CN110283322A - A kind of silicon composition - Google Patents
A kind of silicon composition Download PDFInfo
- Publication number
- CN110283322A CN110283322A CN201910375574.XA CN201910375574A CN110283322A CN 110283322 A CN110283322 A CN 110283322A CN 201910375574 A CN201910375574 A CN 201910375574A CN 110283322 A CN110283322 A CN 110283322A
- Authority
- CN
- China
- Prior art keywords
- silicon composition
- polysiloxane
- silicon
- gross mass
- catalyst
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 62
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010703 silicon Substances 0.000 title claims abstract description 60
- -1 polysiloxane Polymers 0.000 claims abstract description 96
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 31
- 238000010792 warming Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 230000002209 hydrophobic effect Effects 0.000 claims description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- ADYYRXNLCZOUSU-UHFFFAOYSA-M potassium;propan-2-ol;hydroxide Chemical compound [OH-].[K+].CC(C)O ADYYRXNLCZOUSU-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([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
- 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
- 239000012808 vapor phase Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 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
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000002947 alkylene 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
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([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
- 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
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910020485 SiO4/2 Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 claims description 2
- 239000010970 precious metal Substances 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
- 125000001424 substituent group Chemical group 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 229920002050 silicone resin Polymers 0.000 claims 1
- 239000002518 antifoaming agent Substances 0.000 abstract description 21
- 230000003254 anti-foaming effect Effects 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 229920006037 cross link polymer Polymers 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000009969 flowable effect Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 8
- 239000006210 lotion Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 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
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000007799 cork Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 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
- JYTNGEWJAZCVAN-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O JYTNGEWJAZCVAN-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000010165 autogamy Effects 0.000 description 1
- 238000005815 base catalysis Methods 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001155 polypropylene 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
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-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
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 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 present invention provides a kind of silicon compositions and preparation method thereof, hydrogeneous polysiloxane is reacted with unsaturated polyether, hydrosilylation occurs with dimethyl hydrogen-based sealing end vinyl polysiloxane again after the reaction was completed to react and carry out alkali process, crosslinked viscosity is efficiently controlled by hydrogeneous polysiloxane, form the flowable state cross-linked polymer with space structure, the addition of unsaturated polyether simultaneously, improve the dispersion performance of silicon composition, organic polysiloxane defoaming agent can be prepared based on above-mentioned silicon composition, it has good antifoaming performance in high temperature alkali system, the silicon composition has good dispersibility in use process simultaneously, it is not easily formed agglomeration precipitation, the application performance in later period is enhanced while improving suds suppressing properties.
Description
Technical field
The present invention relates to a kind of crosslinkable silicon compositions, belong to technical field of fine chemical preparations.
Background technique
Paper industry is an important industry closely bound up with the national economic development, although defoaming agent is in paper industry
Dosage it is seldom, but play the role of extremely important.In paper industry pulping process, due to containing a large amount of rouge in slurry
Fat acid soap, resin acid soaps foamer, along with the foam stabilizing substance of cellulose, slurry transport is easy to produce a large amount of foam, gives
Production brings unnecessary trouble and loss, and alkaline slurry also brings the problem in health to direct labor.The papermaking of early stage
Factory inhibits the generation of foam using the method for " clear water pressure bubble ", but the effect is unsatisfactory.With the rise of organosilicon industry with
And the continuous attention that people endanger foam, organopolysiloxane class defoaming agent start to be widely used in paper industry.
Early in nineteen sixty-eight, foreign countries just have begun the preparation research for carrying out organopolysiloxane class defoaming agent, such as
Defoaming agent composition is prepared in US3383327 based on dimethyl silicone polymer, but since its structure is excessively single, antifoaming ability
It can be poor.In later period research, US3455839 elaborates a kind of side for preparing crosslinkable organopolysiloxane defoaming agent composition
Method, and it has been put forward for the first time the technique reacted using vinyl polysiloxane with hydrogen containing siloxane, improve the defoaming agent later period
Foam inhibition ability, but it still has certain deficiency on antifoam performance；US4690713 points out to introduce second in polysiloxane
Alkenyl group and phenyl group, and be crosslinked under conditions of platinum catalyst catalysis with hydrogen containing siloxane, obtain defoaming agents
Object, but its suds suppressing properties can not fully meet the actual needs of production；US4639489 has used the poly- silicon oxygen of high viscosity terminal hydroxy group
Alkane reacts under conditions of base catalysis with ethyl polysilicate prepares organic polysiloxane defoaming agent, but due to its prepare it is organic
Silicon polymer viscosity is larger, does not have good antifoam performance；It is set forth in WO2013043487 using containing the organic of hydroxyl
Polysiloxanes is crosslinked with the organopolysiloxane crosslinking that end chain contains amino to react, the method for preparing defoaming agent composition,
But its cross-linked structure is more weak, is difficult to play good foam-inhibiting effect in alkali system.
Summary of the invention
The present invention relates to a kind of silicon compositions, and hydrogeneous polysiloxane is reacted with unsaturated polyether, has been reacted
Cheng Houzai reacts with dimethyl hydrogen-based sealing end vinyl polysiloxane generation hydrosilylation and carries out alkali process, by hydrogeneous
Polysiloxane efficiently controls crosslinked viscosity, forms the flowable state cross-linked polymer with space structure, while unsaturated
The addition of polyethers improves the dispersion performance of silicon composition, can be prepared based on above-mentioned silicon composition organic
Polysiloxane defoaming agent has good antifoaming performance, while the organosilicon in use process in high temperature alkali system
Composition has good dispersibility, it is not easy to form agglomeration precipitation, enhance the application in later period while improving suds suppressing properties
Performance.
Technical solution
A kind of silicon composition, which is characterized in that by following material composition:
A. dimethyl hydrogen-based blocks vinyl polysiloxane
Dimethyl hydrogen-based of the present invention sealing end vinyl polysiloxane refer at least containing there are two with silicon bonding second
Alkenyl group, general structure are as follows:
Wherein Me is methyl, and Vi is vinyl；R1、R2For alkyl, it is selected from alkyl, aryl, alkylene, wherein alkyl is selected from first
Base, ethyl, n-propyl, normal-butyl, isobutyl group, n-pentyl, cyclopenta, n-hexyl, n-heptyl, n-octyl, iso-octyl, positive nonyl
Base, positive decyl, dodecyl and n-octadecane base；Aryl is selected from phenyl, benzyl；Alkylene is selected from vinyl, allyl
Base.R1、R2It is preferred that methyl, but the R being connected on the same silicon atom1With R2It cannot simultaneously be vinyl, can simultaneously be first
Base.The integer that subscript p is 100~2000, preferably 500~1500 integer；The integer that subscript q is 2~500, preferably 40~
300 integer.Kinematic viscosity range of the dimethyl hydrogen-based sealing end vinyl polysiloxane at 25 DEG C 100~
Between 200,000mPa.s, preferred viscosity ranges are between 3,000~100,000mPa.s.The dimethyl hydrogen-based blocks second
Alkenyl polysiloxane dosage accounts for the 20%~50% of silicon composition gross mass, preferably 30%~40%.
B. hydrogeneous polysiloxane
Hydrogeneous polysiloxane of the present invention refers at least containing there are three the poly organos with silicon-bonded hydrogen groups
Alkane:
Wherein Me is methyl, R3、R4For alkyl, it is selected from alkyl, aryl, wherein alkyl is selected from methyl, ethyl, n-propyl, positive fourth
Base, isobutyl group, n-pentyl, cyclopenta, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, dodecyl
With n-octadecane base；Aryl is selected from phenyl, benzyl.R3、R4It is preferred that methyl.The integer that subscript m is 5~350, preferably 35~
200 integer；The integer that subscript n is 15~30.Kinematic viscosity of the hydrogeneous polysiloxane at 25 DEG C 10~1,
Between 000mPa.s, preferred movement viscosity is between 40~500mPa.s.The dosage of the hydrogeneous polysiloxane occupies machine
The 0.01~30% of silicon composition gross mass, preferably 5~19%.
C. unsaturated polyether
The unsaturated polyether, general formula of molecular structure are as follows:
XO(EO) e (PO) f R5
All R in molecular structure5It can be identical or different.The substituted carbon atom number that it includes hydrogen atom or monovalence is 1~4
Alkyl, be selected from methyl, ethyl, propyl, n-propyl, butyl, preferably 80% or more substituent group R5It is hydrogen atom.X is starting
Agent group, be 3 ~ 10 unsaturated linear chain or branched chain alkyl, including allyl,αCyclobutenyl,αPentenyl,αHexenyl,αHeptenyl,αOctenyl,αNonenyl,αDecene base.The preferred allyl of X.Subscripte、fFor the degree of polymerization,eFor 1 ~ 100 it is whole
Number, preferably 1 ~ 40,fFor 0 ~ 80 integer, preferably 0 ~ 60.The dosage of the unsaturated polyether accounts for silicon composition gross mass
0.5 ~ 10%, preferably 1 ~ 5%.
D. catalyst
CatalystIt is the precious metal catalyst for promoting hydrosilylation, selected from platinum -ol complex compound, platinum-alkene complexing
Object, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complex compound, chloroplatinic acid concentration be 1% isopropyl alcohol solution of chloroplatinic acid,
The isopropyl alcohol solution of chloroplatinic acid that rhodium -ol complex compound, rhodium -ol salt complex, preferably chloroplatinic acid concentration are 1%.CatalystDosage accounts for
The 0.0001% ~ 0.001% of silicon composition gross mass, preferably 0.0005% ~ 0.001%.
E. catalyst
CatalystSelected from potassium hydroxide-isopropanol solution, potassium hydroxide-methanol solution, potassium hydroxide-ethanol solution, hydrogen-oxygen
Change potassium-methyl polysiloxane mixture, preferably potassium hydroxide-isopropanol solution.CatalystIt is total that dosage accounts for silicon composition
The 0.1% ~ 5% of quality, preferably 1% ~ 3%.
F. silica
Inventive silica is hydrophobic silica, is chosen in particular from vapor phase method hydrophobic silica, precipitation method hydrophobic titanium dioxide
Silicon, specific surface area are 50~500m2/g.Silica content accounts for the 2% ~ 15% of silicon composition gross mass, preferably 4%
~ 8%。
G. organic siliconresin
Organic siliconresin of the present invention refers to the organic siliconresin containing M and Q unit, and organic siliconresin is by chain link
CH3SiOl/2(M unit) and chain link SiO4/2(Q unit) composition, molar ratio between the two is 0.4:1.0 ~ 1.2:1.0, excellent
Select 0.5:1.0 ~ 0.8:1.0.The dosage of organic siliconresin accounts for the 1% ~ 15% of silicon composition gross mass, preferably 4% ~ 8%.
H. solvent
Reaction medium of the solvent of the present invention as various reactants is selected from alkane, polysiloxanes.Wherein alkane be C6 ~
The saturated hydrocarbons of C20 is chosen in particular from hexamethylene, dodecane, hexadecane；Polysiloxanes is the polysiloxanes without active group, tool
Body is selected from polymethyl siloxane, polyethylsiloxane, the preferred polymethyl siloxane of polysiloxanes, and the kinematic viscosity of the solvent exists
Between 500 ~ 2000mPa.s.Solvent usage accounts for the 20% ~ 70% of silicon composition gross mass, preferably 40% ~ 50%.
A kind of silicon composition preparation process is as follows:
(1) hydrogeneous polysiloxane B, organic siliconresin G, unsaturated polyether C and solvent H, mixing are added in the reactor to stir
It is even and be warming up to 50 DEG C of addition catalyst I, 1 ~ 2h is reacted at 50 ~ 90 DEG C, heat preservation is added dimethyl hydrogen-based and blocks vinyl
Polysiloxane A, mixing stirs evenly under heat-retaining condition that the reaction was continued 1 ~ 2h；
(2) composition in step (1) continuously adds catalyst II, is warming up to 0.5 ~ 1h of reaction at 100 ~ 140 DEG C, and heat preservation adds
Enter silica, mixing stirs evenly under heat-retaining condition that the reaction was continued 0.5 ~ 1h is cooled to room temperature, obtains silicon composition.
Prepared by the method silicon composition can be used well-known technique and be prepared into emulsion form, by defoaming composition
It is mixed with emulsifier, and is gradually added water and thickener, after mixing by mechanical equipment, such as colloidal mill, homogenizer,
Oil-in-water type organic silicon emulsion is prepared.
The emulsifier includes nonionic surfactant and anionic surfactant.Nonionic surfactant is selected from
Nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether, lauric acid polyoxyethylene ether, oleic acid polyoxyethylene, anhydrous sorbitol
Monostearate, sorbitan monooleate, anhydrous sorbitol tristearate, sorbitan trioleate, dehydration mountain
Pears alcohol monostearate polyoxyethylene ether-ester, anhydrous sorbitol list oleic acid polyoxyethylene ester, three stearic acid polyoxy of anhydrous sorbitol
Ethylene ether-ether, castor oil polyoxyethylene ether.
Anionic surfactant is selected from dodecyl polyoxyethylene ether sodium sulphate, lauryl sodium sulfate, dodecyl
Benzene sulfonic acid sodium salt, dodecyl sodium sulfate, sodium cetanesulfonate, cetyl benzenesulfonic acid sodium, dodecyl diphenyl oxide disulfonic acid
Sodium.
Mentioned emulsifier is used alone or is used in mixed way with arbitrary proportion.
Thickener is selected from xanthan gum, guar gum, polyvinyl alcohol, sodium carboxymethylcellulose, hydroxyethyl cellulose, polypropylene
Acid, polyacrylamide, polyacrylate.
Specific embodiment
Embodiment 1
(1) (Me) that 100g viscosity is 90mPa.s is added in the reactor2HSiO(Me2SiO)50(MeHSiO)20SiH(Me)2、
Polymethyl siloxane that 40g organic siliconresin (M:Q=0.5:1.0), 493g viscosity are 500mPa.s, 12g structure are CH2=CHCH2
(EO)20(PO)60The unsaturated polyether of H；Mixing stirs evenly the isopropyl alcohol solution of chloroplatinic acid that 0.005g1% is added when being warming up to 50 DEG C,
After 50 DEG C of heat preservation the reaction was continued 2h, the H (Me) that 300g viscosity is 3000mPa.s is added2SiO(Me2SiO)500(MeViSiO)40SiH(Me)2, mixing stirs evenly at 50 DEG C that the reaction was continued 2h；(2) 14.995g hydrogen-oxygen is continuously added in the composition of step (1)
Change potassium-aqueous isopropanol, and is warming up to 100 DEG C of reaction 1h；It is 300m that 40g specific surface area, which is added, in heat preservation2The precipitation method of/g are hydrophobic
Silica, mixing stirs evenly at 100 DEG C that the reaction was continued 1h are cooled to room temperature, obtain silicon composition S1.
Embodiment 2
(1) (Me) that 50g viscosity is 500mPa.s is added in the reactor2HSiO(Me2SiO)200(MeHSiO)30SiH
(Me)2, 80g organic siliconresin (M:Q=0.8:1.0), 400g viscosity be 2000mPa.s polymethyl siloxane, 10g structure be
CH2=CHCH2(EO)40(PO)30The unsaturated polyether of H；Mixing stirs evenly the chloroplatinic acid isopropyl that 0.01g1% is added when being warming up to 50 DEG C
After being continuously heating to 90 DEG C of reaction 1h, the H (Me) that 400g viscosity is 100000mPa.s is added in alcoholic solution2SiO(Me2SiO)1500
(MeViSiO)300SiH(Me)2, mixing, which stirs evenly, to be continued to react 0.5h at 90 DEG C；(2) it is continuously added in step (1) composition
10g potassium hydroxide-isopropanol solution, and it is warming up to 140 DEG C of reaction 30min；It is 500m that 49.99g specific surface area, which is added, in heat preservation2/g
Vapor phase method hydrophobic silica, mixing stirs evenly at 140 DEG C that the reaction was continued 30min is cooled to room temperature, obtains organosilicon combination
Object S2.
Embodiment 3
(1) (Me) that 190g viscosity is 40mPa.s is added in the reactor2HSiO(Me2SiO)35(MeHSiO)15SiH(Me)2、
Polymethyl siloxane that 40g organic siliconresin (M:Q=0.6:1.0), 500g viscosity are 1000mPa.s, 15g structure are CH2=
CHCH2(EO) (PO)40The unsaturated polyether of H；The chloroplatinic acid isopropanol that mixing stirs evenly addition 0.008g1% when being warming up to 50 DEG C is molten
After being continuously heating to 70 DEG C of reaction 0.8h, the H (Me) that 300g viscosity is 5000mPa.s is added in liquid2SiO(Me2SiO)600
(MeViSiO) 60SiH(Me)2, mixing, which stirs evenly, to be continued to react 1.5h at 70 DEG C；(2) it is continuously added in step (1) composition
15.008g potassium hydroxide-isopropanol solution, and it is warming up to 120 DEG C of reaction 0.6h；It is 50m that 40g specific surface area, which is added, in heat preservation2/g
Precipitation method hydrophobic silica, mixing stirs evenly at 120 DEG C that the reaction was continued 30min is cooled to room temperature, obtains organosilicon combination
Object S3.
Embodiment 4
(1) (Me) that 159.994g viscosity is 200mPa.s is added in the reactor2HSiO(Me2SiO)100(MeHSiO)25SiH
(Me)2, 40g organic siliconresin (M:Q=0.7:1.0), 400g viscosity be 800mPa.s hexadecane, 50g structure be CH2=
CHCH2(EO)30The unsaturated polyether of H；Mixing stirs evenly the isopropyl alcohol solution of chloroplatinic acid that 0.006g1% is added when being warming up to 50 DEG C, after
Continue after being warming up to 80 DEG C of reaction 1h, the H (Me) that 350g viscosity is 10000mPa.s is added2SiO(Me2SiO)700(MeViSiO)150SiH(Me)2, mixing, which stirs evenly, to be continued to react 1h at 80 DEG C；(2) 10g potassium hydroxide-is continuously added in step (1) composition
Aqueous isopropanol, and it is warming up to 130 DEG C of reaction 1h；It is 260m that 40g specific surface area, which is added, in heat preservation2The precipitation method hydrophobic titanium dioxide of/g
Silicon, mixing stirs evenly at 130 DEG C that the reaction was continued 30min are cooled to room temperature, obtain silicon composition S4.
Embodiment 5
(1) (Me) that 59.995g viscosity is 400mPa.s is added in the reactor2HSiO(Me2SiO)175(MeHSiO)25SiH
(Me)2, 40g organic siliconresin (M:Q=0.6:1.0), 500g viscosity be 1500mPa.s polymethyl siloxane, 10g structure be
CH2=CHCH2(EO)15 (PO)15The unsaturated polyether of H；The chloroplatinic acid that mixing stirs evenly addition 0.005g1% when being warming up to 50 DEG C is different
After being continuously heating to 60 DEG C of reaction 1h, the H (Me) that 300g viscosity is 30000mPa.s is added in propanol solution2SiO(Me2SiO)1000
(MeViSiO)240SiH(Me)2, mixing, which stirs evenly, to be continued to react 1h at 60 DEG C；(2) 10g is continuously added in step (1) composition
Potassium hydroxide-isopropanol solution, and it is warming up to 115 DEG C of reaction 1h；It is 150m that 80g specific surface area, which is added, in heat preservation2The vapor phase method of/g
Hydrophobic silica, mixing stirs evenly at 115 DEG C that the reaction was continued 30min are cooled to room temperature, obtain silicon composition S5.
Embodiment 6
(1) (Me) that 50g viscosity is 70mPa.s is added in the reactor2HSiO(Me2SiO)50(MeHSiO)15SiH(Me)2、
Polymethyl siloxane that 60g organic siliconresin (M:Q=0.5:1.0), 449.993g viscosity are 600mPa.s, 30g structure are CH2
=CHCH2(EO)10 (PO)5The unsaturated polyether of H；Mixing stirs evenly the chloroplatinic acid isopropanol that 0.007g1% is added when being warming up to 50 DEG C
After being continuously heating to 85 DEG C of reaction 1h, the H (Me) that 340g viscosity is 50000mPa.s is added in solution2SiO(Me2SiO)1200
(MeViSiO)150SiH(Me)2, mixing, which stirs evenly, to be continued to react 1h at 85 DEG C；(2) 30g is continuously added in step (1) composition
Potassium hydroxide-isopropanol solution, and it is warming up to 120 DEG C of reaction 1h；It is 300m that 40g specific surface area, which is added, in heat preservation2The precipitation method of/g
Hydrophobic silica, mixing stirs evenly at 120 DEG C that the reaction was continued 1h are cooled to room temperature, obtain silicon composition S6.
Embodiment 7
(1) (Me) that 130g viscosity is 300mPa.s is added in the reactor2HSiO(Me2SiO)140(MeHSiO)20SiH
(Me)2, 50g organic siliconresin (M:Q=0.7:1.0), 420g viscosity be 1200mPa.s polymethyl siloxane, 24.995g knot
Structure is CH2=CHCH2(EO)5(PO)25The unsaturated polyether of H；Mixing stirs evenly the chloroplatinic acid that 0.005g1% is added when being warming up to 50 DEG C
After being continuously heating to 70 DEG C of reaction 1h, the H (Me) that 300g viscosity is 80000mPa.s is added in aqueous isopropanol2SiO
(Me2SiO)1500(MeViSiO)190SiH(Me)2, mixing, which stirs evenly, to be continued to react 1h at 70 DEG C；(2) step (1) composition relays
It is continuous that 20g potassium hydroxide-isopropanol solution is added, and it is warming up to 110 DEG C of reaction 2h；It is 200m that 55g specific surface area, which is added, in heat preservation2/g
Vapor phase method hydrophobic silica, mixing stirs evenly at 110 DEG C that the reaction was continued 1h is cooled to room temperature, obtains silicon composition
S7。
Comparative example 1
(1) (Me) that 100g viscosity is 90mPa.s is added in the reactor2HSiO(Me2SiO)50(MeHSiO)20SiH(Me)2、
40g organic siliconresin (M:Q=0.5:1.0), the polymethyl siloxane that 505g viscosity is 500mPa.s；Mixing, which stirs evenly, is warming up to 50
DEG C when be added the isopropyl alcohol solution of chloroplatinic acid of 0.005g1%, after 50 DEG C of heat preservation the reaction was continued 2h, 300g viscosity, which is added, is
The H (Me) of 3000mPa.s2SiO(Me2SiO)500(MeViSiO)40SiH(Me)2, mixing stirs evenly at 50 DEG C that the reaction was continued 2h；
(2) 14.995g potassium hydroxide-isopropanol solution is continuously added in the composition of step (1), and is warming up to 100 DEG C of reaction 1h；It protects
It is 300m that 40g specific surface area, which is added, in temperature2The precipitation method hydrophobic silica of/g, mixing stirs evenly at 100 DEG C that the reaction was continued 1h are cold
But to room temperature, silicon composition S8 is obtained.
Comparative example 2
(1) (Me) that 50g viscosity is 500mPa.s is added in the reactor2HSiO(Me2SiO)200(MeHSiO)30SiH
(Me)2, 80g organic siliconresin (M:Q=0.8:1.0), 800g viscosity be 2000mPa.s polymethyl siloxane, 10g structure be
CH2=CHCH2(EO)40(PO)30The unsaturated polyether of H；Mixing stirs evenly the chloroplatinic acid isopropyl that 0.01g1% is added when being warming up to 50 DEG C
Alcoholic solution is continuously heating to 90 DEG C of reaction 1.5h；(2) to continuously add 10g potassium hydroxide-isopropanol in step (1) composition molten
Liquid, and it is warming up to 140 DEG C of reaction 30min；It is 500m that 49.99g specific surface area, which is added, in heat preservation2The vapor phase method hydrophobic titanium dioxide of/g
Silicon, mixing stirs evenly at 140 DEG C that the reaction was continued 30min are cooled to room temperature, obtain silicon composition S9.
Comparative example 3
(1) (Me) that 190g viscosity is 40mPa.s is added in the reactor2HSiO(Me2SiO)35(MeHSiO)15SiH(Me)2、
Polymethyl siloxane that 40g organic siliconresin (M:Q=0.6:1.0), 500g viscosity are 1000mPa.s, 300g viscosity are
The H (Me) of 5000mPa.s2SiO(Me2SiO)600(MeViSiO) 60SiH(Me)2；Mixing stirs evenly addition when being warming up to 50 DEG C
The isopropyl alcohol solution of chloroplatinic acid of 0.008g1%, after being continuously heating to 70 DEG C of reaction 0.8h, addition 15g structure is CH2=CHCH2
(EO) (PO)40The unsaturated polyether of H, mixing stir evenly continuation and react 1.5h at 70 DEG C；(2) continue to add in step (1) composition
Enter 15.008g potassium hydroxide-isopropanol solution, and is warming up to 120 DEG C of reaction 0.6h；It is 50m that 40g specific surface area, which is added, in heat preservation2/
The precipitation method hydrophobic silica of g, mixing stirs evenly at 120 DEG C that the reaction was continued 30min are cooled to room temperature, obtain organosilicon group
Close object S10.
Embodiment 11 ~ 20
Organic polysiloxane defoaming agent composition emulsion is prepared using S1 ~ S10, the preparation method is as follows:
At room temperature, by 40g organopolysiloxane defoaming agent composition, 8g sorbitan trioleate and 12g oleic acid polyoxy second
Alkene ether is sufficiently mixed 1h under stiring, and the temperature of above-mentioned system is increased to 80 DEG C after the completion, then keeps system temperature, slowly
40g water is added in ground, and improving mixing speed makes it become emulsion oil-in-water from water-in-oil emulsion, continues plus 20g water is to required
The mass concentration wanted is 50%, and thick lotion is further emulsified by colloid mill, is finally diluted to solid content with acrylic acid viscous water
For 10% organopolysiloxane defoaming agent composition lotion M1 ~ M10.
Antifoaming performance test
Organopolysiloxane defoaming agent composition using autogamy cork liquid, in circulation bubbling instrument in testing example 11-20
The antifoaming performance of lotion.It is heating in the hard glass cylinder of 5cm that 600mL cork liquid, which is injected internal diameter in circulation bubbling instrument,
And 90 DEG C are maintained, liquid circulation switch is opened, controls flow to 6L/min, when foam height rises in glass cylinder
When 300mL, injects 0.4mL organopolysiloxane defoaming agent composition lotion and start timing, while recording foam height, until
Foam height is gone up again to 300mL, stop liquid circulation.Foam drops at 250mL after defoaming agent composition lotion is added
Speed it is faster, minimum foam height is lower, illustrates that antifoam performance is better；The time required to when foam gos up again to 300mL about
Length illustrates that defoaming agent composition suds suppressing properties are better.Test result is shown in Table 1.
1 antifoaming performance test result of table
| 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 |
It can be seen from Table 1 that it is very fast with lotion test process mid-early stage foam fall off rate prepared by S1 ~ S7 in embodiment,
The foam rise time in later period is slower；In testing, defoaming early period rate is slower for the lotion of S8, S9 and S10 preparation in comparative example,
The amplitude of foam decline is small, and later period foam rise speed is fast.
Claims (11)
1. a kind of silicon composition, it is characterised in that composed of the following components:
A. dimethyl hydrogen-based blocks vinyl polysiloxane: the dimethyl hydrogen-based blocks vinyl polysiloxane
Refer at least containing there are two with silicon bonding vinyl groups, general structure is as follows:
Wherein Me is methyl, and Vi is vinyl；R1、R2For alkyl, be selected from alkyl, aryl, alkylene, wherein alkyl be selected from methyl,
Ethyl, n-propyl, normal-butyl, isobutyl group, n-pentyl, cyclopenta, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, just
Decyl, dodecyl and n-octadecane base；Aryl is selected from phenyl, benzyl；Alkylene is selected from vinyl, allyl；Connection
R on the same silicon atom1With R2It cannot simultaneously be vinyl, can simultaneously be methyl；Subscript p be 100~2000 it is whole
Number；The integer that subscript q is 2~500, kinematic viscosity model of the methyl hydrogen-based sealing end vinyl polysiloxane at 25 DEG C
It is trapped among between 100~200,000mPa.s, the dimethyl hydrogen-based sealing end vinyl polysiloxane dosage accounts for organosilicon group
Close the 20%~50% of object gross mass；
B. hydrogeneous polysiloxane: the hydrogeneous polysiloxane refer at least containing there are three and silicon-bonded hydrogen groups
Polysiloxane:
Wherein Me is methyl, R3、R4For alkyl, it is selected from alkyl, aryl, wherein alkyl is selected from methyl, ethyl, n-propyl, positive fourth
Base, isobutyl group, n-pentyl, cyclopenta, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, dodecyl
With n-octadecane base；Aryl is selected from phenyl, benzyl；The integer that subscript m is 5~350；The integer that subscript n is 15~30；It is described
Kinematic viscosity of the hydrogeneous polysiloxane at 25 DEG C between 10~1,000mPa.s, the hydrogeneous polysiloxane
Dosage accounts for the 0.01~30% of silicon composition gross mass；
C. unsaturated polyether: the unsaturated polyether, general formula of molecular structure are as follows:
XO(EO)e(PO)fR5
Wherein R5It can be identical or different；It include hydrogen atom or monovalence substituted carbon atom number be 1~4 alkyl, be selected from first
Base, ethyl, propyl, n-propyl, butyl, preferably 80% or more substituent group R5It is hydrogen atom；X be initiator group, be 3~
The alkyl of 10 unsaturated linear chain or branched chain, including allyl, alpha-butylene base, α-pentenyl, α-hexenyl, α-heptenyl, α-
Octenyl, α-nonenyl, α-decene base；Subscript e, f is the degree of polymerization, and the integer that integer that e is 1~100, f are 0~80 is described
The dosage of unsaturated polyether accounts for the 0.5~10% of silicon composition gross mass；
D. catalyst I: the catalyst I is the precious metal catalyst for promoting hydrosilylation, is selected from platinum -ol network
Close object, platinum-alkene complex, platinum -ol salt complex, platinum-ether complexes, platinum -one complex compound, the chlorine that chloroplatinic acid concentration is 1%
Platinic acid aqueous isopropanol, rhodium -ol complex compound, rhodium -ol salt complex, catalyst I dosage account for silicon composition gross mass
0.0001%~0.001%；
E. catalyst II: the catalyst II potassium hydroxide-isopropanol solution, potassium hydroxide-methanol solution, hydroxide are selected from
Potassium-ethanol solution, potassium hydroxide-methyl polysiloxane mixture, catalyst II dosage account for silicon composition gross mass
0.1%~5%；
F. silica: the silica is hydrophobic silica, is chosen in particular from vapor phase method hydrophobic silica, the precipitation method
Hydrophobic silica, specific surface area are 50~500m2/g；Silica content account for silicon composition gross mass 2%~
15%；
G. organic siliconresin: the organic siliconresin refers to the organic siliconresin containing M and Q unit, and organic siliconresin is by chain
Save CH3SiOl/2(M unit) and chain link SiO4/2(Q unit) composition, molar ratio between the two are 0.4:1.0~1.2:1.0, are had
The dosage of machine silicone resin accounts for the 1%~15% of silicon composition gross mass；
H. solvent: reaction medium of the agent as various reactants is selected from alkane, polysiloxanes, wherein alkane be C6~
The saturated hydrocarbons of C20 is chosen in particular from hexamethylene, dodecane, hexadecane；Polysiloxanes is the polysiloxanes without active group, tool
Body is selected from polymethyl siloxane, polyethylsiloxane, and the kinematic viscosity of the solvent between 500~2000mPa.s, use by solvent
Amount accounts for the 20%~70% of silicon composition gross mass；
A kind of silicon composition the preparation method is as follows:
(1) hydrogeneous polysiloxane B, organic siliconresin G, unsaturated polyether C and solvent H, mixing are added in the reactor to stir
It is even and be warming up to 50 DEG C of addition catalyst I, 1~2h is reacted at 50~90 DEG C, heat preservation is added dimethyl hydrogen-based and blocks vinyl
Polysiloxane A, mixing stirs evenly under heat-retaining condition that the reaction was continued 1~2h；
(2) composition in step (1) continuously adds catalyst II, is warming up to 0.5~1h of reaction at 100~140 DEG C, and heat preservation adds
Enter silica, mixing stirs evenly under heat-retaining condition that the reaction was continued 0.5~1h is cooled to room temperature, obtains silicon composition.
2. silicon composition as described in claim 1, dimethyl hydrogen-based is blocked in vinyl polysiloxane, R1、R2It is excellent
Select methyl, the integer of subscript p preferably 500~1500, the integer of subscript q preferably 40~300.
3. silicon composition as described in claim 1, dimethyl hydrogen-based blocks vinyl polysiloxane, preferred viscosities
For range between 3,000~100,000mPa.s, dosage preferably accounts for the 30%~40% of machine silicon composition gross mass.
4. silicon composition as described in claim 1, in hydrogeneous polysiloxane, R3、R4It is preferred that methyl, subscript m is preferred
35~200 integer.
5. silicon composition as described in claim 1, kinematic viscosity of the hydrogeneous polysiloxane at 25 DEG C preferably 40
Between~500mPa.s, dosage preferably accounts for the 5~19% of silicon composition gross mass.
6. silicon composition as described in claim 1, in unsaturated polyether, the preferred allyl of X；Subscript e's preferably 1~40
Integer, subscript f preferably 0~60.
7. silicon composition as described in claim 1, unsaturated polyether dosage preferably accounts for the 1 of silicon composition gross mass
~5%.
8. silicon composition as described in claim 1, the chloroplatinic acid isopropanol that the preferred chloroplatinic acid concentration of catalyst I is 1%
Solution, dosage preferably account for the 0.0005%~0.001% of silicon composition gross mass.
9. silicon composition as described in claim 1, the preferred potassium hydroxide-isopropanol solution of catalyst II, dosage are preferred
Account for the 1%~3% of silicon composition gross mass.
10. silicon composition as described in claim 1, the preferred polymethyl siloxane of polysiloxanes in solvent.
11. silicon composition as described in claim 1, solvent usage preferably account for silicon composition gross mass 40%~
50%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111054100A (en) * | 2019-12-03 | 2020-04-24 | 江苏四新科技应用研究所股份有限公司 | Organic silicon composition and preparation method thereof |
| CN113797600A (en) * | 2020-06-16 | 2021-12-17 | 江苏四新科技应用研究所股份有限公司 | Organosilicon defoaming composition and preparation method thereof |
| WO2021254170A1 (en) * | 2020-06-16 | 2021-12-23 | 江苏四新科技应用研究所股份有限公司 | Organic silicon defoaming composition |
| CN114605647A (en) * | 2022-03-10 | 2022-06-10 | 江西蓝星星火有机硅有限公司 | Trapezoidal organic silicon modified polyether compound 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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