CN119505243A - Room-temperature-cured water-based high-temperature-resistant silicone resin emulsion and preparation method and application thereof - Google Patents
Room-temperature-cured water-based high-temperature-resistant silicone resin emulsion and preparation method and application thereof Download PDFInfo
- Publication number
- CN119505243A CN119505243A CN202510083810.6A CN202510083810A CN119505243A CN 119505243 A CN119505243 A CN 119505243A CN 202510083810 A CN202510083810 A CN 202510083810A CN 119505243 A CN119505243 A CN 119505243A
- Authority
- CN
- China
- Prior art keywords
- water
- silicone resin
- resin emulsion
- temperature resistant
- emulsion
- 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.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 96
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004945 emulsification Methods 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 40
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract description 17
- 239000006227 byproduct Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 125000005375 organosiloxane group Chemical group 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012875 nonionic emulsifier Substances 0.000 claims description 6
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003141 primary amines Chemical class 0.000 claims description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- MFIBZDZRPYQXOM-UHFFFAOYSA-N [dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C1OC1COCCC[Si](C)(C)O[Si](C)(C)CCCOCC1CO1 MFIBZDZRPYQXOM-UHFFFAOYSA-N 0.000 claims description 2
- 229920013822 aminosilicone Polymers 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims 1
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- -1 methyl siloxane Chemical class 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000000413 hydrolysate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004447 silicone coating 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
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- RGKUSPKMWIGVLG-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;trimethoxy(propyl)silane Chemical compound NCCNCCN.CCC[Si](OC)(OC)OC RGKUSPKMWIGVLG-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
本发明公开了一种室温固化水性耐高温硅树脂乳液及其制备方法和应用，涉及耐高温涂层技术领域，制备包括以下步骤：S1、将含有伯胺或仲胺的有机硅氧烷单体和甲基硅氧烷单体混合，在酸性条件下进行水解反应生成含有氨基的硅氧烷预聚物，加碱中和脱除醇类副产物；S2、将乳化剂和水搅拌分散均匀加入含有氨基的硅氧烷预聚物，高速剪切乳化生成预聚物乳液；S3、滴加碱性催化剂和苯基硅氧烷单体，制得水性耐高温硅树脂乳液，加酸中和脱除醇类副产物；S4、向硅树脂乳液中加入环氧硅烷水解液固化剂，搅拌均匀，制得室温固化水性耐高温硅树脂乳液。本发明整个制备过程稳定，工艺流程短、易于控制，制备出的产品满足环境友好耐高温水性涂料的应用需求。The invention discloses a room temperature curing water-based high temperature resistant silicone resin emulsion and a preparation method and application thereof, and relates to the technical field of high temperature resistant coatings. The preparation comprises the following steps: S1, mixing an organic siloxane monomer containing a primary amine or a secondary amine and a methyl siloxane monomer, performing a hydrolysis reaction under acidic conditions to generate a siloxane prepolymer containing an amino group, and neutralizing and removing alcohol byproducts by adding a base; S2, stirring and dispersing an emulsifier and water, uniformly adding the siloxane prepolymer containing an amino group, and emulsifying at a high speed to generate a prepolymer emulsion; S3, dripping an alkaline catalyst and a phenyl siloxane monomer to obtain a water-based high temperature resistant silicone resin emulsion, neutralizing and removing alcohol byproducts by adding an acid; S4, adding an epoxy silane hydrolyzate curing agent to the silicone resin emulsion, stirring evenly, and obtaining a room temperature curing water-based high temperature resistant silicone resin emulsion. The whole preparation process of the invention is stable, the process flow is short, and it is easy to control, and the prepared product meets the application requirements of environmentally friendly high temperature resistant water-based coatings.
Description
Technical Field
The invention relates to the technical field of high-temperature-resistant coatings, in particular to a room-temperature-cured water-based high-temperature-resistant silicone resin emulsion, and a preparation method and application thereof.
Background
With the development of modern industry, more and more devices need to be in service under high temperature conditions, such as a high-temperature furnace, a high-temperature pipeline, an aircraft engine, an exhaust pipe and the like, and compared with the development of expensive alloy materials to resist high-temperature corrosion, the application of the high-temperature resistant protective coating on the surface of the materials is simpler and more efficient, so that the high-temperature resistant coating applied to different temperatures and different fields is continuously developed. The high-temperature resistant coating generally consists of high-temperature resistant resin, pigment and filler and related auxiliary agents, at present, the most widely applied organosilicon high-temperature resistant coating on the market is generally solvent-based organosilicon resin, the problem of high VOC content exists, great potential safety hazards are caused to people and environment in the construction process, the current development trend of green low carbon is not met, and a paint film generally needs high-temperature curing (150-250 ℃ for 0.5-1 h) to achieve the optimal performance, so that the limitation of application range and the increase of resource energy consumption are caused, and therefore, in the actual use, the organosilicon high-temperature resistant coating is gradually developed to the water-based and low-curing temperature direction by the organosilicon resin.
The organic silicon resin emulsion is used as a novel green environment-friendly material, and can be applied to the field of environment-friendly high-temperature-resistant paint due to the excellent high-low temperature resistance, weather resistance, physiological inertia and flame resistance. At present, the preparation method of the organic silicon resin emulsion mainly comprises a mechanical emulsification method and an emulsion polymerization method.
The mechanical emulsification method is a method for forming polymer emulsion by mechanically stirring highly crosslinked silicone resin under the action of an external emulsifier or hydrophilic group, and can greatly reduce the VOC content of the organic silicone resin product after the water-based treatment and endow the organic silicone resin product with good environmental-friendly characteristics. The epoxy modified organic silicon resin, the anionic and nonionic emulsifier and the cosolvent are stirred uniformly in Chinese patent CN108641097A, and are slowly added into deionized water, and the water-based organic silicon emulsion is prepared by a high-speed emulsification reverse conversion method. However, the silicone resin emulsion prepared by the method generally has the problems of large emulsifier consumption and high VOC content. Hydrophilic polyether chain segments, carboxylate or sulfonate groups are introduced in the synthesis of the organic silicon resin, and stable silicon resin emulsion can be prepared by self-emulsification. For example, in chinese patent CN109400913B, a pre-dispersion of polyether modified polysiloxane and silicone polymer is added into an emulsifying kettle containing nonionic emulsifier, auxiliary emulsifier and water, and after heating and rapid emulsification, a thickener is added to obtain silicone emulsion product.
The emulsion polymerization method is the most studied type of silicone emulsion preparation method in recent years, and the silicone emulsion is prepared by an emulsion polymerization method through the action of a catalyst, an initiator, a surfactant and the like by using an organosilicon monomer. Compared with the mechanical emulsification method of solvent type silicon resin, the method does not need complex processes such as water diversion, water washing, concentration, polycondensation, desolventizing, emulsification and the like after reaction, can realize polymerization and emulsification by a one-step method, avoids introducing harmful organic solvents, and has the advantages of short flow, low cost and low VOC. Chinese patent CN 118185014A is prepared by dripping siloxane monomers with different functionalities into mixed liquid of anionic and nonionic surfactant, catalyst and deionized water, heating and stirring to perform emulsion polymerization to obtain the water-based high-temperature-resistant methylphenyl silicone resin emulsion. However, because the solubility of the alkoxy silane with different functionality in water is large, the hydrolysis and condensation rates of the monomers are different, the homogeneous phase nucleation and the liquid drop nucleation of the silane monomer occur synchronously in the emulsion polymerization process, and a part of the siloxane prepolymer is polymerized in the water phase to be easily gelled, so that the emulsion stability is poor, and the large-scale preparation difficulty is increased.
From the above reported patent information, it is known that aqueous silicone resin emulsion can be prepared by emulsion polymerization of alkoxysilane, but emulsion stability is not high, and high-temperature curing is required for preparing high-temperature resistant coating, resulting in limitation of application range and increase of resource energy consumption. Meanwhile, the existing silicone resin emulsion products basically have the problem of high VOC caused by organic solvents or alcohols, and severely restrict the application and popularization of the silicone resin emulsion products in the field of green low carbon.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a room-temperature-curing water-based high-temperature-resistant silicone resin emulsion, and a preparation method and application thereof.
The aim of the invention is realized by the following technical scheme:
the preparation method of the room-temperature-cured water-based high-temperature-resistant silicone resin emulsion comprises the following steps:
S1, mixing an organic siloxane monomer containing primary amine or secondary amine and a methyl organic siloxane monomer at room temperature, dropwise adding acid, controlling the pH of a reaction system to be 4-5, heating to 40-50 ℃ after the acid is dropwise added, performing heat preservation reaction for 2-3 h to generate a siloxane prepolymer containing amino, and then neutralizing with alkali and removing alcohol byproducts;
s2, uniformly stirring and dispersing an emulsifying agent and water at room temperature, adding an aminosilicone-containing prepolymer, controlling the dripping time to be 1-2 h, and stirring and emulsifying at a high speed to be 1-2 h to prepare a prepolymer emulsion;
S3, raising the temperature to 50-70 ℃, respectively dropwise adding an alkaline catalyst and a phenyl siloxane monomer into the prepolymer emulsion, controlling the pH of a reaction system to be 11-13, dropwise adding the phenyl siloxane monomer for 2-3h, stirring and preserving heat for 2-3 hours to prepare a water-based high-temperature-resistant silicone resin emulsion, adding acid for neutralization and removing alcohol byproducts;
s4, adding an epoxy silane hydrolysate curing agent into the water-based high-temperature-resistant silicone resin emulsion, and uniformly stirring to obtain the room-temperature-cured water-based high-temperature-resistant silicone resin emulsion.
Specifically, the organic siloxane monomer containing primary amine or secondary amine in S1 comprises one or more of N- (2-amino ethyl) -3-amino propyl trimethoxy silane, (3-amino propyl) triethoxy silane, (3-amino propyl) trimethoxy silane, [3- (methylamino) propyl ] trimethoxy silane and diethylenetriamine propyl trimethoxy silane, the organic siloxane monomer containing methyl comprises one or more of methyl trimethoxy silane, dimethyl dimethoxy silane, methyl triethoxy silane and dimethyl diethoxy silane, the acid is any one of hydrochloric acid, formic acid and acetic acid aqueous solution, and the alkali is any one of sodium hydroxide, tetramethyl ammonium hydroxide and ammonia water.
The emulsifier comprises any one or a combination of a cationic emulsifier and a nonionic emulsifier, wherein the cationic emulsifier is one or a mixture of dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium chloride, and the nonionic emulsifier is one or a mixture of octyl phenol polyoxyethylene ether series and isomeric tridecyl polyoxyethylene ether series.
The alkaline catalyst in the step S3 is 0.1 mol/L of ammonia water solution, the phenyl siloxane monomer is one or a mixture of more of phenyl trimethoxy silane, phenyl triethoxy silane, diphenyl dimethoxy silane and diphenyl diethoxy silane, and the acid is any one of hydrochloric acid, formic acid and acetic acid water solution.
The epoxy silane hydrolysate curing agent is any one or combination of 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane, 1, 3-bis (3-glycidoxypropyl) tetramethyl disiloxane and 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane hydrolysate.
The alcohol byproducts are removed by reduced pressure distillation, the material temperature is 50-60 ℃ during reduced pressure distillation, the vacuum degree is-0.08 MPa, the reduced pressure distillation time is 1-2 hours, and the distillation is stopped when the alcohol content in the emulsion is detected to be less than or equal to 1g/L through gas chromatography.
The epoxy silane hydrolysis liquid curing agent comprises, by mass, 5% -10% of the total mass of the whole siloxane monomer, wherein the total mass of the whole siloxane monomer is the total mass of the epoxy siloxane monomer, the methyl-containing siloxane monomer, the phenyl-containing siloxane monomer and the amino-containing organosiloxane monomer.
The second aspect of the invention provides a room temperature curing aqueous high temperature resistant silicone resin emulsion which is prepared by the preparation method.
The third aspect of the invention provides application of the room-temperature-cured water-based high-temperature-resistant silicone resin emulsion as a high-temperature-resistant water-based paint.
The beneficial effects of the invention are as follows:
According to the invention, silane monomers with different hydrophilias are dropwise added into a water-emulsifier system in batches, so that in the emulsion polymerization process, siloxane oligomers generated by hydrolysis of siloxane monomers with good hydrophilias and siloxane oligomers formed by nucleation of liquid drops of siloxane monomers with poor hydrophilias enter micelles for copolycondensation, and the amino-containing silicone resin emulsion with excellent emulsion stability is prepared by virtue of the charge repulsion stabilization effect of a composite emulsifying system;
No organic solvent is added in the reaction, and the content of alcohol byproducts in the silicone resin emulsion is less than or equal to 0.1 percent by reduced pressure distillation and online monitoring, so that the silicone resin emulsion has the environment-friendly characteristic of low VOC;
After the silicone resin emulsion is cured into a film at room temperature, the 5% weight loss temperature exceeds 370 ℃, the high temperature resistance is excellent, and the performance test performance after room temperature curing is good and is superior to that of similar products at home and abroad. The whole preparation process is stable, the process flow is short, the operation is convenient, the control is easy, and the prepared product meets the application requirements of environment-friendly high-temperature-resistant water-based paint.
The organic silicon resin emulsion with amino can be subjected to ring-opening reaction with an epoxy silane hydrolysate curing agent to form organic silicon resin with high curing activity, so that the room-temperature curing of the silicon resin emulsion is realized;
because the resin emulsion contains two heat-resistant elements of nitrogen and silicon, the resin emulsion can also be applied to the aspect of environment-friendly high polymer flame retardant, and the application range of the resin emulsion is widened.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without any inventive effort, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Examples
Sequentially stirring 10.0 g N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 10.0 g methyltrimethoxysilane and 5g dimethyldimethoxy silane, 5.0g water and 0.5g 0.01mol/L HCl to react for 2h at room temperature to generate amino-containing siloxane prepolymer, adding alkali to neutralize and transferring the silicone resin emulsion into a distillation device, filtering after removing low-boiling alcohol byproducts by pressure, stirring 100g water, 2.3g dodecyl trimethyl ammonium bromide and 3.7g of isomeric tridecanol polyoxyethylene ether 1307 uniformly, dripping the synthesized amino-containing siloxane prepolymer, controlling dripping time to be 1h, simultaneously performing high-speed shearing and emulsifying for 2h to generate prepolymer emulsion, heating to 50 ℃, simultaneously dripping 0.5ml ammonia water and 20.0g phenyl trimethoxy silane into the prepolymer emulsion, controlling monomer dripping time to be 2h, continuing stirring and reacting for 2h to prepare aqueous high-temperature resistant silicone resin emulsion, cooling to room temperature, adding hydrochloric acid and transferring the silicone resin to the distillation device, removing the high-temperature resistant silicone resin to obtain the aqueous high-temperature resistant silicone resin emulsion, filtering to remove the low-boiling alcohol byproducts by pressure, stirring the aqueous high-temperature resistant silicone resin emulsion, cooling to obtain the aqueous high-temperature resistant silicone resin emulsion, filtering, dispersing the aqueous high-temperature resistant silicone resin emulsion, cooling to obtain the aqueous high-temperature resistant silicone resin emulsion, and solidifying the aqueous high-temperature resistant silicone resin emulsion, filtering to obtain the aqueous high-resistant silicone resin emulsion, and drying by stirring 4 dispersing and drying under the conditions.
Examples
Sequentially stirring 10.0 g (3-aminopropyl) triethoxysilane, 10.0 g methyltrimethoxysilane and 5g dimethyldimethoxysilane, 5.0g water and 0.5g 0.01mol/L HCl to react 2h at room temperature to generate an amino-containing siloxane prepolymer, adding alkali to neutralize and transferring the silicone resin emulsion to a distillation device, decompressing and removing low-boiling-point alcohol byproducts to obtain a water-based high-temperature resistant silicone resin emulsion, filtering, stirring 100g water, 2.7g dodecyl trimethyl ammonium chloride and 3.9g isomeric tridecanol polyoxyethylene ether 1309 uniformly, dripping the synthesized amino-containing siloxane prepolymer, controlling the total dripping time to be 1h, simultaneously heating to 50 ℃, simultaneously dripping 0.5ml ammonia water and 20.0g diphenyldimethoxysilane into the prepolymer emulsion, controlling the dripping time to be 2h, continuously stirring and reacting for 2h to obtain the water-based high-temperature resistant silicone resin emulsion, cooling to room temperature, adding hydrochloric acid to neutralize and transferring the silicone resin to the distillation device, dripping the synthesized amino-containing siloxane prepolymer to obtain the water-based high-temperature resistant silicone resin emulsion, controlling the total dripping time to be 1h, simultaneously shearing and emulsifying 2h to generate a prepolymer emulsion, heating to 50 ℃, dripping the 0.01 ml ammonia water and 20.0g diphenyldimethoxysilane into the prepolymer emulsion, continuously stirring the water-based high-temperature resistant silicone resin emulsion, decompressing and stirring to obtain the water-based high-temperature resistant silicone resin emulsion, filtering, drying, and solidifying the water-soluble silicone resin after the water-soluble high-phase emulsion.
Examples
Sequentially stirring 10.0g (3-aminopropyl) trimethoxysilane, 10.0g methyltrimethoxysilane and 5g dimethyldimethoxysilane, 5.0g water and 0.5g 0.01mol/L HCl to react 2h at room temperature to generate an amino-containing siloxane prepolymer, adding alkali to neutralize and transferring the silicone resin emulsion to a distillation device, decompressing and removing low-boiling-point alcohol byproducts to obtain a high-temperature resistant silicone resin emulsion, filtering, stirring 100g water, 2.2g dodecyl dimethyl benzyl ammonium bromide and 3.2g of isomeric tridecyl polyoxyethylene ether 1303 uniformly, dropwise adding the synthesized amino-containing siloxane prepolymer, controlling the total dropwise adding time to be 1h, simultaneously shearing and emulsifying 2h at a high speed to generate a prepolymer emulsion, heating to 50 ℃, simultaneously dropwise adding 0.5ml ammonia water and 20.0g phenyl triethoxysilane into the prepolymer emulsion, controlling the dropwise adding time to be 2h, continuously stirring and reacting for 2h to obtain the water-based high-temperature resistant silicone resin emulsion, cooling to room temperature, adding hydrochloric acid to neutralize and transferring the silicone resin to the low-boiling-point alcohol byproducts, stirring to obtain the water-based high-temperature resistant silicone resin emulsion, cooling the water-soluble silicone resin emulsion, dispersing the water-soluble silicone resin emulsion to obtain the water-soluble silicone resin emulsion, stirring uniformly, cooling the water-soluble silicone resin emulsion, filtering, and dissolving the water-soluble silicone resin emulsion with 4 g to obtain the water-soluble silicone resin emulsion, and solidifying the water-soluble silicone resin after the water-soluble silicone resin solution.
Examples
Sequentially stirring 10.0 g [3- (methylamino) propyl ] trimethoxy silane, 10.0 g methyltriethoxysilane and 5g dimethyldiethoxysilane, 5.0g water and 0.5g 0.01mol/L HCl to react for 2h at room temperature to generate amino-containing siloxane prepolymer, adding alkali to neutralize and transferring the silicone resin emulsion to a distillation device, filtering after removing low-boiling-point alcohol byproducts by pressure, stirring 100g water, 2.3g cetyltrimethylammonium bromide and 3.7g octylphenol polyoxyethylene ether OP-10 uniformly, dripping the synthesized amino-containing siloxane prepolymer, controlling the total dripping time to be 1h, simultaneously shearing and emulsifying 2h at high speed to generate prepolymer emulsion, heating to 50 ℃, simultaneously dripping 0.5ml ammonia water and 20.0g phenyl trimethoxy silane into the prepolymer emulsion, controlling the dripping time to be 2h, continuing stirring and reacting for 2h to prepare aqueous high-temperature resistant silicone resin emulsion, cooling to room temperature, adding hydrochloric acid and transferring the silicone resin to the distillation device, dripping the synthesized amino-containing siloxane prepolymer to obtain the amino-containing siloxane prepolymer, controlling the total dripping time to be 1h, simultaneously shearing and emulsifying 2.0 g phenyl trimethoxy silane to obtain the aqueous high-prepolymer emulsion, heating to obtain the aqueous high-temperature resistant silicone resin, cooling the aqueous high-phase liquid-4 g water-soluble silicon alcohol-soluble by-3-propyl ether-containing siloxane emulsion, filtering, dispersing the aqueous high-phase alcohol-soluble silicon resin-drying liquid-reducing water-soluble silicon resin-soluble water-soluble silicon resin, and drying water-borne silicon resin.
The room temperature-curable aqueous high temperature resistant silicone resin emulsion prepared in the example was subjected to performance test, and the results are shown in table 1.
TABLE 1
Note that T 5% represents the temperature corresponding to 5% mass loss of the silicone emulsion after curing, which is defined as the initial decomposition temperature, to evaluate the high temperature resistance of the silicone emulsion.
After the prepared silicone emulsion is compounded with relevant assistants such as high temperature resistant pigment and filler, dispersing agent, wetting agent, defoamer and the like, the viscosity of the system is regulated by a thickener, a water-based silicone coating is obtained after filtering by a filter screen, the water-based silicone coating is coated on a stainless steel plate, a water-based silicone coating sample (thickness: 20-30 mu m) is obtained after room temperature curing, and performance test is carried out on the coating, as shown in Table 2:
TABLE 2
In conclusion, the room-temperature-curable water-based high-temperature-resistant silicone resin emulsion prepared by the invention has good stability, can be cured at room temperature, has excellent high-temperature resistance, is safe and environment-friendly, and has higher application value.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510083810.6A CN119505243A (en) | 2025-01-20 | 2025-01-20 | Room-temperature-cured water-based high-temperature-resistant silicone resin emulsion and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510083810.6A CN119505243A (en) | 2025-01-20 | 2025-01-20 | Room-temperature-cured water-based high-temperature-resistant silicone resin emulsion and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN119505243A true CN119505243A (en) | 2025-02-25 |
Family
ID=94660979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202510083810.6A Pending CN119505243A (en) | 2025-01-20 | 2025-01-20 | Room-temperature-cured water-based high-temperature-resistant silicone resin emulsion and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119505243A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006119916A1 (en) * | 2005-05-12 | 2006-11-16 | Wacker Chemie Ag | Method for producing crosslinkable organopolysiloxane dispersions |
| CN102898647A (en) * | 2012-10-22 | 2013-01-30 | 湖北大学 | Method for preparing organic silicone homopolymerized or copolymerized emulsion with different organic functional groups and non-functional groups by emulsion polymerization |
| CA2859353A1 (en) * | 2011-12-15 | 2013-06-20 | Sumi Dinkar | Moisture curable organopolysiloxane compositions |
| CN114702673A (en) * | 2022-04-02 | 2022-07-05 | 武汉绿凯科技有限公司 | Electrophoresis type high-temperature-resistant water-based silicone resin emulsion and preparation method thereof |
| CN117552243A (en) * | 2024-01-11 | 2024-02-13 | 吴江市汉塔纺织整理有限公司 | Preparation method of anti-scalding fabric |
-
2025
- 2025-01-20 CN CN202510083810.6A patent/CN119505243A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006119916A1 (en) * | 2005-05-12 | 2006-11-16 | Wacker Chemie Ag | Method for producing crosslinkable organopolysiloxane dispersions |
| CN101171290A (en) * | 2005-05-12 | 2008-04-30 | 瓦克化学有限公司 | Method for producing crosslinkable organopolysiloxane dispersions |
| CA2859353A1 (en) * | 2011-12-15 | 2013-06-20 | Sumi Dinkar | Moisture curable organopolysiloxane compositions |
| CN102898647A (en) * | 2012-10-22 | 2013-01-30 | 湖北大学 | Method for preparing organic silicone homopolymerized or copolymerized emulsion with different organic functional groups and non-functional groups by emulsion polymerization |
| CN114702673A (en) * | 2022-04-02 | 2022-07-05 | 武汉绿凯科技有限公司 | Electrophoresis type high-temperature-resistant water-based silicone resin emulsion and preparation method thereof |
| CN117552243A (en) * | 2024-01-11 | 2024-02-13 | 吴江市汉塔纺织整理有限公司 | Preparation method of anti-scalding fabric |
Non-Patent Citations (1)
| Title |
|---|
| 董晓娜;谌开红;程斌;金贞玉;: "新型无溶剂有机硅耐高温树脂的制备及性能研究", 广东化工, no. 03, 25 March 2010 (2010-03-25), pages 101 - 103 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111004395B (en) | A kind of preparation method of low-solvent block type polyether amino silicone oil | |
| CN103113578B (en) | Modified carboxyl-terminated hyperbranched polyamide resin, as well as preparation method and application thereof | |
| CN103214679B (en) | The preparation method of amido Siloxane-Oxyalkylene Copolymers defoamer | |
| CN103804689B (en) | A kind of silicone oligomer of the special resistance to anti-soil of polyureas and preparation method thereof | |
| EP0989153A1 (en) | Emulsions containing ultrahigh viscosity silicone polymers | |
| WO2008147072A1 (en) | Polyalkylsilsesquioxane particulates and a preparation method thereof | |
| CN107602866B (en) | Fluorosilicone surfactant and preparation method thereof | |
| CN110172154A (en) | A kind of amino-modified silicone oil and preparation method thereof containing chain alkyl | |
| JP2008095002A (en) | Emulsion composition for coating | |
| CN103172867A (en) | Preparation method of long-chain alkane and epoxy co-modified amino-terminated silicone oil | |
| CN106916529B (en) | A kind of super-hydrophobic leather coating of durability polysilsesquioxane nano hybridization and preparation method thereof | |
| CN102964592A (en) | Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin | |
| CN111793215B (en) | Modified organopolysiloxane, preparation method and application thereof | |
| CN109810261A (en) | A kind of preparation method of organic siliconresin microemulsion | |
| JP5064190B2 (en) | Silicone resin aqueous emulsion | |
| CN105040449B (en) | A kind of smoothing agent for fabric of organosilicon and preparation method thereof | |
| CN112876684B (en) | Micron-level high-crosslinking-degree organic silicon polymer microspheres with controllable particle sizes and preparation method thereof | |
| CN119505243A (en) | Room-temperature-cured water-based high-temperature-resistant silicone resin emulsion and preparation method and application thereof | |
| CA2152763A1 (en) | Functional polyorganosiloxane emulsions from dihydrolyzable silanes and photocurable compositions therefrom | |
| JP3778847B2 (en) | Aqueous silicone composition | |
| CN107254048B (en) | A kind of fluorosilicone type release agent resin, emulsion type fluorosilicon release agent and preparation method thereof | |
| TW201307485A (en) | Method for producing polyoxyxene rubber compound and polyoxyethylene rubber composition | |
| WO2024221779A1 (en) | Organic silicon composition and preparation method therefor | |
| JP2000119393A (en) | Production of organopolysiloxane emulsion | |
| JP3891566B2 (en) | Aqueous dispersion of silicone elastomer particles |
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 |