CN110283322B - Organic silicon composition - Google Patents
Organic silicon composition Download PDFInfo
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- CN110283322B CN110283322B CN201910375574.XA CN201910375574A CN110283322B CN 110283322 B CN110283322 B CN 110283322B CN 201910375574 A CN201910375574 A CN 201910375574A CN 110283322 B CN110283322 B CN 110283322B
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- organic silicon
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- polyorganosiloxane
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- 239000000203 mixture Substances 0.000 title claims abstract description 98
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- 239000010703 silicon Substances 0.000 title claims abstract description 40
- -1 polysiloxane Polymers 0.000 claims abstract description 96
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 54
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 21
- 229920002050 silicone resin Polymers 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 230000002209 hydrophobic effect Effects 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- ADYYRXNLCZOUSU-UHFFFAOYSA-M potassium;propan-2-ol;hydroxide Chemical compound [OH-].[K+].CC(C)O ADYYRXNLCZOUSU-UHFFFAOYSA-M 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 claims description 2
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 238000004132 cross linking Methods 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 22
- 239000002518 antifoaming agent Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000007799 cork Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 description 1
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an organic silicon composition and a preparation method thereof, wherein hydrogen-containing polysiloxane reacts with unsaturated polyether, and then the hydrogen-containing polysiloxane and dimethyl hydrogen-terminated vinyl polysiloxane are subjected to hydrosilylation reaction and alkali treatment after the reaction is finished, the cross-linking viscosity is effectively controlled through the hydrogen-containing polysiloxane, a fluid state cross-linking polymer with a space structure is formed, and meanwhile, the addition of the unsaturated polyether improves the dispersion performance of the organic silicon composition.
Description
Technical Field
The invention relates to a crosslinkable organic silicon composition, and belongs to the technical field of fine chemical preparations.
Background
The paper industry is an important industry closely related to the development of national economy, and although the dosage of the defoaming agent in the paper industry is small, the defoaming agent plays an extremely important role. In the pulping process of the paper industry, because the pulp contains a large amount of fatty acid soap and resin acid soap foaming substances and cellulose foam stabilizing substances, a large amount of foam is easily generated in the transportation of the pulp, unnecessary troubles and loss are brought to the production, and the alkaline pulp also brings health problems to production workers. Early paper mills used a "clean water bubble" approach to suppress foam formation, but the effect was not ideal. With the rise of the silicone industry and the continuous attention paid to the harm of foam, organopolysiloxane antifoaming agents are beginning to be widely used in the paper industry.
As early as 1968, the preparation research of organopolysiloxane antifoaming agents has been carried out abroad, for example, in US3383327, an antifoaming agent composition is prepared by taking polydimethylsiloxane as a main body, but the antifoaming agent composition has poor foam inhibition performance due to too single structure. In later researches, US3455839 describes a method for preparing a crosslinkable organopolysiloxane defoaming agent composition, and firstly proposes a process for reacting vinyl polysiloxane with hydrogen-containing polysiloxane, so that the later-stage foam inhibition capability of the defoaming agent is improved, but the defoaming property of the defoaming agent is still insufficient; US4690713 teaches to introduce vinyl and phenyl groups into polyorganosiloxanes and to crosslink with hydrogenpolysiloxanes under conditions catalysed by platinum catalysts to give antifoam compositions whose foam suppressing properties do not fully meet the practical requirements of production; US4639489 uses high viscosity hydroxyl terminated polysiloxane to react with ethyl polysilicate under base catalysis to prepare an organopolysiloxane defoamer, but the prepared organosilicon polymer has high viscosity and does not have good defoaming performance; WO2013043487 discloses a method for preparing a defoaming agent composition by crosslinking an organopolysiloxane containing hydroxyl and an organopolysiloxane containing amino at the end chain to generate a crosslinking reaction, but the crosslinking structure is weak, and the defoaming agent composition cannot play a good foam inhibition role in a strong alkali system.
Disclosure of Invention
The invention relates to an organic silicon composition, which is prepared by reacting hydrogen-containing polysiloxane with unsaturated polyether, performing hydrosilylation reaction with dimethyl hydrogen-terminated vinyl polysiloxane after the reaction is finished, performing alkali treatment, effectively controlling crosslinking viscosity through the hydrogen-containing polysiloxane, forming a flowing state crosslinking polymer with a space structure, simultaneously adding the unsaturated polyether, and improving the dispersion performance of the organic silicon composition.
Technical scheme
A silicone composition characterized by consisting of:
A. dimethyl radical end capping vinyl polyorganosiloxane
The dimethyl hydrogen-based end-capped vinyl polyorganosiloxane provided by the invention at least contains two vinyl groups bonded with silicon, and has the following structural general formula:
wherein Me is methyl and Vi is vinyl; r1、R2Is a hydrocarbon radical selected from alkyl radicalsAryl, alkenyl, wherein alkyl is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, cyclopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-dodecyl, and n-octadecyl; aryl is selected from phenyl and benzyl; the alkenyl group is selected from vinyl and allyl. R1、R2Preferably methyl, but R is bound to the same silicon atom1And R2It may not be both vinyl groups and may be both methyl groups. The subscript p is an integer of 100-2000, preferably 500-1500; the subscript q is an integer of 2 to 500, preferably 40 to 300. The kinematic viscosity of the dimethyl hydrogen-terminated vinyl polyorganosiloxane at 25 ℃ is within the range of 100-200,000 mPa.s, and the preferable viscosity is within the range of 3,000-100,000 mPa.s. The amount of the dimethyl hydrogen-based end-capped vinyl polyorganosiloxane accounts for 20-50%, preferably 30-40% of the total mass of the organosilicon composition.
B. Hydrogen-containing polyorganosiloxanes
The hydrogen-containing polyorganosiloxane of the invention refers to polyorganosiloxane containing at least three hydrogen groups bonded to silicon:
wherein Me is methyl, R3、R4Is a hydrocarbyl group selected from the group consisting of alkyl groups, aryl groups, wherein the alkyl groups are selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, cyclopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-dodecyl, and n-octadecyl; aryl is selected from phenyl and benzyl. R3、R4Methyl is preferred. The subscript m is an integer of 5-350, preferably an integer of 35-200; the subscript n is an integer of 15-30. The hydrogen-containing polyorganosiloxane has a kinematic viscosity of 10 to 1,000mPa.s at 25 ℃, and preferably has a kinematic viscosity of 40 to 500 mPa.s. The dosage of the hydrogen-containing polyorganosiloxane accounts for 0.01-30%, preferably 5-19% of the total mass of the organic silicon composition.
C. Unsaturated polyethers
The molecular structure general formula of the unsaturated polyether is as follows:
XO(EO)e(PO)fR5
all R in the molecular structure5May be the same or different. It comprises hydrogen atom or monovalent substituted C1-4 alkyl selected from methyl, ethyl, propyl, n-propyl, butyl, preferably more than 80% of substituted groups R5Is a hydrogen atom. X is an initiator group and is 3-10 unsaturated straight chain or branched chain alkyl, including allyl, alpha-butenyl, alpha-pentenyl, alpha-hexenyl, alpha-heptenyl, alpha-octenyl, alpha-nonenyl and alpha-decenyl. X is preferably allyl. Subscripts e and f are polymerization degrees, e is an integer of 1-100, preferably 1-40, and f is an integer of 0-80, preferably 0-60. The dosage of the unsaturated polyether accounts for 0.5-10%, preferably 1-5% of the total mass of the organic silicon composition.
D. Catalyst I
The catalyst I is a noble metal catalyst for promoting hydrosilylation, and is selected from platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, chloroplatinic acid isopropyl alcohol solutions having a chloroplatinic acid concentration of 1%, rhodium-alcohol complexes, rhodium-alkoxide complexes, and preferably chloroplatinic acid isopropyl alcohol solutions having a chloroplatinic acid concentration of 1%. The amount of the catalyst I is 0.0001 to 0.001%, preferably 0.0005 to 0.001%, based on the total mass of the silicone composition.
E. Catalyst II
The catalyst II is selected from potassium hydroxide-isopropanol solution, potassium hydroxide-methanol solution, potassium hydroxide-ethanol solution, potassium hydroxide-methyl polysiloxane mixture, preferably potassium hydroxide-isopropanol solution. The amount of the catalyst II is 0.1-5%, preferably 1-3% of the total weight of the organosilicon composition.
F. Silicon dioxide
The silicon dioxide is hydrophobic silicon dioxide, specifically selected from gas-phase hydrophobic silicon dioxide and precipitation hydrophobic silicon dioxide, and the specific surface area of the silicon dioxide is 50-500 m2(ii) in terms of/g. The content of the silicon dioxide accounts for 2-15 percent of the total mass of the organic silicon composition, and the optimal content is 4 percent～8％。
G. Silicone resin
The organic silicon resin is organic silicon resin containing M and Q units, and the organic silicon resin is formed by chain links CH3SiOl/2(M units) and SiO units4/2(Q unit) in a molar ratio of 0.4:1.0 to 1.2:1.0, preferably 0.5:1.0 to 0.8: 1.0. The amount of the organic silicon resin is 1-15%, preferably 4-8% of the total mass of the organic silicon composition.
H. Solvent(s)
The solvent of the invention is used as a reaction medium of various reactants and is selected from alkane and polysiloxane. Wherein the alkane is C6-C20 saturated hydrocarbon, and is specifically selected from cyclohexane, dodecane and hexadecane; the polysiloxane is polysiloxane without active groups, specifically selected from polymethylsiloxane and polyethylsiloxane, preferably polymethylsiloxane, and the kinematic viscosity of the solvent is 500-2000 mPa.s. The amount of the solvent is 20-70%, preferably 40-50% of the total mass of the organosilicon composition.
A silicone composition is prepared by the following steps:
(1) adding hydrogen-containing polysiloxane B, organic silicon resin G, unsaturated polyether C and a solvent H into a reactor, mixing and stirring uniformly, heating to 50 ℃, adding a catalyst I, reacting for 1-2H at 50-90 ℃, preserving heat, adding dimethyl hydrogen terminated vinyl polysiloxane A, mixing, stirring uniformly, preserving heat, and continuing to react for 1-2H;
(2) and (2) continuing adding a catalyst II into the composition in the step (1), heating to 100-140 ℃, reacting for 0.5-1 h, preserving heat, adding silicon dioxide, mixing, stirring uniformly, reacting for 0.5-1 h under the condition of preserving heat, and cooling to room temperature to obtain the organic silicon composition.
The silicone composition prepared by the present invention can be prepared in the form of an emulsion by a known technique, and the defoaming composition and the emulsifier are mixed, and water and the thickener are gradually added, and after being uniformly mixed, the oil-in-water silicone emulsion is prepared by a mechanical device such as a colloid mill and a homogenizer.
The emulsifier comprises a nonionic surfactant and an anionic surfactant. The nonionic surfactant is selected from polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauric acid, polyoxyethylene oleic ether, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, polyoxyethylene sorbitan monostearate ether ester, polyoxyethylene sorbitan monooleate ether ester, polyoxyethylene sorbitan tristearate ether ester and polyoxyethylene castor oil polyoxyethylene ether.
The anionic surfactant is selected from sodium dodecyl polyoxyethylene ether sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium hexadecyl benzene sulfonate, and sodium dodecyl diphenyl ether disulfonate.
The above emulsifiers are used alone or in admixture in any proportion.
The thickener is selected from xanthan gum, guar gum, polyvinyl alcohol, sodium carboxymethylcellulose, hydroxyethyl cellulose, polyacrylic acid, polyacrylamide, and polyacrylate.
Detailed Description
Example 1
(1) Into the reactor was charged 100g of (Me) having a viscosity of 90mPa.s2HSiO(Me2SiO)50(MeHSiO)20SiH(Me)240g of a silicone resin (M: Q: 0.5:1.0), 493g of a polymethylsiloxane having a viscosity of 500mPa.s, and 12g of a silicone resin having a CH structure2＝CHCH2(EO)20(PO)60H, an unsaturated polyether; mixing, stirring, heating to 50 deg.C, adding 0.005g 1% chloroplatinic acid isopropanol solution, keeping the temperature at 50 deg.C, reacting for 2 hr, adding 300g H (Me) with viscosity of 3000mPa.s2SiO(Me2SiO)500(MeViSiO)40SiH(Me)2Mixing and stirring evenly, and continuing to react for 2 hours at 50 ℃; (2) 14.995g of potassium hydroxide-isopropanol solution is continuously added into the composition in the step (1), and the temperature is raised to 100 ℃ for reaction for 1 h; keeping the temperature, adding 40g of the mixture with the specific surface area of 300m2The hydrophobic silicon dioxide is mixed and stirred evenly for reaction for 1 hour at the temperature of 100 ℃, and the mixture is cooled to the room temperature to obtain the organic silicon composition S1.
Example 2
(1) 50g of (Me) having a viscosity of 500 mPas are charged into the reactor2HSiO(Me2SiO)200(MeHSiO)30SiH(Me)280g of a silicone resin (M: Q ═ 0.8:1.0), 400g of a polymethylsiloxane having a viscosity of 2000mPa.s, and 10g of a silicone resin having a structure of CH2＝CHCH2(EO)40(PO)30H, an unsaturated polyether; mixing, stirring, heating to 50 deg.C, adding 0.01g 1% chloroplatinic acid isopropanol solution, heating to 90 deg.C, reacting for 1h, adding 400g H (Me) with viscosity of 100000mPa.s2SiO(Me2SiO)1500(MeViSiO)300SiH(Me)2Mixing and stirring evenly, and continuously reacting for 0.5h at 90 ℃; (2) continuously adding 10g of potassium hydroxide-isopropanol solution into the composition in the step (1), and heating to 140 ℃ for reaction for 30 min; keeping the temperature, adding 49.99g of the mixture with the specific surface area of 500m2The hydrophobic silicon dioxide of the gas phase method is mixed and stirred evenly, the reaction is continued for 30min at the temperature of 140 ℃, and the organosilicon composition S2 is obtained after the reaction is cooled to the room temperature.
Example 3
(1) 190g of (Me) having a viscosity of 40mPa.s are charged into the reactor2HSiO(Me2SiO)35(MeHSiO)15SiH(Me)240g of a silicone resin (M: Q: 0.6:1.0), 500g of a polymethylsiloxane having a viscosity of 1000mPa.s, and 15g of a silicone resin having a CH structure2＝CHCH2(EO)(PO)40H, an unsaturated polyether; mixing, stirring, heating to 50 deg.C, adding 0.008g 1% chloroplatinic acid isopropanol solution, heating to 70 deg.C, reacting for 0.8h, adding 300g H (Me) with viscosity of 5000mPa.s2SiO(Me2SiO)600(MeViSiO)60SiH(Me)2Mixing and stirring evenly, and continuously reacting for 1.5h at 70 ℃; (2) 15.008g of potassium hydroxide-isopropanol solution is continuously added into the composition in the step (1), and the temperature is raised to 120 ℃ for reaction for 0.6 h; keeping the temperature, adding 40g of the mixture with the specific surface area of 50m2The hydrophobic silicon dioxide is mixed and stirred evenly at 120 ℃ for further reaction for 30min, and is cooled to room temperature to obtain the organic silicon composition S3.
Example 4
(1) 159.994g of (Me) having a viscosity of 200mPa.s were charged into the reactor2HSiO(Me2SiO)100(MeHSiO)25SiH(Me)240g of a silicone resin (M: Q ═ 0.7:1.0), 400g of hexadecane having a viscosity of 800mPa.s, and 50g of a compound having a structure of CH2＝CHCH2(EO)30H, an unsaturated polyether; mixing, stirring, heating to 50 deg.C, adding 0.006g 1% chloroplatinic acid isopropanol solution, heating to 80 deg.C, reacting for 1h, adding 350g H (Me) with viscosity of 10000mPa.s2SiO(Me2SiO)700(MeViSiO)150SiH(Me)2Mixing and stirring evenly, and continuously reacting for 1h at 80 ℃; (2) continuously adding 10g of potassium hydroxide-isopropanol solution into the composition in the step (1), and heating to 130 ℃ for reaction for 1 h; keeping the temperature, adding 40g of the mixture with the specific surface area of 260m2The hydrophobic silicon dioxide is mixed and stirred evenly for further reaction for 30min at the temperature of 130 ℃, and the mixture is cooled to room temperature to obtain the organic silicon composition S4.
Example 5
(1) 59.995g of (Me) having a viscosity of 400mPa.s were charged into the reactor2HSiO(Me2SiO)175(MeHSiO)25SiH(Me)240g of a silicone resin (M: Q: 0.6:1.0), 500g of a polymethylsiloxane having a viscosity of 1500mPa.s, and 10g of a silicone resin having a CH structure2＝CHCH2(EO)15(PO)15H, an unsaturated polyether; mixing, stirring, heating to 50 deg.C, adding 0.005g 1% chloroplatinic acid isopropanol solution, heating to 60 deg.C, reacting for 1h, adding 300g H (Me) with viscosity of 30000mPa.s2SiO(Me2SiO)1000(MeViSiO)240SiH(Me)2Mixing and stirring evenly, and continuously reacting for 1h at 60 ℃; (2) continuously adding 10g of potassium hydroxide-isopropanol solution into the composition in the step (1), and heating to 115 ℃ for reacting for 1 h; keeping the temperature, adding 80g of the mixture with the specific surface area of 150m2The hydrophobic silicon dioxide of the gas phase method is mixed and stirred evenly, the reaction is continued for 30min at the temperature of 115 ℃, and the organosilicon composition S5 is obtained after the reaction is cooled to the room temperature.
Example 6
(1) 50g of (Me) having a viscosity of 70mPa.s are charged into the reactor2HSiO(Me2SiO)50(MeHSiO)15SiH(Me)260g of a silicone resin (M: Q: 0.5:1.0), 449.993g of a polymethylsiloxane having a viscosity of 600mPa.s, and 30g of a silicone resin having a CH structure2＝CHCH2(EO)10(PO)5H, an unsaturated polyether; mixing, stirring, heating to 50 deg.C, adding 0.007g 1% chloroplatinic acid isopropanol solution, heating to 85 deg.C, reacting for 1h, adding 340g H (Me) with viscosity of 50000mPa.s2SiO(Me2SiO)1200(MeViSiO)150SiH(Me)2Mixing and stirring evenly, and continuously reacting for 1h at 85 ℃; (2) continuously adding 30g of potassium hydroxide-isopropanol solution into the composition in the step (1), and heating to 120 ℃ for reacting for 1 h; keeping the temperature, adding 40g of the mixture with the specific surface area of 300m2The hydrophobic silicon dioxide is mixed and stirred evenly for further reaction for 1 hour at the temperature of 120 ℃, and the mixture is cooled to the room temperature to obtain the organic silicon composition S6.
Example 7
(1) 130g of (Me) having a viscosity of 300 mPas are charged into the reactor2HSiO(Me2SiO)140(MeHSiO)20SiH(Me)250g of a silicone resin (M: Q ═ 0.7:1.0), 420g of a polymethylsiloxane having a viscosity of 1200mPa.s, and 24.995g of a silicone resin having a structure of CH2＝CHCH2(EO)5(PO)25H, an unsaturated polyether; mixing, stirring, heating to 50 deg.C, adding 0.005g 1% chloroplatinic acid isopropanol solution, heating to 70 deg.C, reacting for 1h, adding 300g H (Me) with viscosity of 80000mPa.s2SiO(Me2SiO)1500(MeViSiO)190SiH(Me)2Mixing and stirring evenly, and continuously reacting for 1h at 70 ℃; (2) continuously adding 20g of potassium hydroxide-isopropanol solution into the composition in the step (1), and heating to 110 ℃ for reaction for 2 hours; keeping the temperature, adding 55g of the mixture with the specific surface area of 200m2The hydrophobic silicon dioxide of the gas phase method is mixed and stirred evenly, and the reaction is continued for 1h at the temperature of 110 ℃, and the organosilicon composition S7 is obtained after the cooling to the room temperature.
Comparative example 1
(1) Into the reactor was charged 100g of (Me) having a viscosity of 90mPa.s2HSiO(Me2SiO)50(MeHSiO)20SiH(Me)240g of a silicone resin (M: Q ═ 0.5:1.0), 505g of polymethylsiloxane having a viscosity of 500 mpa.s; mixing, stirring, heating to 50 deg.C, adding 0.005g 1% chloroplatinic acid isopropanol solution, keeping the temperature at 50 deg.C, reacting for 2 hr, adding 300g H (Me) with viscosity of 3000mPa.s2SiO(Me2SiO)500(MeViSiO)40SiH(Me)2Mixing and stirring evenly, and continuing to react for 2 hours at 50 ℃; (2) 14.995g of potassium hydroxide-isopropanol solution is continuously added into the composition in the step (1), and the temperature is raised to 100 ℃ for reaction for 1 h; keeping the temperature, adding 40g of the mixture with the specific surface area of 300m2The hydrophobic silicon dioxide is mixed and stirred evenly for reaction for 1 hour at the temperature of 100 ℃, and the mixture is cooled to the room temperature to obtain the organic silicon composition S8.
Comparative example 2
(1) 50g of (Me) having a viscosity of 500 mPas are charged into the reactor2HSiO(Me2SiO)200(MeHSiO)30SiH(Me)280g of a silicone resin (M: Q ═ 0.8:1.0), 800g of a polymethylsiloxane having a viscosity of 2000mPa.s, and 10g of a silicone resin having a structure of CH2＝CHCH2(EO)40(PO)30H, an unsaturated polyether; mixing, stirring, heating to 50 deg.C, adding 1% chloroplatinic acid isopropanol solution 0.01g, and heating to 90 deg.C for reaction for 1.5 hr; (2) continuously adding 10g of potassium hydroxide-isopropanol solution into the composition in the step (1), and heating to 140 ℃ for reaction for 30 min; keeping the temperature, adding 49.99g of the mixture with the specific surface area of 500m2The hydrophobic silicon dioxide of the gas phase method is mixed and stirred evenly, the reaction is continued for 30min at the temperature of 140 ℃, and the organosilicon composition S9 is obtained after the reaction is cooled to the room temperature.
Comparative example 3
(1) 190g of (Me) having a viscosity of 40mPa.s are charged into the reactor2HSiO(Me2SiO)35(MeHSiO)15SiH(Me)240g of silicone resin (M: Q ═ 0.6:1.0), 500g of polymethylsiloxane having a viscosity of 1000mPa.s, 300g of H (Me) having a viscosity of 5000mPa.s2SiO(Me2SiO)600(MeViSiO)60SiH(Me)2(ii) a Mixing, stirring, heating to 50 deg.C, adding 0.008g 1% chloroplatinic acid isopropanol solution, heating to 70 deg.C, reacting for 0.8h, adding 15g CH2＝CHCH2(EO)(PO)40Mixing unsaturated polyether of H, stirring uniformly, and continuously reacting for 1.5H at 70 ℃; (2) 15.008g of potassium hydroxide-isopropanol solution is continuously added into the composition in the step (1), and the temperature is raised to 120 ℃ for reaction for 0.6 h; keeping the temperature, adding 40g of the mixture with the specific surface area of 50m2Precipitation process hydrophobic silica/gMixing, stirring uniformly, continuing to react for 30min at 120 ℃, and cooling to room temperature to obtain the organic silicon composition S10.
Examples 11 to 20
The organopolysiloxane antifoam composition emulsions were prepared using S1-S10 by the following method:
at room temperature, 40g of the organopolysiloxane antifoam composition, 8g of sorbitan trioleate and 12g of polyoxyethylene oleate are fully mixed for 1 hour under stirring, the temperature of the system is raised to 80 ℃ after completion, then the temperature of the system is kept, 40g of water is slowly added, the stirring speed is increased to change the water-in-oil emulsion into the oil-in-water emulsion, 20g of water is continuously added until the required mass concentration is 50%, the crude emulsion is further emulsified by a colloid mill, and finally, the organopolysiloxane antifoam composition emulsion M1-M10 with the solid content of 10% is diluted by acrylic acid thickening water.
Defoaming and foam suppressing performance test
The organopolysiloxane defoamer composition emulsions of examples 11-20 were tested for defoaming and foam suppressing properties in a circulating bubbler using a self-dispensing cork liquid. Injecting 600mL of cork liquid into a hard glass cylinder with the inner diameter of 5cm in a circulating bubbler, heating and maintaining at 90 ℃, opening a liquid circulating switch, controlling the flow to be 6L/min, injecting 0.4mL of organopolysiloxane antifoaming agent composition emulsion when the foam height in the glass cylinder rises to 300mL, starting timing, simultaneously recording the foam height until the foam height rises to 300mL again, and stopping liquid circulation. The higher the speed of the foam falling to 250mL after the defoamer composition emulsion is added, the lower the minimum foam height is, and the better the defoaming performance is; the longer the time taken for the foam to rise back to 300mL again indicates the better foam suppression of the defoamer composition. The test results are shown in Table 1.
TABLE 1 defoaming and foam suppressing Properties test results
| Time/s | M1 | M2 | M3 | M4 | M5 | M6 | M7 | M8 | M9 | M10 |
| 0 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 |
| 5 | 280 | 280 | 280 | 280 | 280 | 270 | 280 | 280 | 300 | 300 |
| 10 | 240 | 240 | 240 | 240 | 240 | 230 | 240 | 280 | 290 | 290 |
| 15 | 210 | 220 | 210 | 210 | 210 | 210 | 210 | 280 | 290 | 290 |
| 30 | 210 | 220 | 200 | 200 | 210 | 210 | 210 | 270 | 280 | 300 |
| 60 | 210 | 220 | 200 | 200 | 210 | 210 | 210 | 250 | 280 | |
| 90 | 210 | 220 | 200 | 200 | 210 | 200 | 210 | 250 | 270 | |
| 120 | 210 | 220 | 200 | 200 | 210 | 200 | 210 | 260 | 260 | |
| 150 | 210 | 220 | 210 | 210 | 210 | 200 | 210 | 280 | 290 | |
| 180 | 210 | 230 | 210 | 210 | 210 | 200 | 210 | 290 | 300 | |
| 210 | 220 | 230 | 210 | 210 | 220 | 200 | 220 | 300 | ||
| 240 | 220 | 230 | 210 | 210 | 230 | 210 | 220 | |||
| 270 | 240 | 240 | 210 | 210 | 240 | 230 | 240 | |||
| 300 | 260 | 260 | 240 | 240 | 280 | 240 | 260 | |||
| 330 | 280 | 300 | 270 | 270 | 300 | 260 | 280 | |||
| 360 | 300 | 300 | 300 | 260 | 300 | |||||
| 390 | 280 | |||||||||
| 420 | 300 |
As can be seen from Table 1, the emulsions prepared in examples S1-S7 exhibited a faster foam reduction rate in the early stage and a slower foam rise time in the later stage during the testing; in the tests of the emulsions prepared in S8, S9 and S10 of the comparative examples, the defoaming rate in the early stage was slow, the foam decreasing amplitude was small, and the foam rising speed in the later stage was fast.
Claims (11)
1. An organosilicon composition, characterized by consisting of:
A. dimethyl hydrogen group-terminated vinyl polyorganosiloxane: the dimethyl hydrogen-terminated vinyl polyorganosiloxane at least contains two vinyl groups bonded with silicon, and has the following structural general formula:
wherein Me is methyl and Vi is vinyl; r1、R2Is a hydrocarbyl group selected from the group consisting of alkyl, aryl, alkenyl, wherein alkyl is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, cyclopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-dodecyl, and n-octadecyl; aryl is selected from phenyl and benzyl; the alkenyl is selected from vinyl and allyl; r bound to the same silicon atom1And R2Can not be simultaneously vinyl and can be simultaneously methyl; the subscript p is an integer of 100-2000; the subscript q is an integer of 2-500, the kinematic viscosity of the methyl hydrogen end-capped vinyl polyorganosiloxane at 25 ℃ ranges from 100-200,000 mPa.s, and the using amount of the dimethyl hydrogen end-capped vinyl polyorganosiloxane accounts for 20-50% of the total mass of the organic silicon composition;
B. hydrogen-containing polyorganosiloxane: the hydrogen-containing polyorganosiloxane refers to polyorganosiloxane containing at least three hydrogen groups bonded with silicon:
wherein Me is methyl, R3、R4Is a hydrocarbyl group selected from the group consisting of alkyl groups, aryl groups, wherein the alkyl groups are selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, cyclopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-dodecyl, and n-octadecyl; aryl is selected from phenyl and benzyl; the subscript m is an integer of 5-350; the subscript n is an integer of 15-30; the kinematic viscosity of the hydrogen-containing polyorganosiloxane at 25 ℃ is 10-1,000 mPa.s, and the usage of the hydrogen-containing polyorganosiloxane accounts for 0.01-30% of the total mass of the organic silicon composition;
C. unsaturated polyether: the molecular structure general formula of the unsaturated polyether is as follows:
XO(EO)e(PO)fR5
wherein R is5May be the same or different; the alkyl is a hydrogen atom or monovalent substituted alkyl with 1-4 carbon atoms, and is specifically selected from methyl, ethyl, propyl, n-propyl, butyl and hydrogen atoms; x is an initiator group, is an unsaturated straight chain or branched chain alkyl group of 3-10, and is selected from allyl, alpha-butenyl, alpha-pentenyl, alpha-hexenyl, alpha-heptenyl, alpha-octenyl, alpha-nonenyl and alpha-decenyl; subscripts e and f are polymerization degrees, e is an integer of 1-100, f is an integer of 0-80, and the using amount of the unsaturated polyether accounts for 0.5-10% of the total mass of the organic silicon composition;
D. catalyst I: the catalyst I is a noble metal catalyst for promoting hydrosilylation reaction and is selected from platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution with the chloroplatinic acid concentration of 1%, rhodium-alcohol complex and rhodium-alkoxide complex, and the dosage of the catalyst I accounts for 0.0001-0.001% of the total mass of the organic silicon composition;
E. catalyst II: the catalyst II is selected from potassium hydroxide-isopropanol solution, potassium hydroxide-methanol solution, potassium hydroxide-ethanol solution and potassium hydroxide-methyl polysiloxane mixture, and the dosage of the catalyst II accounts for 0.1-5% of the total weight of the organic silicon composition;
F. silicon dioxide: the silicon dioxide is hydrophobic silicon dioxide, specifically selected from gas-phase hydrophobic silicon dioxide and precipitation hydrophobic silicon dioxide, and the specific surface area of the silicon dioxide is 50-500 m2(ii)/g; the silicon dioxide accounts for 2-15% of the total mass of the organic silicon composition;
G. silicone resin: the organic silicon resin is organic silicon resin containing M and Q units, and the organic silicon resin is formed by chain links CH3SiOl/2(M units) and SiO units4/2(Q unit) with the molar ratio of 0.4: 1.0-1.2: 1.0, wherein the usage amount of the organic silicon resin accounts for 1-15% of the total mass of the organic silicon composition;
H. solvent: the solvent is used as a reaction medium of various reactants and is selected from alkane and polysiloxane, wherein the alkane is C6-C20 saturated hydrocarbon, and is specifically selected from cyclohexane, dodecane and hexadecane; the polysiloxane is polysiloxane without active groups, and is specifically selected from polymethyl siloxane and polyethyl siloxane, the kinematic viscosity of the solvent is 500-2000 mPa.s, and the using amount of the solvent accounts for 20-70% of the total mass of the organosilicon composition;
the preparation method of the composition comprises the following steps:
(1) adding hydrogen-containing polysiloxane B, organic silicon resin G, unsaturated polyether C and a solvent H into a reactor, mixing and stirring uniformly, heating to 50 ℃, adding a catalyst I, reacting for 1-2H at 50-90 ℃, preserving heat, adding dimethyl hydrogen terminated vinyl polysiloxane A, mixing, stirring uniformly, preserving heat, and continuing to react for 1-2H;
(2) and (2) continuing adding a catalyst II into the composition in the step (1), heating to 100-140 ℃, reacting for 0.5-1 h, preserving heat, adding silicon dioxide, mixing, stirring uniformly, reacting for 0.5-1 h under the condition of preserving heat, and cooling to room temperature to obtain the organic silicon composition.
2. The silicone composition of claim 1, wherein in said dimethyl hydrogen terminated vinyl polyorganosiloxane, R is1、R2Is methyl, the subscript p is an integer of 500 to 1500The index q is an integer of 40 to 300.
3. The silicone composition according to claim 1, wherein the dimethyl hydrogen group-terminated vinyl polyorganosiloxane has a viscosity ranging from 3,000 to 100,000mpa.s, and is used in an amount of 30% to 40% based on the total mass of the silicone composition.
4. The silicone composition according to claim 1, wherein R is hydrogen-containing polyorganosiloxane3、R4Is methyl, and the subscript m is an integer of 35-200.
5. The silicone composition according to claim 1, wherein the hydrogen-containing polyorganosiloxane has a viscosity of 40 to 500mpa.s and is used in an amount of 5 to 19% by mass based on the total mass of the silicone composition.
6. The silicone composition of claim 1, wherein in said unsaturated polyether, X is allyl; subscript e is an integer of 1 to 40, and subscript f is 0 to 60.
7. The silicone composition according to claim 1, wherein the unsaturated polyether is used in an amount of 1 to 5% by mass based on the total mass of the silicone composition.
8. The silicone composition of claim 1, wherein catalyst I is a chloroplatinic acid isopropanol solution having a chloroplatinic acid concentration of 1% in an amount of 0.0005% to 0.001% by weight of the total silicone composition.
9. The organosilicon composition according to claim 1, wherein the catalyst II is a potassium hydroxide-isopropanol solution, and is used in an amount of 1-3% by weight based on the total weight of the organosilicon composition.
10. The silicone composition of claim 1, wherein the polysiloxane in the solvent is a polymethylsiloxane.
11. The silicone composition according to claim 1, wherein the amount of the solvent is 40% to 50% of the total mass of the silicone composition.
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| CN113797600B (en) * | 2020-06-16 | 2023-10-31 | 江苏四新科技应用研究所股份有限公司 | Organic silicon defoaming composition and preparation method thereof |
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| CN114316599B (en) * | 2021-06-07 | 2023-04-07 | 南京瑞思化学技术有限公司 | Preparation method of organic silicon composition |
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| CN114478947B (en) * | 2021-12-23 | 2023-12-08 | 山东华夏神舟新材料有限公司 | Novel photo-curing 3D printing resin material and preparation method thereof |
| CN114605647B (en) * | 2022-03-10 | 2023-07-04 | 江西蓝星星火有机硅有限公司 | Trapezoidal organosilicon modified polyether compound and preparation method thereof |
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| CN104436766A (en) * | 2014-12-19 | 2015-03-25 | 南京四新科技应用研究所有限公司 | Organosilicone composition |
| JP2016016368A (en) * | 2014-07-08 | 2016-02-01 | サンノプコ株式会社 | Powder defoaming agent |
| CN106669539A (en) * | 2016-12-30 | 2017-05-17 | 定远县新海岸生态园林有限公司 | Composite modified organosilicon surfactant |
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| DE102008043245A1 (en) * | 2008-10-29 | 2010-05-06 | Evonik Goldschmidt Gmbh | Silicone polyether copolymer systems and processes for their preparation by alkoxylation reaction |
| CN101884852A (en) * | 2010-06-30 | 2010-11-17 | 南京四新科技应用研究所有限公司 | Method for improving properties of polyether defoaming agent |
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| EP0341952A2 (en) * | 1988-05-09 | 1989-11-15 | Dow Corning Corporation | Silicone foam control composition |
| CN102407033A (en) * | 2011-06-29 | 2012-04-11 | 南京四新科技应用研究所有限公司 | Preparation method of particle defoaming agent |
| CN103819630A (en) * | 2014-03-05 | 2014-05-28 | 威尔（福建）生物有限公司 | Polyether modified organic silicon defoamer, and preparation method and application thereof |
| JP2016016368A (en) * | 2014-07-08 | 2016-02-01 | サンノプコ株式会社 | Powder defoaming agent |
| CN104436766A (en) * | 2014-12-19 | 2015-03-25 | 南京四新科技应用研究所有限公司 | Organosilicone composition |
| CN106669539A (en) * | 2016-12-30 | 2017-05-17 | 定远县新海岸生态园林有限公司 | Composite modified organosilicon surfactant |
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