Chinese patent: the invention patent of application number 201910096687.6 and application date 20191 month 31 discloses a silicon-boron-carbon-nitrogen ceramic composite material and a preparation method thereof, and the specific steps are as follows: firstly mixing silicon powder, graphite powder and hexagonal boron nitride powder, performing ball milling in a ball milling tank to obtain SiBCN amorphous powder, then mixing SiBCN amorphous powder with titanium reinforced phase powder, performing ball milling in the ball milling tank to obtain composite powder, and finally performing hot press sintering on the composite powder under the conditions of 1700-2100 ℃ and 30-90 MPa. The method has the following problems:
1. in the preparation process, hot press sintering is required under the conditions of ultrahigh temperature and high pressure, which can cause high energy consumption and high cost of the whole reaction;
2. because the final product is solid, the product needs to be compounded on the surface of the matrix in an ablative way, and the use is very inconvenient.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide the silicon-boron-carbon-nitrogen composite adhesive with excellent high temperature resistance, simple preparation process and convenient use and the preparation and application methods thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the silicon-boron-carbon-nitrogen composite adhesive comprises the following raw materials in parts by weight: 30-50 parts of methyl vinyl phenyl silazane melamine, 5-15 parts of hexagonal boron nitride, 40-50 parts of tackifier and 5-10 parts of epoxy T-type structural multifunctional silane.
The methyl vinyl phenyl silazane melamine comprises the following raw materials in parts by mole: melamine cyanurate 1, silicon tetrachloride 1-2, methyl vinyl dichlorosilane 1-2 and phenyl trichlorosilane 1-1.5.
The tackifier is S1001, and the epoxy T-shaped structure multifunctional silane is SHY301000.
The raw material composition of the adhesive also comprises a dispersion stabilizer, wherein the weight ratio of the dispersion stabilizer to the methyl vinyl phenyl silazane melamine is 1-3:30-50.
The dispersion stabilizer is acetylacetone.
A preparation method of a silicon-boron-carbon-nitrogen composite adhesive specifically comprises the following steps: the raw materials are uniformly mixed according to the required proportion, and then are placed in a yarn mill modifier to react under the conditions of 200-300 ℃ and more than or equal to 2MPa, so that the fluid silicon-boron-carbon-nitrogen composite adhesive is formed, and the particle diameter in the silicon-boron-carbon-nitrogen composite adhesive is 100-500nm.
The preparation method of the methyl vinyl phenyl silazane melamine sequentially comprises the following steps:
step one, adding melamine cyanurate, silicon tetrachloride, methyl vinyl dichlorosilane and phenyl trichlorosilane into a vulcanization bed according to the molar ratio of 1:1-2:1-2:1-1.5, and carrying out polycondensation reaction at 130-180 ℃ until no hydrogen chloride gas is released, so as to obtain a polymer material;
and step two, washing the polymer material, removing the low-boiling-point material in the polymer material at 100-120 ℃, cooling the rest material, filtering, taking a filter cake, and washing and drying the filter cake in sequence to obtain white particles, namely the methyl vinyl phenyl silazane melamine.
A method of using a silicon boron carbon nitrogen composite adhesive, comprising: firstly, adding a solvent into the silicon-boron-carbon-nitrogen composite adhesive for dilution and mixing, and then spraying the mixture on the surface of a substrate to form a film, wherein the volume ratio of the silicon-boron-carbon-nitrogen composite adhesive to the solvent is 1:1-1.5, and the solvent is at least one of alcohols, ketones and lipids.
When the base material is metal, after film formation, plasma laser is adopted to heat the base material to more than 1000 ℃ so as to enable the film to be closely attached to the surface of the base material.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a silicon-boron-carbon-nitrogen composite adhesive, which comprises the following raw materials in parts by weight: 30-50 parts of methyl vinyl phenyl silazane melamine, 5-15 parts of hexagonal boron nitride, 40-50 parts of tackifier and 5-10 parts of epoxy T-shaped structural multifunctional silane, during preparation, the raw materials are uniformly mixed according to a required proportion, then the mixture is placed in a yarn mill modifier to react at 200-300 ℃ and more than or equal to 2MPa to form a fluid silicon boron carbon nitrogen composite adhesive, on one hand, the adhesive is a prepolymer, and can be gradually ceramic in a high-temperature use environment to form silicon boron carbon nitrogen ceramic particles, so that excellent high-temperature resistance is achieved, on the other hand, the preparation process is relatively simple, and the final product is fluid, and is sprayed on the surfaces of base materials such as plastics, wood, metal and the like to form a film after the solvent is added during use. Therefore, the invention not only has excellent high temperature resistance, but also has simple preparation process and convenient use.
Drawings
FIG. 1 is a microstructure of a sample after ablation testing at various temperatures, in which A:800 ℃, B:1200 ℃, C:1500 ℃, D:1800 ℃.
FIG. 2 is a graph of a sample after an ablation test at 1800 ℃.
Detailed Description
The invention is further described below with reference to the detailed description and the accompanying drawings.
The silicon-boron-carbon-nitrogen composite adhesive comprises the following raw materials in parts by weight: 30-50 parts of methyl vinyl phenyl silazane melamine, 5-15 parts of hexagonal boron nitride, 40-50 parts of tackifier and 5-10 parts of epoxy T-type structural multifunctional silane.
The methyl vinyl phenyl silazane melamine comprises the following raw materials in parts by mole: melamine cyanurate 1, silicon tetrachloride 1-2, methyl vinyl dichlorosilane 1-2 and phenyl trichlorosilane 1-1.5.
The tackifier is S1001, and the epoxy T-shaped structure multifunctional silane is SHY301000.
The raw material composition of the adhesive also comprises a dispersion stabilizer, wherein the weight ratio of the dispersion stabilizer to the methyl vinyl phenyl silazane melamine is 1-3:30-50.
The dispersion stabilizer is acetylacetone.
A preparation method of a silicon-boron-carbon-nitrogen composite adhesive specifically comprises the following steps: the raw materials are uniformly mixed according to the required proportion, and then are placed in a yarn mill modifier to react under the conditions of 200-300 ℃ and more than or equal to 2MPa, so that the fluid silicon-boron-carbon-nitrogen composite adhesive is formed, and the particle diameter in the silicon-boron-carbon-nitrogen composite adhesive is 100-500nm.
The preparation method of the methyl vinyl phenyl silazane melamine sequentially comprises the following steps:
step one, adding melamine cyanurate, silicon tetrachloride, methyl vinyl dichlorosilane and phenyl trichlorosilane into a vulcanization bed according to the molar ratio of 1:1-2:1-2:1-1.5, and carrying out polycondensation reaction at 130-180 ℃ until no hydrogen chloride gas is released, so as to obtain a polymer material;
and step two, washing the polymer material, removing the low-boiling-point material in the polymer material at 100-120 ℃, cooling the rest material, filtering, taking a filter cake, and washing and drying the filter cake in sequence to obtain white particles, namely the methyl vinyl phenyl silazane melamine.
A method of using a silicon boron carbon nitrogen composite adhesive, comprising: firstly, adding a solvent into the silicon-boron-carbon-nitrogen composite adhesive for dilution and mixing, and then spraying the mixture on the surface of a substrate to form a film, wherein the volume ratio of the silicon-boron-carbon-nitrogen composite adhesive to the solvent is 1:1-1.5, and the solvent is at least one of alcohols, ketones and lipids.
When the base material is metal, after film formation, plasma laser is adopted to heat the base material to more than 1000 ℃ so as to enable the film to be closely attached to the surface of the base material.
The physicochemical properties of the silicon-boron-carbon-nitrogen composite adhesive provided by the invention are as follows:
appearance: white milk-like;
specific gravity: 1.30-1.40 g/cm 3 ；
Viscosity: 950-1050cps.
The tackifier S1001 and the epoxy T-shaped structure multifunctional silane SHY301000 adopted by the invention are produced by Hubei Limeida silicon fluorine technology Co., ltd, wherein,
s1001 is a stainless steel tackifier, is a special auxiliary agent for bonding stainless steel, plastic steel and other base materials with lower surface energy, and is developed aiming at medium permeation circulation glue, has strong adhesive force and good reinforcing effect, and is particularly suitable for silicone glue with medium permeation 107 content of about 35 percent. Can also be used for tackifying in heterochromatic glue. The product is colorless and transparent, and has a specific gravity of 1.05 shi 0.08g/cm 3 The using method and the adding amount are as follows: the cross-linking agent is added after the glue preparation process, the total weight of the cross-linking agent is about 4-6 per mill, other coupling agents are reduced or not added, and each manufacturer can adjust and add the cross-linking agent under the guidance of engineers. Note that the product is stored in a sealed state at normal temperature, and the effective period is one year. The thickening phenomenon occurs when the hydroxyl or the water content in the added glue is too high.
SHY301000 is epoxy T-shaped structural multifunctional silane, has the characteristics of good compatibility and strong adhesive force, and is particularly suitable for various alloys and simple substance metal materials. Physicochemical properties of pale yellow or colorless transparent, viscosity of 500+ -100 Cs, and densityThe degree of the mixture is 0.98+/-0.05 g/cm 3 . The use and preservation method comprises the following steps: adding 2% of the total material into the base material, uniformly dispersing, and preserving heat for 9 months at normal temperature, wherein the application test or viscosity test is required to be carried out for more than the time.
For the metal substrate, plasma laser is adopted to heat the metal substrate to more than 1000 ℃ after film formation, so that the film is tightly attached to the surface of the metal substrate, and the wear resistance of the film can be effectively improved.
Example 1:
the silicon-boron-carbon-nitrogen composite adhesive comprises the following raw materials in parts by weight: 40 parts of methyl vinyl phenyl silazane melamine, 10 parts of hexagonal boron nitride, 1001 45 parts of tackifier S, 301000 7 parts of epoxy T-type structural multifunctional silane SHY and 1 part of dispersion stabilizer acetylacetone, wherein the raw materials of the methyl vinyl phenyl silazane melamine comprise the following components in parts by mole: 1 part of melamine cyanurate, 1.5 parts of silicon tetrachloride, 1.5 parts of methyl vinyl dichlorosilane, 1 part of phenyl trichlorosilane and 1 part of catalyst nano copper chloride.
The preparation method of the silicon-boron-carbon-nitrogen composite adhesive comprises the following steps in sequence:
step one, adding melamine cyanurate, silicon tetrachloride, methyl vinyl dichlorosilane and phenyl trichlorosilane into a fluidized bed according to a required proportion, and performing polycondensation reaction at 150 ℃ until no hydrogen chloride gas is released, so as to obtain a polymer material;
step two, washing a polymer material, removing low-boiling-point materials in the polymer material under the conditions of 110 ℃ and minus 0.09MPa, cooling the rest materials, filtering, taking a filter cake, and washing and drying the filter cake in sequence to obtain white granular methyl vinyl phenyl silazane melamine;
step three, uniformly mixing methyl vinyl phenyl silazane melamine, hexagonal boron nitride, tackifier S1001, epoxy T-type structural multifunctional silane SHY301000 and dispersion stabilizer acetylacetone according to a required proportion, and then placing the mixture in a yarn mill modifier for reaction at the temperature of 250 ℃ and under the pressure of 2.5MPa to form a fluid milky-white silicon boron carbon nitrogen composite adhesive, wherein the particle diameter of the silicon boron carbon nitrogen composite adhesive is 100-500nm.
The application method of the silicon-boron-carbon-nitrogen composite adhesive comprises the following steps: firstly adding a solvent methanol into a silicon-boron-carbon-nitrogen composite adhesive for dilution and mixing, spraying the mixture on the surface of a steel plate for film formation, and then heating the steel plate to above 1000 ℃ by adopting plasma laser to enable the film to be closely attached to the surface of the steel plate, wherein the volume ratio of the silicon-boron-carbon-nitrogen composite adhesive to the solvent is 1:1, and the solvent is methanol.
Example 2:
the difference from example 1 is that:
the silicon-boron-carbon-nitrogen composite adhesive comprises the following raw materials in parts by weight: 50 parts of methyl vinyl phenyl silazane melamine, 12 parts of hexagonal boron nitride, 1001 50 parts of tackifier S, 301000 10 parts of epoxy T-type structural multifunctional silane SHY and 2 parts of dispersion stabilizer acetylacetone;
the organosilicon hybridized melamine cyanurate comprises the following raw materials in parts by mole: 1 part of melamine cyanurate, 2 parts of silicon tetrachloride, 2 parts of methyl vinyl dichlorosilane, 1.5 parts of phenyl trichlorosilane and 1 part of catalyst nano copper chloride.
The application method of the silicon-boron-carbon-nitrogen composite adhesive comprises the following steps: firstly, adding solvent acetone into the silicon-boron-carbon-nitrogen composite adhesive for dilution and mixing, and then spraying the mixture on the surface of a plastic substrate for film formation, wherein the volume ratio of the silicon-boron-carbon-nitrogen composite adhesive to the solvent is 1:1.
Example 3:
the difference from example 1 is that:
the organic silicon hybrid melamine cyanurate comprises the following raw materials in parts by mole: melamine cyanurate 1, silicon tetrachloride 1.5, methyl vinyl dichlorosilane 1.5, phenyl trichlorosilane 1 and catalyst nano copper chloride 1.5.
In the first step, the temperature of the polycondensation reaction is 130 ℃;
in the second step, the conditions for removing the low boiling point materials are as follows: 100 ℃ and-0.098 MPa.
Example 4:
the difference from example 1 is that:
the silicon-boron-carbon-nitrogen composite adhesive comprises the following raw materials in parts by weight: 30 parts of methyl vinyl phenyl silazane melamine, 7 parts of hexagonal boron nitride, 1001 40 parts of tackifier S, 301000 6 parts of epoxy T-type structural multifunctional silane SHY and 1.5 parts of dispersion stabilizer acetylacetone;
the solvent adopted in the using method of the silicon-boron-carbon-nitrogen composite adhesive is acetone.
Example 5:
the difference from example 2 is that:
the silicon-boron-carbon-nitrogen composite adhesive comprises the following raw materials in parts by weight: 36 parts of methyl vinyl phenyl silazane melamine, 15 parts of hexagonal boron nitride, 1001 42 parts of tackifier S, 301000 8 parts of epoxy T-type structural multifunctional silane SHY and 2 parts of dispersion stabilizer acetylacetone;
the application method of the silicon-boron-carbon-nitrogen composite adhesive comprises the following steps: adding solvent ethanol into the silicon-boron-carbon-nitrogen composite adhesive for dilution and mixing, and then spraying the mixture on the surface of a wood substrate to form a film, wherein the volume ratio of the silicon-boron-carbon-nitrogen composite adhesive to the solvent is 1:1.2.
In order to examine the high temperature resistance of the product of the invention, the following tests are carried out:
the film-forming product obtained in example 1 was divided into 4 parts, and plasma laser ablation was performed at 800℃and 1200℃and 1500℃and 1800℃respectively, and the surface structure of the ablated metal substrate was observed with a microscope (. Times.200 times), and the results are shown in FIGS. 1 and 2.
As can be seen from fig. 1 and 2, the granularity of the film on the surface of the steel plate gradually increases with the continuous increase of the ablation temperature, because the components in the film gradually ceramic with the increase of the temperature, the complete form of the film can be maintained when the temperature is 1500 ℃, and part of the steel plate substrate is melted under the condition that the temperature reaches 1800 ℃, and the form of the film is destroyed, so that ceramic particles are attached to the surface of the substrate.
Claims (4)
1. A silicon-boron-carbon-nitrogen composite adhesive is characterized in that:
the adhesive comprises the following raw materials in parts by weight: 30-50 parts of methyl vinyl phenyl silazane melamine, 5-15 parts of hexagonal boron nitride, 5-50 parts of tackifier S1001 40-50 parts of epoxy T-type structural multifunctional silane SHY301000 5-10 parts of dispersion stabilizer 1-3 parts;
the methyl vinyl phenyl silazane melamine comprises the following raw materials in parts by mole: melamine cyanurate 1, silicon tetrachloride 1-2, methyl vinyl dichlorosilane 1-2 and phenyl trichlorosilane 1-1.5;
the preparation method of the adhesive comprises the following steps: the raw materials are uniformly mixed according to the required proportion, and then are placed in a sanding modifier to react under the conditions of 200-300 ℃ and more than or equal to 2MPa, so that the fluid silicon-boron-carbon-nitrogen composite adhesive is formed, and the particle diameter in the silicon-boron-carbon-nitrogen composite adhesive is 100-500nm.
2. A silicon boron carbon nitrogen composite adhesive according to claim 1, wherein: the dispersion stabilizer is acetylacetone.
3. A method of using the silicon-boron-carbon-nitrogen composite adhesive of claim 1, wherein:
the using method comprises the following steps: firstly, adding a solvent into the silicon-boron-carbon-nitrogen composite adhesive for dilution and mixing, and then spraying the mixture on the surface of a substrate to form a film, wherein the volume ratio of the silicon-boron-carbon-nitrogen composite adhesive to the solvent is 1:1-1.5, and the solvent is at least one of alcohols, ketones and esters.
4. A method of using a silicon boron carbon nitrogen composite adhesive according to claim 3, wherein: when the base material is metal, after film formation, plasma laser is adopted to heat the base material to more than 1000 ℃ so as to enable the film to be closely attached to the surface of the base material.
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| CN106190018A (en) * | 2016-08-08 | 2016-12-07 | 岳胜武 | Sprayable self-adhesion direct type environment-friendly silica gel glue and preparation method thereof |
| CN111534271A (en) * | 2020-05-12 | 2020-08-14 | 广东圣堡达高新科技有限公司 | Glue for roads and bridges and preparation method thereof |
| CN114106340A (en) * | 2021-12-28 | 2022-03-01 | 力美达新材料科技研究开发(广东)有限公司 | Organic silicon hybrid melamine cyanurate, and preparation method and application thereof |
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| CN106190018A (en) * | 2016-08-08 | 2016-12-07 | 岳胜武 | Sprayable self-adhesion direct type environment-friendly silica gel glue and preparation method thereof |
| CN111534271A (en) * | 2020-05-12 | 2020-08-14 | 广东圣堡达高新科技有限公司 | Glue for roads and bridges and preparation method thereof |
| CN114106340A (en) * | 2021-12-28 | 2022-03-01 | 力美达新材料科技研究开发(广东)有限公司 | Organic silicon hybrid melamine cyanurate, and preparation method and application thereof |
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