CN115028790B - High-temperature-resistant epoxy resin curing agent and preparation method thereof - Google Patents
High-temperature-resistant epoxy resin curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN115028790B CN115028790B CN202210709374.5A CN202210709374A CN115028790B CN 115028790 B CN115028790 B CN 115028790B CN 202210709374 A CN202210709374 A CN 202210709374A CN 115028790 B CN115028790 B CN 115028790B
- Authority
- CN
- China
- Prior art keywords
- curing agent
- cardanol
- epoxy resin
- parts
- anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 96
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical class OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 93
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 37
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 37
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 20
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 20
- 150000008064 anhydrides Chemical class 0.000 claims description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 17
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 14
- 239000002516 radical scavenger Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 17
- 238000004132 cross linking Methods 0.000 abstract description 10
- 239000004593 Epoxy Substances 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 6
- 238000001723 curing Methods 0.000 description 91
- 230000000052 comparative effect Effects 0.000 description 17
- 230000004580 weight loss Effects 0.000 description 15
- 238000005886 esterification reaction Methods 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- -1 modified phenolic aldehyde Chemical class 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The application relates to the technical field of epoxy curing agents, and particularly discloses a high-temperature-resistant epoxy resin curing agent and a preparation method thereof. The high-temperature-resistant epoxy resin curing agent comprises the following components in parts by weight: 360-480 parts of modified cardanol; 30-40 parts of paraformaldehyde; 150-190 parts of amine; 2-10 parts of a catalyst B; the preparation method of the modified cardanol comprises the following steps: adding organic silicon and a catalyst A into the cardanol solution, and stirring and mixing to obtain a mixed solution A; and adding citric acid into the mixed solution A, adding a water removing agent and absolute ethyl alcohol during stirring, stirring and mixing, and distilling to obtain the modified cardanol. The composition has the advantages of increasing the crosslinking density between the curing agent and the epoxy resin and improving the heat resistance of the generated polymer.
Description
Technical Field
The application relates to the technical field of epoxy curing agents, in particular to a high-temperature-resistant epoxy resin curing agent and a preparation method thereof.
Background
The epoxy resin curing agent is a chemical substance which reacts with the epoxy resin to form a netlike three-dimensional polymer, and can be divided into a low-temperature curing agent, a room-temperature curing agent, a medium-temperature curing agent and a high-temperature curing agent according to the curing temperature, and a curing agent with high curing temperature can be used for obtaining a curing product with better heat resistance.
Common epoxy resin curing agents include aliphatic amine curing agents, aromatic polyamine curing agents, modified polyamine curing agents, polythiol curing agents, anhydride curing agents, wherein the modified polyamine curing agents have different excellent properties and become the most diverse curing agents.
In the related art, there is an epoxy resin curing agent based on cardanol, which consists of bisphenol a, cardanol, paraformaldehyde, zinc acetate and diethylenetriamine, and the prepared curing agent has a shore hardness of 90 degrees at 25 ℃, a shore hardness of 70 degrees at 100 ℃ for 0.5 h.
For the above related art, the inventors found that the curing agent has a certain high temperature resistance, but the strength loss of the curing agent in the environment of 100 ℃ and 0.5h is as high as 22.2%, which indicates that the high temperature resistance is still to be improved.
Disclosure of Invention
In order to improve the heat resistance of the cardanol-based curing agent, the application provides a high-temperature-resistant epoxy resin curing agent and a preparation method thereof.
In a first aspect, the present application provides a high temperature resistant epoxy resin curing agent, which adopts the following technical scheme:
the high-temperature-resistant epoxy resin curing agent comprises the following components in parts by weight:
360-480 parts of modified cardanol;
30-40 parts of paraformaldehyde;
150-190 parts of amine;
2-10 parts of a catalyst B;
the preparation method of the modified cardanol comprises the following steps: adding organic silicon and a catalyst A into the cardanol solution, and stirring and mixing to obtain a mixed solution A; and adding citric acid into the mixed solution A, adding a water removing agent and absolute ethyl alcohol during stirring, stirring and mixing, and distilling to obtain the modified cardanol.
By adopting the technical scheme, the organic silicon has better heat resistance, and can directly improve the high temperature resistance of the curing agent; the carboxyl in the citric acid and the phenolic hydroxyl in the cardanol are subjected to esterification reaction to form ester bonds, the number of chemical bonds of the curing agent, which can be crosslinked with the epoxy resin, is increased, so that the crosslinking point between the curing agent and the epoxy resin is increased, the crosslinking density is increased, the initial thermal decomposition temperature of the polymer is improved due to the high crosslinking density, the stability of the polymer at high temperature is better, the polymer is not easy to be thermally decomposed, and the high temperature resistance of the curing agent is indirectly improved.
The hardness loss of the polymer prepared by using the curing agent is 17.6% at maximum and H is tested by high temperature resistance 150 The temperature is at least 338 degrees up to 86 degrees and the thermal weight loss is 5 percent, and compared with the curing agent prepared by using the non-modified cardanol, the curing agent has lower hardness loss, higher weight loss temperature and better heat resistance.
The direct use of anhydride and cardanol esterification has lower reactivity than citric acid, and may result in incomplete reaction, 21.7% loss of hardness, H 150 The temperature at which the thermal weight loss was 5% was 83℃and the heat resistance was poor. The citric acid used in the application is dehydrated to form anhydride and then reacts with cardanol, so that the citric acid has higher reactivity, the amount of carboxylic acid groups participating in the reaction is increased, the density of generated ester bonds is higher, and meanwhile, the chemical properties of the formed ester bonds are stable. Meanwhile, through esterification with phenolic hydroxyl groups, adsorption sites of water molecules are reduced, the hydrophobicity of cardanol is further improved, and through detection, the waterproof performance of the modified phenolic aldehyde modified polyester is as high as 320 hours, so that the waterproof performance of the modified phenolic aldehyde modified polyester is better, the surface drying time is less than 1.5 hours, the modified phenolic aldehyde modified polyester is short in curing time and not easy to drip during use, and the modified phenolic aldehyde modified polyester is convenient to use.
Preferably, the weight ratio of the cardanol to the organic silicon to the citric acid is (3-5): 0.5-1): 1.
By adopting the technical scheme, when the weight ratio of the lumbar phenol to the organic silicon to the citric acid is in the range, the synergistic effect of the organic silicon and the citric acid is better, the hardness loss of the obtained curing agent is reduced to 15.5-16.2%, and the temperature at the time of 5% of thermal weight loss is increased to 342-343.5 ℃.
Preferably, the weight ratio of the cardanol to the citric acid is (3-4): 1.
By adopting the technical scheme, the weight ratio of cardanol to citric acid is further optimized, and the prepared curing agent has better heat resistance when various performances are compared with other weight ratios. The analysis is possible because, by increasing the specific gravity of the citric acid, the greater the content of the citric acid, the greater the esterification degree, the more chemical crosslinking points are generated by the curing agent, and the heat resistance of the curing agent is better.
Preferably, the catalyst A is NaHSO 4 、ZnCl 2 、CaCl 2 、MgCl 2 、AlCl 3 A mixture of one or more of the above.
By adopting the technical scheme, when the catalyst A adopts NaHSO 4 、ZnCl 2 、CaCl 2 、MgCl 2 、AlCl 3 One of (a)When the mixture of one or more components is used, the hardness loss is further reduced by 0.4 to 0.6 percent compared with the use of KOH as a catalyst, and the heat resistance of the curing agent is better.
Preferably, the water scavenger is one or more of N, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and dicyclohexylcarbodiimide.
By adopting the technical scheme, when the catalyst adopts the substances, the catalyst can be used as a water scavenger to remove water in the reaction so as to prevent the reverse reaction, and meanwhile, the catalyst can be used as a catalyst to play a role in promoting the reaction.
Preferably, in the process of adding the organosilicon and the catalyst A into the cardanol, anhydride is also added;
the weight ratio of the addition amount of the anhydride to the cardanol is 1 (4-6).
By adopting the technical scheme, the acid anhydride reacts with unreacted cardanol, so that the esterification reaction is more sufficient, a more compact cross-linked structure is formed, and the heat resistance of the curing agent is further improved. The curing agent using anhydride in the present application reduced the polymer hardness loss by 1.5% and increased the temperature at 5% thermal weight loss by 3.1 ℃ compared to the curing agent without anhydride.
Preferably, the anhydride consists of phthalic anhydride, maleic anhydride, methyl nadic anhydride.
By adopting the technical scheme, the high temperature resistance of the curing agent can be improved by using phthalic anhydride, maleic anhydride and methyl nadic anhydride, and the heat resistance of the cured polymer is improved to the maximum extent by compounding the phthalic anhydride, the maleic anhydride, the methyl nadic anhydride and the methyl nadic anhydride, compared with the polymer prepared by the curing agent of phthalic anhydride which is singly used, the hardness loss of the curing agent is reduced to 12.2 percent, the temperature of the curing agent when the thermal weight loss is 5 percent is increased to 353.0 ℃, and the heat resistance of the curing agent is good.
Preferably, the weight ratio of the phthalic anhydride to the maleic anhydride to the methyl nadic anhydride is 1 (1-2) to 1-1.5.
By adopting the technical scheme: when phthalic anhydride, maleic anhydride, methyl nadic anhydrideWhen the weight ratio is in the range, the curing agent has better synergistic effect, the performance of the polymer formed by polymerizing the curing agent and the epoxy resin is detected, the hardness loss is reduced to 11.4-11.7%, the temperature is increased to 355.1-355.5 ℃ when the thermal weight loss is 5%, and H 150 Up to 92 degrees, the heat resistance of the curing agent is excellent.
Preferably, the composition comprises the following components in parts by weight:
420-460 parts of modified cardanol;
33-37 parts of paraformaldehyde;
160-180 parts of amine;
4-8 parts of catalyst B.
In a second aspect, the present application provides a method for preparing a high temperature resistant epoxy resin curing agent, which adopts the following technical scheme:
a preparation method of a high-temperature-resistant epoxy resin curing agent comprises the following steps:
s1, adding modified cardanol and amine into a catalyst B, and stirring and mixing to obtain a mixed solution B;
s2, adding paraformaldehyde into the mixed solution, stirring, mixing and distilling to obtain the high-temperature-resistant epoxy resin curing agent.
By adopting the technical scheme: the method is simple and efficient, is suitable for industrial mass production, and ensures that the epoxy resin curing agent has higher heat resistance, so that the prepared epoxy resin polymer has better heat resistance and is not easy to deform, melt drop and decompose at high temperature.
1. According to the preparation method, the citric acid and the organic silicon modified cardanol are used, the heat resistance of the curing agent is directly improved through the organic silicon, the citric acid and the cardanol are used for esterification to form ester bonds, and the crosslinking point between the curing agent and the epoxy resin is increased, so that the crosslinking density is improved, the formed polymer has higher thermal decomposition temperature, and the heat resistance is excellent;
2. in the method, the weight ratio of the citric acid to the cardanol is controlled, so that the ratio of the citric acid is increased, the esterification reaction is more complete, the crosslinking density is higher, and the heat resistance is further improved;
3. the acid anhydride is used for carrying out esterification reaction with part of unreacted cardanol, so that the heat resistance is further improved.
Detailed Description
The present application is described in further detail below with reference to examples.
Preparation example
Preparation example 1
A preparation method of the modified cardanol comprises the following steps: adding 4kg of organic silicon and 0.5kg of catalyst A into 25kg of cardanol solution, stirring and mixing, and reacting for 10 hours at 120 ℃ to obtain a mixed solution A; adding 10kg of citric acid into the mixed solution A, adding 0.2kg of a water removing agent and 1.5kg of absolute ethyl alcohol into the mixed solution A while stirring, stirring and mixing, reacting for 20 hours at 150 ℃, and distilling to obtain a modified cardanol crude product; adding the modified cardanol crude product into absolute ethyl alcohol with the volume being 3 times that of the modified cardanol crude product, washing, and filtering to remove sediment to obtain modified cardanol;
wherein the organosilicon is polydimethylsiloxane;
catalyst A is KOH;
the water scavenger is 4A molecular sieve.
Preparation examples 2 to 6
The modified cardanol is different from the preparation example 1 in that: the weight ratios of cardanol, silicone and citric acid were different, and are shown in table 1.
TABLE 1 Components in preparation examples 1-6 and weights (kg)
Preparation example 7
The modified cardanol is different from the preparation example 4 in that: the catalyst A was used in different conditions using the same amount of NaHSO 4 Instead of KOH.
Preparation example 8
The modified cardanol is different from the preparation example 4 in that: the catalyst A was used in different conditions using an equal amount of CaCl 2 Instead of KOH.
Preparation example 9
The modified cardanol is different from the preparation example 4 in that: the catalyst A was used in different conditions and in equal amounts from NaHSO 4 、CaCl 2 The mixture with the weight ratio of 1:1 replaces KOH.
Preparation example 10
Modified cardanol differing from preparation example 9 in that: the use of the water scavenger is different, and the equivalent amount of N, N' -diisopropylcarbodiimide is used to replace the 4A molecular sieve.
PREPARATION EXAMPLE 11
Modified cardanol differing from preparation example 9 in that: the use of the water scavenger is different, and the equivalent amount of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is used to replace the 4A molecular sieve.
Preparation example 12
Modified cardanol differing from preparation example 9 in that: the use condition of the water scavenger is different, and the equal amount of the mixture of N, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the weight ratio of 1:1 is used for replacing the 4A molecular sieve.
Preparation example 13
Modified cardanol differing from preparation example 12 in that: in the process of adding the organic silicon and the catalyst A into the cardanol, anhydride which is phthalic anhydride is also added;
the weight ratio of the addition amount of phthalic anhydride to cardanol is 1:4.
PREPARATION EXAMPLE 14
Modified cardanol differing from preparation example 13 in that: the weight ratio of the addition amount of phthalic anhydride to cardanol is 1:5.
Preparation example 15
Modified cardanol differing from preparation example 13 in that: the weight ratio of the addition amount of phthalic anhydride to cardanol is 1:6.
PREPARATION EXAMPLE 16
Modified cardanol differing from preparation example 14 in that: the anhydride was used in different ways, and the phthalic anhydride was replaced by an equal amount of a mixture of phthalic anhydride, maleic anhydride, methylnadic anhydride in a weight ratio of 1:0.5:0.5.
Preparation example 17
Modified cardanol differing from preparation example 16 in that: the weight ratio of phthalic anhydride, maleic anhydride and methyl nadic anhydride is 1:1:1.
PREPARATION EXAMPLE 18
Modified cardanol differing from preparation example 16 in that: the weight ratio of phthalic anhydride, maleic anhydride and methyl nadic anhydride is 1:1.5:1.2.
Preparation example 19
Modified cardanol differing from preparation example 16 in that: the weight ratio of phthalic anhydride, maleic anhydride and methyl nadic anhydride is 1:2:1.5.
Preparation example 20
The modified cardanol is different from the preparation example 1 in that: an equivalent amount of maleic anhydride was used instead of citric acid.
Examples
Example 1
The high temperature resistant epoxy resin curing agent is prepared from the following components in parts by weight as shown in Table 3:
s1, adding modified cardanol and amine into a catalyst B, stirring and mixing, and reacting for 2 hours at 60 ℃ to obtain a mixed solution B;
s2, adding paraformaldehyde into the mixed solution B, stirring and mixing, reacting for 3 hours at 80 ℃, and distilling to remove water to obtain the high-temperature-resistant epoxy resin curing agent;
wherein, the modified cardanol is prepared and obtained by a preparation example 1;
the catalyst B is N, N-dimethyl cyclohexane;
the amine is triethylene tetramine;
examples 2 to 5
The high temperature resistant epoxy resin curing agent is different from example 1 in that the components are different in weight, and the specific weight is shown in table 3.
Examples 6 to 10
The difference between the high temperature resistant epoxy resin curing agent and the example 3 is that the modified cardanol is used in different conditions, and the specific conditions are shown in table 3.
Examples 11 to 13
The difference between the high temperature resistant epoxy resin curing agent and the modified cardanol in example 8 is that the modified cardanol was used in different conditions, as shown in table 3.
Examples 14 to 16
The difference between the high temperature resistant epoxy resin curing agent and the modified cardanol in example 12 is that the modified cardanol was used in different conditions, as shown in table 3.
Examples 17 to 19
The difference between the high temperature resistant epoxy resin curing agent and the modified cardanol in example 15 is that the modified cardanol was used in different conditions, as shown in table 3.
Example 20
The difference between the high temperature resistant epoxy resin curing agent and the example 3 is that the modified cardanol is used in different conditions, and the specific conditions are shown in table 3.
Examples 21 to 23
The difference between the high temperature resistant epoxy resin curing agent and the example 20 is that the modified cardanol was used in different conditions, as shown in Table 3.
Comparative example
Comparative example 1
A high temperature resistant epoxy curing agent is distinguished from example 1 in that cardanol is used in place of modified cardanol in an equivalent amount.
Comparative example 2
The difference between the high temperature resistant epoxy resin curing agent and the modified cardanol in example 1 is that the modified cardanol is used in different conditions, and in the preparation process of the modified cardanol, the same amount of maleic anhydride is used to replace citric acid.
Comparative examples 3 to 4
The high temperature resistant epoxy resin curing agent is different from example 1 in that the components are different in weight, and the specific weight is shown in table 2.
TABLE 2 weight (kg) of the components in examples 1-5, comparative examples 3-4
Performance detection
Detection method
The high temperature resistant epoxy curing agents prepared in examples and comparative examples were mixed with bisphenol A type epoxy resin, and cured to form a polymer, which was prepared into a test piece having a side length of 50mm and a thickness of 6mm, and the test patterns were subjected to the following test, and the test results are shown in Table 3.
Test one, shore hardness test:
the sample was placed in a laboratory incubator at 25℃and 100℃and 150℃for 0.5h, and Shore hardness was measured in units of degrees according to GB/T531.1-2008 "method for hardness test for indentation of vulcanized rubber or thermoplastic rubber".
According to the Shore hardness values of the patterns at 100 ℃ and 25 ℃, the hardness loss is calculated, and the calculation formula is as follows:
test two, thermal weight loss test:
cutting the sample to 100g, performing thermogravimetric analysis on the sample by using a Q50-TGA thermogravimetric analyzer, heating at 10 ℃/min and 25-800 ℃, and recording the corresponding temperature value (T) of the sample when the mass loss is 5% 5％ ) Higher temperature values indicate better thermal stability of the sample in degrees celsius.
Test three, water resistance test:
the heat-resistant epoxy curing agent prepared in the examples and the comparative examples is added into an epoxy resin emulsion with a solid content of 52%, the weight ratio of the epoxy curing agent to the epoxy resin emulsion is 1:1, a coating is prepared, and the coating is coated and cast into a film. The coatings prepared from the epoxy curing agents of the present application were tested for their barrier properties according to GB/T1733-1993 determination of water resistance of paint films. The time in h at which the surface of the coating began to develop rust was recorded, the longer the time indicated the better the water resistance of the coating.
Test IV, surface dry time test: the detection is carried out according to GB/T1728-1979 method for measuring the drying time of paint film putty film.
TABLE 3 Performance test results for examples 1-23, comparative examples 1-4
In connection with examples 1-23, comparative examples 1-4, and the corresponding data in Table 3, a high temperature resistant epoxy resin curing agent prepared in the present application is described below.
In example 1, the hardness loss of the polymer copolymerized with the epoxy resin was 17.6% and H was found to be 17.6% due to the use of the curing agent obtained by modifying cardanol in preparation example 1 150 The temperature is 338 ℃ when the temperature is 86 ℃ and the thermal weight loss is 5%; in comparative example 1, however, the hardness loss of the polymer obtained was 22.1% and H was found to be high because the modified cardanol was not used 150 The temperature at which the thermal weight loss was 5% was 80℃and 268.5 ℃. The lower the hardness loss, H 150 The higher the heat loss is, the higher the temperature is at 5% of the heat loss is, the better the heat resistance of the curing agent is, and therefore, the heat resistance of the curing agent can be obviously improved by using the modified cardanol.
The reason for analysis may be that the esterification of citric acid and cardanol forms ester bonds, which increases the number of chemical bonds between the curing agent and the epoxy resin, thereby increasing the crosslinking points, and further improving the crosslinking density between the curing agent and the epoxy resin, so that the cured polymer needs to be decomposed at a higher temperature, i.e. has higher thermal stability and heat resistance.
Meanwhile, compared with comparative example 1, the water resistance in example 1 is as high as 320h, the surface drying time is less than 1.5h, and the performance is better than that of comparative example 1, wherein the reason for the great improvement of the water resistance is probably that the phenolic hydroxyl groups are esterified, so that the adsorption sites of water molecules are reduced, and the polymer is more water-resistant and has better water resistance.
Comparative example 2 is different from example 1 in that an equivalent amount of maleic anhydride was used instead of citric acid in comparative example 2 to prepare modified cardanol. The hardness loss in comparative example 2 was 21.7%, H 150 At 83 degrees, the temperature at 5% thermal weight loss was 317℃and was inferior to example 1. The reason for analysis may be that in the reaction process of citric acid, anhydride is dehydrated first and then esterified with cardanol, so that the reaction is more sufficient compared with the direct use of anhydride for esterification, and the heat resistance of the curing agent is enhanced. The direct esterification of the acid anhydride ensures that the curing agent has poor water resistance of 317 hours, which indicates that the application uses the citric acid, so that the curing agent has better performance.
Examples 2-5, comparative examples 3-4 differ from example 1 in the weight of each component. The hardness loss in examples 1 to 5 was 17.0 to 17.6%, H 150 The temperature at 86-87 degrees and 5% weight loss on heating is 338-339.7 degrees C, which is superior to that of comparative examples 3-4, indicating that the heat resistance of the curing agent obtained is better when the weight of each component is in the range of examples 1-5, wherein example 3 is the preferred example.
Examples 6 to 10 are different from example 3 in that the weight ratio of cardanol, silicone, citric acid is different in the preparation process of modified cardanol. The hardness loss was reduced to 16.2-15.5% H in examples 6-10 as compared to example 3 150 The temperature is 342-343.5 ℃ when the temperature is 88-89 ℃ and the thermal weight loss is 5%, which shows that when the weight ratio is in the range of examples 6-10, the compounding effect of cardanol, organic silicon and citric acid is better, the organic silicon directly acts, and the citric acid indirectly acts, so that the compounding system can exert better high temperature resistance under the condition of better compounding effect.
Examples 11 to 13 are different from example 7 in that catalyst A was used in the preparation of modified cardanol when NaHSO was used 4 、CaCl 2 And NaHSO 4 、CaCl 2 When the mixture is used, the hardness loss of the prepared curing agent is reduced by 0.4-0.6%, and the high temperature resistance of the curing agent is better. ZnCl 2 、MgCl 2 、AlCl 3 The action and effect of (C) can be analogized to NaHSO 4 、CaCl 2 Indicating that when catalyst A employs NaHSO 4 、CaCl 2 、ZnCl 2 、MgCl 2 、AlCl 3 When the mixture is formed by one or more of the components, the high temperature resistance of the curing agent is further improved.
Examples 14-16 differ from example 13 in that in the preparation of modified cardanol, the use of the water scavenger is different, and when the water scavenger is N, N '-diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, and a mixture of N, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, each performance is improved, and the effect of dicyclohexylcarbodiimide can be compared with that of N, N '-diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, indicating that when the water scavenger is a mixture of one or more of N, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, the progress of esterification reaction can be ensured.
Examples 17-19 differ from example 16 in that different weights of anhydride were also added during the preparation of the modified cardanol. Compared with example 16, the properties of examples 17-19 are all improved, especially in example 18, the hardness loss is reduced by 1.5%, the temperature at 5% thermal weight loss is increased by 3.1 ℃, which shows that the use of anhydride can enhance the heat resistance of the curing agent, but the reason why the performance of the curing agent cannot be greatly improved is as follows: the citric acid and cardanol react more fully, and unreacted cardanol is less.
Example 20 differs from example 18 in that the use of anhydride is probably due to the fact that by using phthalic anhydride, maleic anhydride, methyl nadic anhydride, all esterified with cardanol, the cross-linking point between the curing agent and the epoxy resin is increased together, the hardness loss of the curing agent is reduced to 12.2%, the temperature at 5% of thermal weight loss is increased to 353.0 ℃, and the heat resistance is better.
Examples 21 to 23 are different from example 20 in that the weight ratio of phthalic anhydride, maleic anhydride, methyl nadic anhydride is different, and when the weight ratio of phthalic anhydride, maleic anhydride, methyl nadic anhydride is in the range of examples 21 to 23, the synergistic effect is superior, and the heat resistance of the obtained curing agent is better.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. The high-temperature-resistant epoxy resin curing agent is characterized by comprising the following components in parts by weight:
360-480 parts of modified cardanol;
30-40 parts of paraformaldehyde;
150-190 parts of triethylene tetramine;
2-10 parts of N, N-dimethyl cyclohexane;
the preparation method of the modified cardanol comprises the following steps: adding organic silicon and a catalyst A into the cardanol solution, and stirring and mixing to obtain a mixed solution A; adding citric acid into the mixed solution A, adding a water removing agent and absolute ethyl alcohol during stirring, stirring and mixing, and distilling to obtain modified cardanol;
the weight ratio of the cardanol to the organic silicon to the citric acid is (3-5) (0.5-1) 1;
the catalyst A is a mixture composed of one or more of NaHSO4, znCl2, caCl2, mgCl2 and AlCl 3.
2. The high temperature resistant epoxy resin curing agent according to claim 1, wherein: the weight ratio of the cardanol to the citric acid is (3-4): 1.
3. The high temperature resistant epoxy resin curing agent according to claim 1, wherein: the water scavenger is one or a mixture of more of N, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and dicyclohexylcarbodiimide.
4. The high temperature resistant epoxy resin curing agent according to claim 1, wherein: in the process of adding the organic silicon and the catalyst A into the cardanol, acid anhydride is also added;
the weight ratio of the addition amount of the anhydride to the cardanol is 1 (4-6).
5. The high temperature resistant epoxy resin curing agent according to claim 4, wherein: the anhydride consists of phthalic anhydride, maleic anhydride and methyl nadic anhydride.
6. The high temperature resistant epoxy resin curing agent according to claim 5, wherein: the weight ratio of the phthalic anhydride to the maleic anhydride to the methyl nadic anhydride is 1 (1-2) to 1-1.5.
7. The high temperature resistant epoxy resin curing agent according to claim 1, wherein: comprises the following components in parts by weight:
420-460 parts of modified cardanol;
33-37 parts of paraformaldehyde;
160-180 parts of triethylene tetramine;
4-8 parts of N, N-dimethyl cyclohexane.
8. A method for preparing a high temperature resistant epoxy resin curing agent according to any one of claims 1 to 7, comprising the steps of:
s1, adding modified cardanol and triethylene tetramine into N, N-dimethyl cyclohexane, and stirring and mixing to obtain a mixed solution B;
s2, adding paraformaldehyde into the mixed solution B, stirring, mixing and distilling to obtain the high-temperature-resistant epoxy resin curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210709374.5A CN115028790B (en) | 2022-06-22 | 2022-06-22 | High-temperature-resistant epoxy resin curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210709374.5A CN115028790B (en) | 2022-06-22 | 2022-06-22 | High-temperature-resistant epoxy resin curing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115028790A CN115028790A (en) | 2022-09-09 |
| CN115028790B true CN115028790B (en) | 2024-02-09 |
Family
ID=83127599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210709374.5A Active CN115028790B (en) | 2022-06-22 | 2022-06-22 | High-temperature-resistant epoxy resin curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115028790B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009132774A (en) * | 2007-11-29 | 2009-06-18 | Showa Highpolymer Co Ltd | Cashew novolac resin, its preparation method and curing agent for epoxy resin |
| CN103739828A (en) * | 2013-12-19 | 2014-04-23 | 上海美东生物材料有限公司 | Preparation method of cardanol-based high temperature-resistant epoxy resin curing agent |
| CN107057009A (en) * | 2017-06-01 | 2017-08-18 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of the modified amine of polyphenol containing anacardol epoxy curing agent |
| CN108148163A (en) * | 2017-12-26 | 2018-06-12 | 上海美东生物材料股份有限公司 | A kind of preparation method of modified by cardanol amine epoxy curing agent |
| CN110790882A (en) * | 2019-11-13 | 2020-02-14 | 浩力森涂料（上海）有限公司 | Organic silicon modified cardanol-based waterborne polyurethane and preparation method thereof |
| CN111793195A (en) * | 2020-06-19 | 2020-10-20 | 华南农业大学 | Cardanol modified amine epoxy resin curing agent and preparation method and application thereof |
| CN112094394A (en) * | 2020-09-24 | 2020-12-18 | 肇庆市海特复合材料技术研究院 | Preparation method of flame-retardant epoxy resin curing agent |
| CN114350232A (en) * | 2022-02-09 | 2022-04-15 | 上海正欧实业有限公司 | Flame-retardant epoxy resin floor coating and preparation method thereof |
-
2022
- 2022-06-22 CN CN202210709374.5A patent/CN115028790B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009132774A (en) * | 2007-11-29 | 2009-06-18 | Showa Highpolymer Co Ltd | Cashew novolac resin, its preparation method and curing agent for epoxy resin |
| CN103739828A (en) * | 2013-12-19 | 2014-04-23 | 上海美东生物材料有限公司 | Preparation method of cardanol-based high temperature-resistant epoxy resin curing agent |
| CN107057009A (en) * | 2017-06-01 | 2017-08-18 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of the modified amine of polyphenol containing anacardol epoxy curing agent |
| CN108148163A (en) * | 2017-12-26 | 2018-06-12 | 上海美东生物材料股份有限公司 | A kind of preparation method of modified by cardanol amine epoxy curing agent |
| CN110790882A (en) * | 2019-11-13 | 2020-02-14 | 浩力森涂料（上海）有限公司 | Organic silicon modified cardanol-based waterborne polyurethane and preparation method thereof |
| CN111793195A (en) * | 2020-06-19 | 2020-10-20 | 华南农业大学 | Cardanol modified amine epoxy resin curing agent and preparation method and application thereof |
| CN112094394A (en) * | 2020-09-24 | 2020-12-18 | 肇庆市海特复合材料技术研究院 | Preparation method of flame-retardant epoxy resin curing agent |
| CN114350232A (en) * | 2022-02-09 | 2022-04-15 | 上海正欧实业有限公司 | Flame-retardant epoxy resin floor coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 腰果酚改性环氧固化剂的制备;张欣妍;王黎;张洋;张素心;马钰骦;;广州化工(07);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115028790A (en) | 2022-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR950005314B1 (en) | Thermosetting resin composition | |
| CN108997245B (en) | Mussel bionic polybenzoxazine containing catechol group and synthesis and application thereof | |
| CN112175210B (en) | Preparation method of organic silicon elastomer based on polyphenol compound crosslinking | |
| KR20080035431A (en) | Amic acid ester oligomer, precursor composition for polyimide resin containing the same, and uses | |
| JP5985977B2 (en) | Polyimide resin solution | |
| CN111499877A (en) | Preparation method of organic silicon modified epoxy resin | |
| CN108164751A (en) | It is a kind of suitable for response type halogen-free flame retardants of TPV and its preparation method and application | |
| CN115028790B (en) | High-temperature-resistant epoxy resin curing agent and preparation method thereof | |
| CN112194822B (en) | Phosphorus-containing flame retardant, preparation method and modified epoxy resin | |
| KR102249696B1 (en) | Silane coupling agent and method for preparing the same, primer composition, and coating composition | |
| US4238579A (en) | Vinylamine aromatic copolymers and salts thereof | |
| CN101451013A (en) | Polyimide material and preparation method thereof | |
| CN105860355B (en) | High ferro high fire-retardance high durable rubber floor covering and preparation method thereof | |
| CN114213707B (en) | Intumescent flame retardant, preparation method and application thereof | |
| CN105505295B (en) | Flame retardant type silicone sealant and preparation method thereof | |
| Ji et al. | Properties and mechanism of EVM–GMA terpolymer elastomer cross-linked by epoxy–anhydride reaction | |
| JP2019500463A (en) | Polyimide block copolymer and polyimide film containing the same | |
| JP2012172001A (en) | Hyperbranched polyimide-based hybrid material | |
| CN111393790A (en) | Preparation process of particle material for remote controller shell | |
| CN111100588A (en) | Insulating flame-retardant potting mixture and preparation method thereof | |
| JP2020164742A (en) | Method for producing polymer-coated inorganic filler | |
| CN102060994B (en) | Precursor composition of polyimide and method for preparing polyimide | |
| CN108164750B (en) | Hindered amine antioxidant and polyethylene material | |
| Shibata et al. | Intermolecular interaction of supramolecular organic–inorganic hybrid composites of sulfonated polystyrene and oligomeric silsesquioxane possessing pyridyl groups | |
| CN111087652A (en) | Silicone rubber heat-resistant additive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |