CN1044708C - 具有亲水基团的硅烷及其制备方法和应用 - Google Patents
具有亲水基团的硅烷及其制备方法和应用 Download PDFInfo
- Publication number
- CN1044708C CN1044708C CN94107821A CN94107821A CN1044708C CN 1044708 C CN1044708 C CN 1044708C CN 94107821 A CN94107821 A CN 94107821A CN 94107821 A CN94107821 A CN 94107821A CN 1044708 C CN1044708 C CN 1044708C
- Authority
- CN
- China
- Prior art keywords
- group
- general formula
- silane
- value
- hydrogen
- 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.)
- Expired - Fee Related
Links
- 229910000077 silane Inorganic materials 0.000 title claims description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 7
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000013543 active substance Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006884 silylation reaction Methods 0.000 claims 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 15
- 239000003513 alkali Substances 0.000 abstract description 4
- 150000004756 silanes Chemical class 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 23
- -1 siloxanes Chemical class 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 150000001721 carbon Chemical group 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 8
- 229940094989 trimethylsilane Drugs 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YBLFGGYJBKJICD-UHFFFAOYSA-N O=C=[SiH2] Chemical class O=C=[SiH2] YBLFGGYJBKJICD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- FTIUOYWRXKQYNI-UHFFFAOYSA-N 6-trimethylsilylhexan-1-ol Chemical compound C[Si](C)(C)CCCCCCO FTIUOYWRXKQYNI-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical group 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical group 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 241000447011 Mycobacterium phage Muddy Species 0.000 description 1
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 102000005262 Sulfatase Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical group C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-O octylazanium Chemical compound CCCCCCCC[NH3+] IOQPZZOEVPZRBK-UHFFFAOYSA-O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 108060007951 sulfatase Proteins 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/54—Silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
- C07F7/0829—Hydrosilylation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/82—Compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/162—Organic compounds containing Si
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/03—Organic sulfoxy compound containing
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Biological Depolymerization Polymers (AREA)
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyethers (AREA)
Abstract
通式
所示的硅烷,式中,R1、R2、及R3为甲基,R4为具有3至14个碳原子的二价烃基,R5为由通式-O(CH2)b-或-(OCnH2n)c-所示的聚醚基团,其中b的值为1至6,n的平均值为2,c的值为1至10,R6为-OSO3X或-OR7基团,其中X为氢离子,碱金属离子或必要时被取代的铵离子,且R7为具有1至4个碳原子的烷基或乙酰基,a为0或1,条件是,当R6为-OR7时,a为1。该硅烷可生物降解,具有抗水解稳定性,并具有明显的表面活性剂特性。
Description
本发明涉及具有亲水基团的新型的硅烷、其制备方法及其在水基介质中作表面活性剂的应用。本发明尤其涉及具有高度降低水基介质表面张力作用的抗水解稳定性硅烷类表面活性剂。在本发明的情况下,“水基”介质的概念,还须理解成那些主要由水组成的并可另外含有水溶性或可与水混合的有机溶剂的介质。
由现有技术已知,取代基团上具有阴离子型基团、阳离子型基团或两性基团的有机改性硅氧烷,例如聚醚硅氧烷或聚硅氧烷,在结构选择适当和亲水基团与疏水基团比例调节得当的情况下,能够显著降低水溶液的表面张力。
在DE-PS4141046中,记载了具有至少3个硅原子的表面活性剂。这类表面活性剂具有下述通式:
式中,
R1为甲基或苯基,但其中至少90%的R1为甲基,
R2与R1相同或为-(CH2)6-OSO-3·M+,其中M+为碱金属离子,1/2碱土金属离子,或可能被烷基取代的铵离子,
R3与R1或R2相同,但平均每个分子中,至少有一个R2或R3基团为-(CH2)6-OSO- 3·M+基团,a为0至5的数值,以及b为0至5的数值。
选出的含有三个硅原子的三硅氧烷己基硫酸盐在中性水基介质中可将界面张力值极好地降到约21mN/m。但是,它们在酸性或碱性溶液中却不稳定,并且由于Si-O-Si键水解和水解产物重新缩合成较高分子量的齐聚物而很快失去其活性,而且有一部分变得不溶于水基介质。
此外,硅原子含量少的表面活性剂记载于EP-OS0367381(A2)及GB-PS1520421中。
EP-OS0367381(A2)涉及下列通式所示的有机硅化合物,式中R分别独立地代表至多有18个碳原子的烷基、芳基、囟代烷基或囟代芳基,
R’为亚烷基,它们以至多6个碳原子将邻近的硅原子分隔开,
并且R”分别独立地代表R,或在a为零时,R”为R3SiR’,
Z是含有硫、氮或磷的亲水取代基团、羧基官能基团或其盐,并且
a的值为0、1或2。
由此得出,硅有机基团根据定义含有至少两个硅原子。制备这种羰硅烷代价较高,例如采用格里尼雅相似法来制备。而后,例如借助烯丙基缩水甘油醚或烯丙基胺的氢化硅烷化(hydrosilylation)和众所周知的后续反应,来合成具有季磺酸盐结构或季甜菜碱结构的羰硅烷表面活性剂。如此制得的物质,能将1%蒸馏水溶液的表面张力降到23-25mN/m。
在GB-PS1520421中,记载了羰硅烷表面活性剂及其制备。其通式为式中,R为甲基、乙基、丙基或三氟丙基,但至少有50%的R基团为甲基,R’为具有1-6个碳原子的烷基,R”为具有2-6个碳原子的二价脂族烃基,该烃基通过一个至少有2个碳原子的桥键把Q和邻近的硅原子连接在一起,Q在此情况下是-O(C2H4O)cX基团,其中c值为3至12,X为氢,R为
或
其中R为含有1-5个碳原子的烷基,a为1或2,b为2或3。
根据定义,在此情况下至少也必须有两个硅原子。这些化合物在进行应用技术测试时、表明具有明显的起泡沫性能。
同时,本领域专业人员还已知,在这些已知的具有可类比的结构的羰硅烷化合物组中,这些化合物的表面活性特性随硅原子数的降低而变差,尤其是硅原子数从4减到3或2时。Neumann理论中反映了此观察结果(A.W.Neumann,,D.Renzow,Zeitschriftf.Phys.Chem.,新版68,11(1969)),该理论表明,硅氧烷构架的全甲基化表面是水溶液表面张力降到30-40mN/m以下的主要原因。
另外,还可参阅H.Maki等人(YUKAGAGU19,No.4,第51页起,及YUKAGAGU19,No.11第23页起,二者出版年代均为1970年)的日本出版物,在这些出版物中记载了所定义的下式所示化合物:
(CH3)3Si(CH2)3(C2H4O)nH及
((CH2)4)3Si(CH2)3(C2H4O)mH,式中,n=4.0或7.7,m=10或17。但这些化合物在1%(重量)溶液中仅能将界面张力值降到≥26.5mN/m。
在这些日本出版物中,同样还记载了下式所示的季氮化合物:
Bu3M(CH2)3N+(CH3)3Cl-(Bu=丁基,M=Sn,Si),
这些化合物虽然在抑制细菌方面有效,但其表面活性特性却不好。这些季氮化合物中的最佳代表性化合物,在1%水溶液中只能将表面张力值降到32mN/m。
本发明基于下述的惊人的发现:与在Neumann理论中体现出来的一般专业知识等相反,选择出来的硅烷,也即只含唯一的一个硅原子的化合物,当其分子的亲水部分和疏水部分的比例调节得当时,这些化合物能异乎寻常地有效降低水的表面张力,并且与硅氧烷表面活性剂相反,即使在酸性和碱性介质中,经数日和数周仍具有抗水解稳定性。本发明硅烷的另一个而且是非预见的优点是可完全生物降解性,这使它们尤其适用作表面活性剂。这种性质特征从现有技术中是推导不出来的,而且也与迄今习常所持的、有关硅有机化合物为了在含水体系中呈降低界面张力的性质所应满足的结构上要求的看法不一致。
因此,本发明的一个主题是下列通式所示的硅烷式中,R1、R2及R3为甲基,R4为具有3-14个碳原子的二价烃基,R5为由通式-O(CH2)b-所示的基团或由通式-(OCnH2n)c-所示的聚醚基团,其中b的值为1至6,n的平均值为2至,c的值为1至10,R6为-OSO3X基团或-OR7基团,其中X为氢、碱金属或可能被取代的铵离子,R7为具有1-4个碳原子的烷基,或乙酰基,以及a为0或1,
附带条件是,当R6为-OR7基团时a=1。
R4为具有3-14个碳原子的二价烃基,例如-C3H6、-C5H10-、-C6H12-或-C11H22。R4基团可被诸如侧链烷基或囟素所取代。但优选是被直链烃基所取代。
R5为由通式-O(CH2)b-所示的基团,或者为由通式-(OCnH2n)’c-所示的聚醚基团,其中b的值为1至6,n的平均值为2,c的值为1至10。此类基团的例子为-O(CH2)4-、-(OC2H2)c-或(OCH(CH3)CH2)c-。
n的值优选为2.0,以便在此情况下,所有亚氧烷基单位都是亚氧乙基单位。下标c标示出这些单位的数目,其值为1至10,优选为3至6。
R6为-OSO3X基团或-OR7基团,其中X为氢、碱金属或可能被取代的铵离子并且R7为具有1至4个碳原子的烷基或乙酰基。尤其可考虑异丙基铵离子、三乙基铵离子、丁基甲基铵离子或辛基铵离子作为被取代的铵离子。当R7为烷基时,优选的是甲基、乙基或丙基。
a的值为0或1。
附带条件是,当R6为-OR7基团时,a=1,由该附带条件保证了下列类型的本发明硅烷被包括在内:
a)具有一个间隔基团的并在该基团上直接连有一个硫酸根络端基的硅烷,
b)具有一个间隔基团的并在该间隔基团上连有一个(聚)-醚基团、并在该(聚)-醚基团的端部连有一个硫酸根络基团的硅烷;
c)具有一个间隔基团的并在该基团上连有一个其自身端部有一个OR7基团的(聚)-醚基团的硅烷。
例如本发明的硅烷是:(CH3)3Si(CH2)3-O-CH2CH2-OCH3;(CH3)3Si(CH2)6-O-[CH2CH2O-]2C2H5(CH3)3Si(CH2)6-O-[CH2CH2O-]4C2H5(CH3)3Si(CH2)6-O-[CH2CH2O-]6COCH3
ⅰ)在氢甲硅烷基化催化剂存在下,加成通式CH2=CH-R8-OH所示(其中R8为一个具有1-12个碳原子的二价脂族烃基)的化合物,并在必要时,在碱性催化剂或路易斯酸存在下,加成c mol通式所示的烯化氧,或者是
ⅱ)在氢甲硅烷基化催化剂存在下,加成通式CH2=CH-R8-(R5)-aOH所示(其中R5和R8的含义上面已子说明)的化合物,或者是
ⅲ)在氢化硅烷化催化剂存在下,加成通式CH2=CH-R8-(R5)a-OR7所示(其中R5、R7及R8的含义上面已予说明)的化合物,以及
氢甲硅烷基化优选是在升温和/或在溶剂存在下进行,而且将铂催化剂用作催化剂。
在进行工艺方案(ⅰ)时,先将端部具有链烯双键的乙醇加成到SiH-硅烷上。然后,在一种已知的烷氧基化催化剂存在下,将c mol环氧乙烷或环氧乙烷混合物加成到所得氢甲硅烷基化产物的-OH端基上。可优先选用碱性催化剂作为烷氧基化催化剂,例如KOH、NaOH、碱金属醇盐或例如BF3醚化物等路易斯酸。接着采用已知的方法将所制得的(聚)醚单醇硫酸化,并在必要时用碱金属氢氧化物或氢氧化铵中和。此时,氢氧化铵的氮原子上氢可被烃基取代。反应过程中生成的铵盐还可以与烷基胺,经复分解反应发生氨解,很容易地转化成相应的烷基铵盐。由于使用了相应的烷基胺,因而可以使所得的硫酸酯盐的特性得以改善,这尤其改善了其润湿特性和起泡沫性能。
本领域专业人员已知,水溶液中的临界胶束形成浓度[cmc]是表征化合物表面活性性能的重要量值,该量值取决于抗衡离子对表面活性基团的键合度。所以当抗衡离子对表面活性基团的键合度增大时,表面活性剂的临界胶束形成浓度就会减小。而键合度取决于抗衡离子的极化度、价数和水合物壳层(hydrathiille)。因此,化合物的表面活性剂特有性质,例如起泡沫性与润湿性、可溶性与表面张力降低性,不仅受表面活性基团影响,而且也受抗衡离子影响。据此,由于有许多可供使用的有机铵阳离子和各种技术上非常简单、可将所要求保护的化合物转化成相应烷基铵衍生物的方法,当然还可以制得许多具有应用价值的化合物,这一点也是显而易见的。
在第二种工艺方案(ⅱ)中,将己烷氧基化的、其端部具有双键的醇加成到氢硅烷上,然后如上所述,使之硫酸盐化并中和。
在第三种工艺方案(ⅲ)中,将烯不饱和化合物CH2=CH-R8-(R5)a-OR7加成到氢硅烷上。即使-OR7端基能发生反应,反应产物大多仍以如此制得的形式予以使用。
为使本发明化合物的界面活化性质达到最佳程度,必须使其亲水基团和疏水基团比例得当。疏水性质可通过R1、R2、R3、R7各基团加以影响。这些基团中碳越多,本发明硅烷就越疏水。亲水性特别由基团R5和阴离子硫酸根所决定。n值在给定范围内越小、c的数值越大,则该硅烷型表面活性剂越亲水。为使专业人员易于理解,将在实施例中对表面活性剂特性的这种影响做进一步阐述。因此,要获得必要的特性时,不需要额外进行任何发明活动只需进行一些预期的初步试验。
本发明的另一个主题是本发明硅烷在水基介质中作表面活性剂的应用。通过添加1%(重量)本发明化合物完全可以使水溶液的表面张力降到大约21mN/m或21mN/m以下。同时,本发明化合物的可生物降解性有着特别的重要作用。此外,硅烷表面活性剂还具有抗水解稳定性。
本发明硅烷表面活性剂的重要用途如下:
用作润湿剂:
在处理植物用的配制品(农艺药剂)中;用于改善低能量基体如聚乙烯表面、聚丙烯表面的润湿性;供制漆工业之用;在制造感光胶片时;在电镀工艺中;
用作分散剂:
供分散染料、颜料及填料之间;
用作乳化剂或纺织工业中制备纺织助剂、油剂、滑润剂、抗静电配制品用的添加剂;用作染色助剂;
用作一般表面活性剂:
用于灭火剂;用作泡沫稳定剂;用作快印油墨、粘合剂、分散粘合剂、热熔性粘合剂的界面活性添加剂;用于洗涤剂;用作工业洗涤剂的添加剂;
用作护肤品、洗发液、浴液等化妆品的原料;
在工业应用和家务应用中:
用作防霉剂;用于餐具洗洁剂、洗涤剂、厕所清洁剂、自增光乳剂。
本发明化合物的制备及其性质将在下列实施例中予以详述。实施例1
a)[6-羟基己基]三甲基硅烷(非本发明的中间产物)的制备
在300ml实验用高压釜(autoclave)中称入28.7g1-己烯-5-醇(0.287mol)和3mg铂催化剂。此后,将高压釜连同内容物在氩保护气体蒸发条件下,置于丙酮/干冰浴中,使之冷却,并将22.4g冷凝态三甲基硅烷(0.299mol,沸点6.7℃)虹吸至高压釜中。将高压釜关闭,并加热至130℃。此时,内压上升至13.7巴,然后又降至约5.7巴,这标志着反应已开始。
然后冷却至室温,使高压釜释压,释压后从内容物(称量:50.7g,质量损耗:0.9g)中滤除铂催化剂。
羟基数量:理论值321.7实测值306经29Si-NMR谱和1H-NMR谱分析,得出下列产物结构:
(CH3)3Si(CH2)6OH
在20℃油泵真空条件下去除该产物中的低挥发性组分。
b)[羟己基]三甲基硅硅烷乙氧基化制备[聚氧亚乙基]三甲基硅烷(非本发明的中间产物)
在一个装设有强力冷却器、温度计、冷却套滴液漏斗及氮气连接管的三颈烧瓶中,装入20.0g(0.11mol)[羟己基]三甲基硅烷和0.82g 50%的三氟化硼-醚合物溶液。然后,缓慢滴入21.1g(0.48mol)冷凝环氧乙烷。为使内部温度不超过20-30℃,用冰浴来冷却放热反应。而后,在室温下搅拌2小时,在用1.50g碳酸氢钠和0.41g水(1%(重量))中和后,在90℃喷水空气泵真空条件下将挥发性组分从产物中分离掉。接着在预加助滤剂条件下进行过滤,得淡黄色透明产物,该产物经H1-NMR谱及凝胶渗透色谱分析,具有4.2个氧亚乙基单元,据此可用下列平均式来表达:
(CH3)Si-(CH2)6-O-[CH2CH2O]4.2-H
在设有回流冷却器和内置式温度计的三颈烧瓶中,将31.45g(0.087mol)产物1b)连同14g(0.3mol)乙酐、1.9g乙酸钠和100ml甲苯一起加入,并回流加热2小时。
蒸除溶剂后,酸值为9.7。为中和所得产物起见,将碳酸氢钠悬浮于一些水中,并添加到初产物中。
而后,在约90℃喷水空气泵真空条件下除去挥发性组分,并滤出所沉淀的盐。
将该产物以1%(重量)或0.1%(重量)的浓度,溶于蒸馏水中。经放置24小时后,在聚丙烯薄膜上试验此等溶液的铺展性(50μl液滴)。
表1
浓度[%(重量)] | 聚丙烯膜上铺展程度[mm] |
1.00.1 | 2010 |
c2)通式(CH3)3Si-(CH2)6-O-[CH2CH2O]4.2-CH3所示的本发明产物的制备。
在装有回流冷凝器,蒸馏桥及内置式温度计三颈烧瓶中加入37.5g(0.1mol)产物1b),并在115℃下慢慢掺加27g甲醇钠溶液(0.15mol;30%甲醇溶液)。同时,通过建立微弱的真空将不断产生的甲醇蒸馏掉。
掺加完毕后,先在喷水真空条件下,然后在油泵真空条件五除去残留的甲醇。接着,在该装置内通以氮气,并在强力搅拌下将二氯乙烷以剧烈物流传输过该装置。采用冰浴冷却方式使内部温度不超过120℃。一旦发觉放热减弱时,可借助外部加热法,使温度保持在115-120℃。
经碱值测定,断定反应物中几乎不再有碱后,可停止二氯乙烷的引入。在将反应混合物冷却到60℃后,添加2ml水,并用30%磷酸水溶液中和。在60℃旋转式蒸发器中和喷水空气泵真空条件下,除去初产物中的挥发性组分,并在添加助滤剂后进行过滤。得一种淡黄色的透明产物它溶于水时复混浊。该产物的水溶液的表面活性剂性质与浓度的关系如下:
表2
实施例2
浓度[%(重量)] | 在聚丙烯膜上铺展[mm] |
1.00.1 | 5030 |
a)用氢甲硅烷基化法制备通式(CH3)3Si(CH2)6[OCH2CH2]4OH所示聚亚氧烷基三甲基硅烷(非本发明的中间产物)。
在300ml实验室用高压釜中,称入88.14g己烯基聚醚(0.3mol,羟基数为203.4,碘值为86.4)及5mg铂催化剂。尔后,将高压釜连同内容物一起,在氩保护气蒸发条件下,在丙酮/干冰浴中冷却,并将23.34g三甲基硅烷(0.315mol)虹吸到其中。关闭高压釜,并加热到130℃。这时,内压升至8.0巴,然后又降至约3.5巴。
高压釜冷却至室温后,使之释压,然后用过滤法从内容物中将铂催化剂滤除(称量:109.0g质量损失:0.6g)。
羟基数:理论152.5 实测158.0
所得产物为透明的,稍具有粘性;当其溶于蒸馏水,浓度为1%时呈混浊状。
b)酰氨基硫酸硫酸盐化制备[异丙基铵-6-硫酸根合己基]碱甲基硅烷(本发明的)
在设有搅拌器、回流冷凝器、温度计和滴液漏斗的100ml四颈烧瓶中,将18.33g[羟己基]三甲基硅烷(0.1mol,实施例1的产物)、10.19g用研钵新研碎的酰氨基硫酸(0.105mol)和9.6g二甲基甲酰胺在氮气蒸发条件下加以混合,并持续加热4小时,使内部温度达85℃。而后,在室温下向反应混合物中添加7.09g异丙胺(0.12mol),并对该混合物加热,使氨气体挥发掉。以此,同时也中和掉存在于产物中的残留酸。尔后,进行过滤,并在85℃油泵真空条件下使产物从N,N-二甲基甲酰胺与过量的异丙胺中分离出来。
所得产物为淡黄色、透明、稍具有粘性,溶于水时清彻不混浊,摇振时大量起泡。溶于蒸馏水的1%溶液具有21.0mN/m的表面张力,在聚丙烯板上产生55mm的铺展。用1H-NMR谱和13C-NMR谱进行的分析试验证实,反应产物具有所预想的结构:表3水溶液浓度与表面张力降低的关系
实施例3
浓度[%(重量)] | 表面张力[mN/m],25℃时 |
1.00.40.30.150.090.07 | 20.921.022.525.127.327.9 |
本发明其它化合物制备及其表面活性剂性质的测定。
如上述实施例所示,用铂作催化剂,在三甲基硅烷上加成烯丙基醇、3-丁烯-1-醇、+-烯-1-醇及带链烯官能团的醚或聚醚,以此制备带羟烷基官能团的三甲基硅烷衍生物,作为其它的原始化合物。此后,将这些化合物用氨基磺酸进行硫酸盐化,并转化成相应的铵盐。
首先配制产物浓度为1%(重量)的各种水溶液,以Du-Nouy法测定其表面张力。测量1%表面活性剂溶液的50μl液滴在聚丙烯薄膜上扩展的最大面积扩展,以测定润湿性。在此条件下,纯水的空白值为8mm。同样,采用观测1%溶液的润湿性的方法也可以跟踪观测其抗水解的长期稳定性。
表4
表中:TMS-PE-SO4 *=TMS-C6-O-[C2H4O]4SO- 3X+TMS-PE-SO4 **=TMS-C3-O-[C2H4O]2SO- 3X+TMS-EO-SO4=TMS-C3-O-CH2CH2OSO- 3X+TMS=三甲基甲硅烷基PE=聚醚基X+=异丙基铵离子
产物 | 溶液 | 表面张力[mN/m] | 铺展[mm],在聚丙烯膜上 |
TMS-C3-SO4TMS-C4-SO4TMS-C6-SO4TMS-C11-SO4TMS-PE-SO4 *TMS-PE-SO** 4TMS-EO-SO4 | 混浊混浊清澈混浊清澈清澈清澈 | 28.426.521.024.232.725.024.7 | 88551581517 |
这些化合物具有明显的表面活性剂特性。硫酸酯[异丙基铵-6-硫酸根络己基]三甲基硅烷的表面活性剂特性最佳。从中可以看出,相同的R1、R2及R3的表面活性剂特性因间隔基团R4的长度而异。因具有3至11个碳原子的同系物系列中,在间隔基具有约6个碳原子时表面活性剂特性最佳。实施例4
以实施例2中所述的相似方式和方法,可借助各种各样的有机胺碱,在释出氨的条件下,将三甲基甲硅烷基己基硫酸酯-铵盐转化成相应的烷基铵盐。通过此致性步骤可制得如下表所示的具有各种降低表面张力、润湿性能及起泡沫性质等特性的产物。
检验本发明物质pH4、pH7及pH12时的抗水解稳定性。
以硫酸酯为例,经试验表明[异丙基铵-6-硫酸根络己基]三甲基硅烷的1%(重量)水溶液的润湿性能与放置时间有关。
表6
室温下放置时间[天] | 在下列pH时的铺展[mm]pH4 pH7 pH12 | 溶液外观 | ||
0123478910707480 | 555055555055555050556065 | 555555555555455050555560 | 454045504545454545505560 | 清澈清澈清澈清澈清澈清澈清澈清澈清澈清澈清澈清澈 |
试验表明,无论在中性pH范围内,还是在碱性和酸性pH范围内,抗水解稳定性均优异。对比例
表7对比试验
室温下放置时间[天] | 不同pH时的铺展[mm]pH4 pH7 pH12 | 溶液外观 | ||
012347>14 | 48n.m.n.m.n.m.n.m.n.m.n.m. | 303840404030n.m. | 35201010n.m.n.m.n.m. | 混浊混浊混浊混浊混浊混浊混浊 |
n.m表示,铺展无法观察到,因而不能测量。
Claims (10)
1、下列通式所示的硅烷,式中,
R1、R2及R3为甲基,
R4为具有3至14个碳原子的二价烃基,
R5为由通式-O(CH2)b-所代表的基团,或由通式-(OCnH2n)c-所代表的聚醚基团,式中b的值为1至6,n的平均值为2,c的值为1至10,
R6为-OSO3X或-OR7基团,式中X为氢离子,碱金属离子或可能被取代的铵离子,且R7为具有1至4个碳原子的烷基或一个乙酰基,
a为0或1,条件是,当R6为-OR7基团时,a为1。
2、据权利要求1所述的硅烷,其特征在于,基团R4为具有3至14个碳原子的二价脂族烃基。
3、据权利要求2所述的硅烷,其特征在于,基团R4为具有3至9个碳原子的二价脂族烃基。
4、据权利要求3所述的硅烷,其特征在于,基团R4为具有3至6个碳原子的二价脂族烃基。
5、据权利要求1-4中任何一项所述的硅烷,其特征在于,R5基团为聚醚基团,其中n的值为2,c的值为3至6。
6、据权利要求1所述的硅烷,其特征在于,X为烷基铵基团,其烷基具有1至10个碳原子。
7、制备权利要求1至6所述的硅烷的方法,其特征在于,
(ⅰ)在氢甲硅烷基化催化剂存在下,加成通式CH2=CH-R8-OH所示的化合物,其中R8为一个具有1至12个碳原子的二价脂族烃基,并在必要时,在碱性催化剂或路易斯酸存在下,加成cmol通式所示的环氧烷,或者是,
(ⅱ)在氢甲硅烷基化催化剂存在下,加成通式CH2=CH-R8-(R5)a-OH所示的化合物,其中R5和R8含义如上所述,或者是
(ⅲ)在氢甲硅烷基化催化剂存在下,加成通式CH2=CH-R8-(R5)a-OR7所示的化合物,其中R5、R7及R8含义如上所述,以及
8、根据权利要求7所述的方法,其特征在于,氢甲硅烷基化反应在加高的温度下及/或在溶剂存在下进行。
9、根据权利要求7或8所述的方法,其特征在于,氢甲硅烷基化反应在铂催化剂存在下进行。
10、权利要求1至6所述的硅烷在含水介质中作可生物降解、抗水解稳定性表面活性剂的应用。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4320920.3 | 1993-06-24 | ||
DE4320920A DE4320920C1 (de) | 1993-06-24 | 1993-06-24 | Silane mit hydrophilen Gruppen, deren Herstellung und Verwendung als Tenside in wäßrigen Medien |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1107477A CN1107477A (zh) | 1995-08-30 |
CN1044708C true CN1044708C (zh) | 1999-08-18 |
Family
ID=6491067
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94107819A Expired - Fee Related CN1046527C (zh) | 1993-06-24 | 1994-06-24 | 具有亲水基团的硅烷及基制备方法和应用 |
CN94107821A Expired - Fee Related CN1044708C (zh) | 1993-06-24 | 1994-06-24 | 具有亲水基团的硅烷及其制备方法和应用 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94107819A Expired - Fee Related CN1046527C (zh) | 1993-06-24 | 1994-06-24 | 具有亲水基团的硅烷及基制备方法和应用 |
Country Status (12)
Country | Link |
---|---|
US (2) | US5430167A (zh) |
EP (2) | EP0630902B1 (zh) |
JP (2) | JP2749520B2 (zh) |
CN (2) | CN1046527C (zh) |
AU (2) | AU668041B2 (zh) |
BR (2) | BR9402516A (zh) |
CA (2) | CA2124877C (zh) |
DE (3) | DE4320920C1 (zh) |
DK (2) | DK0630902T3 (zh) |
ES (2) | ES2128461T3 (zh) |
MX (2) | MX9404816A (zh) |
NZ (2) | NZ260771A (zh) |
Families Citing this family (81)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4330059C1 (de) * | 1993-09-06 | 1994-10-20 | Goldschmidt Ag Th | Silane mit hydrophilen Gruppen, deren Herstellung und Verwendung als Tenside in wäßrigen Medien |
US5496830A (en) * | 1994-09-14 | 1996-03-05 | Johns Hopkins University | Inhibition of hemoflagellates by camptothecin compounds |
DE4433139A1 (de) * | 1994-09-16 | 1996-03-21 | Thera Ges Fuer Patente | Hydrophilierte Zahnabdruckmassen |
DE4439598A1 (de) | 1994-11-05 | 1996-05-09 | Goldschmidt Ag Th | Tensidgemische aus Silantensiden und Polyalkylenoxiden und deren Verwendung |
GB2331457B (en) * | 1997-11-12 | 2001-07-04 | Graviner Ltd Kidde | Fire or explosion suppressants and methods |
CN1065762C (zh) * | 1998-05-15 | 2001-05-16 | 常子元 | 调胰降糖胶囊 |
US6489366B1 (en) | 1998-12-23 | 2002-12-03 | G. D. Searle, Llc | Combinations of cholesteryl ester transfer protein inhibitors and nicotinic acid derivatives for cardiovascular indications |
KR100377405B1 (ko) * | 2000-08-31 | 2003-03-26 | 주식회사피죤 | 김 서림 방지용 코팅 조성물 및 이로부터 얻어지는 코팅제품 |
JP4906203B2 (ja) * | 2001-09-20 | 2012-03-28 | 東レ・ダウコーニング株式会社 | 高純度ポリオキシアルキレン変性ポリシロキサン及びその製造法 |
US6900257B2 (en) * | 2002-08-06 | 2005-05-31 | General Electric Company | Antistatic agents and polymer compositions derived therefrom |
US6841598B2 (en) * | 2002-08-16 | 2005-01-11 | General Electric Company | Antistatic and antidust agents, compositions thereof, and methods of manufacture |
US7405002B2 (en) * | 2004-08-04 | 2008-07-29 | Agency For Science, Technology And Research | Coated water-soluble nanoparticles comprising semiconductor core and silica coating |
US7534489B2 (en) * | 2004-09-24 | 2009-05-19 | Agency For Science, Technology And Research | Coated composites of magnetic material and quantum dots |
US7645720B2 (en) | 2005-12-13 | 2010-01-12 | Momentive Performance Materials Inc. | Extreme environment surfactant compositions comprising hydrolysis resistant organomodified disiloxane surfactants |
US7507775B2 (en) * | 2005-10-13 | 2009-03-24 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified disiloxane surfactants |
US20070131610A1 (en) * | 2005-12-13 | 2007-06-14 | General Electric Company | Membrane-based apparatus and associated method |
US20070131611A1 (en) * | 2005-12-13 | 2007-06-14 | General Electric Company | Membrane-based article and associated method |
US7601680B2 (en) * | 2005-12-13 | 2009-10-13 | Momentive Performance Materials | Gemini silicone surfactant compositions and associated methods |
US20070134283A1 (en) * | 2005-12-13 | 2007-06-14 | General Electric Company | Surfactant-based composition and associated methods |
US7935842B2 (en) * | 2006-02-09 | 2011-05-03 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified trisiloxane surfactants |
US20070197394A1 (en) * | 2006-02-17 | 2007-08-23 | General Electric Company | Hydrolysis resistant organomodified trisiloxane surfactants |
US20070249560A1 (en) * | 2006-04-21 | 2007-10-25 | Leatherman Mark D | Hydrolysis resistant organomodified silyated surfactants |
US7700797B2 (en) * | 2006-05-22 | 2010-04-20 | Momentive Performance Materials Inc. | Use of hydrolysis resistant organomodified silylated surfactants |
US7259220B1 (en) | 2006-07-13 | 2007-08-21 | General Electric Company | Selective hydrosilylation method |
US7678859B2 (en) * | 2006-09-14 | 2010-03-16 | 3M Innovative Properties Company | Preparation and stabilization of fluoropolymer dispersions |
US7399350B2 (en) * | 2006-10-17 | 2008-07-15 | Momentive Performance Materials Inc. | Fluorine-free disiloxane surfactant compositions for use in coatings and printing ink compositions |
US7964032B2 (en) * | 2006-10-17 | 2011-06-21 | Momentive Performance Materials Inc. | Fluorine-free trisiloxane surfactant compositions for use in coatings and printing ink compositions |
US20080167269A1 (en) * | 2006-12-11 | 2008-07-10 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified silylated ionic surfactants |
CN101636079B (zh) * | 2006-12-11 | 2014-04-09 | 莫门蒂夫性能材料股份有限公司 | 抗水解的有机改性硅烷化离子表面活性剂 |
CN101003008B (zh) * | 2006-12-29 | 2010-12-08 | 南京四新科技应用研究所有限公司 | 一种提高乳液稳定性的方法 |
CN101186702B (zh) * | 2007-11-16 | 2011-04-20 | 北京化工大学 | 多乙烯多醇有机硅水溶性聚合物及其制备方法 |
DE102007055484A1 (de) | 2007-11-21 | 2009-05-28 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung von Polydimethylsiloxanen an sulfonsauren Kationenaustauscherharzen |
DE102007055485A1 (de) * | 2007-11-21 | 2009-06-04 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung verzweigter SiH-funktioneller Polysiloxane und deren Verwendung zur Herstellung SiC- und SiOC-verknüpfter, verzweigter organomodifizierter Polysiloxane |
CN101205299B (zh) * | 2007-11-30 | 2011-04-20 | 北京化工大学 | 多乙烯多醇有机硅阳离子聚合物及其制备方法 |
DE102008002713A1 (de) * | 2008-06-27 | 2009-12-31 | Evonik Goldschmidt Gmbh | Neue Polyethersiloxane enthaltende Alkoxylierungsprodukte durch direkte Alkoxylierung organomodifizierter alpha, omega-Dihydroxysiloxane an Doppelmetallcyanid (DMC)-Katalysatoren, sowie Verfahren zu deren Herstellung |
DE102008041601A1 (de) * | 2008-08-27 | 2010-03-04 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung verzweigter SiH-funtioneller Polysiloxane und deren Verwendung zur Herstellung flüssiger, SiC- oder SiOC-verknüpfter, verzweigter organomodifizierter Polysiloxane |
DE102008043218A1 (de) * | 2008-09-24 | 2010-04-01 | Evonik Goldschmidt Gmbh | Polymere Werkstoffe sowie daraus bestehende Kleber- und Beschichtungsmittel auf Basis multialkoxysilylfunktioneller Präpolymerer |
DE102008043245A1 (de) * | 2008-10-29 | 2010-05-06 | Evonik Goldschmidt Gmbh | Siliconpolyether-Copolymersysteme sowie Verfahren zu deren Herstellung durch Alkoxylierungsreaktion |
DE102009022628A1 (de) * | 2008-12-05 | 2010-06-10 | Evonik Goldschmidt Gmbh | Verfahren zur Modifizierung von Oberflächen |
EP2389417B1 (en) | 2009-01-20 | 2017-03-15 | Cabot Corporation | Compositons comprising silane modified metal oxides |
CN102405265B (zh) * | 2009-02-25 | 2016-06-15 | 莫门蒂夫性能材料股份有限公司 | 包含甲硅烷基化聚醚表面活性剂的涂料和印刷油墨组合物以及由其制得的制品 |
DE102009003274A1 (de) * | 2009-05-20 | 2010-11-25 | Evonik Goldschmidt Gmbh | Zusammensetzungen enthaltend Polyether-Polysiloxan-Copolymere |
DE102009022630A1 (de) | 2009-05-25 | 2010-12-02 | Evonik Goldschmidt Gmbh | Emulsionen auf Basis Silylgruppen tragender Hydroxylverbindungen |
DE102009022631A1 (de) | 2009-05-25 | 2010-12-16 | Evonik Goldschmidt Gmbh | Härtbare Silylgruppen enthaltende Zusammensetzungen und deren Verwendung |
DE102009034607A1 (de) * | 2009-07-24 | 2011-01-27 | Evonik Goldschmidt Gmbh | Neuartige Siliconpolyethercopolymere und Verfahren zu deren Herstellung |
DE102009028636A1 (de) * | 2009-08-19 | 2011-02-24 | Evonik Goldschmidt Gmbh | Neuartige Urethangruppen enthaltende silylierte Präpolymere und Verfahren zu deren Herstellung |
DE102010001350A1 (de) | 2010-01-29 | 2011-08-04 | Evonik Goldschmidt GmbH, 45127 | Neuartige lineare Polydimethylsiloxan-Polyether-Copolymere mit Amino- und/oder quaternären Ammoniumgruppen und deren Verwendung |
DE102010001531A1 (de) | 2010-02-03 | 2011-08-04 | Evonik Goldschmidt GmbH, 45127 | Neuartige organomodifizierte Siloxane mit primären Aminofunktionen, neuartige organomodifizierte Siloxane mit quaternären Ammoniumfunktionen und das Verfahren zu deren Herstellung |
DE102010002178A1 (de) * | 2010-02-22 | 2011-08-25 | Evonik Goldschmidt GmbH, 45127 | Verfahren zur Herstellung von Amin-Amid-funktionellen Siloxanen |
DE102010002180A1 (de) * | 2010-02-22 | 2011-08-25 | Evonik Goldschmidt GmbH, 45127 | Stickstoffhaltige silizium-organische Pfropfmischpolymere |
US8318037B2 (en) * | 2010-04-30 | 2012-11-27 | Wisconsin Alumni Research Foundation | Organosilicon glycol-based electrolytes with a hydroxy terminus |
DE102010062156A1 (de) | 2010-10-25 | 2012-04-26 | Evonik Goldschmidt Gmbh | Polysiloxane mit stickstoffhaltigen Gruppen |
TWI479956B (zh) * | 2010-12-09 | 2015-04-01 | Hon Hai Prec Ind Co Ltd | 具有高速差分訊號佈線結構的印刷電路板 |
DE102011076019A1 (de) | 2011-05-18 | 2012-11-22 | Evonik Goldschmidt Gmbh | Alkoxylierungsprodukte und Verfahren zu ihrer Herstellung mittels DMC-Katalysatoren |
DE102011088787A1 (de) | 2011-12-16 | 2013-06-20 | Evonik Industries Ag | Siloxannitrone und deren Anwendung |
DE102012202521A1 (de) | 2012-02-20 | 2013-08-22 | Evonik Goldschmidt Gmbh | Verzweigte Polysiloxane und deren Verwendung |
DE102013102239A1 (de) * | 2013-03-06 | 2014-09-11 | Universität Zu Köln | Carbosilanhaltiger Feuerlöschschaum |
JP6440688B2 (ja) * | 2013-05-08 | 2018-12-19 | ダウ シリコーンズ コーポレーション | 親水性オルガノシラン |
DE102013214081A1 (de) | 2013-07-18 | 2015-01-22 | Evonik Industries Ag | Neue aminosäuremodifizierte Siloxane, Verfahren zu ihrer Herstellung und Anwendung |
DE102014209408A1 (de) | 2014-05-19 | 2015-11-19 | Evonik Degussa Gmbh | Ethoxylatherstellung unter Verwendung hoch aktiver Doppelmetallcyanid-Katalysatoren |
US10913921B2 (en) * | 2014-06-18 | 2021-02-09 | HEX Performance, LLC | Performance gear, textile technology, and cleaning and protecting systems and methods |
EP3020749B1 (de) | 2014-11-12 | 2020-09-30 | Evonik Operations GmbH | Verfahren zur herstellung von platin enthaltenden zusammensetzungen |
US10899937B2 (en) * | 2014-12-22 | 2021-01-26 | U.S.A. As Represented By The Administrator Of The National Aeronautics And Space Administration | Hydrogen-bonding surfaces for ice mitigation |
PL3168273T3 (pl) | 2015-11-11 | 2018-10-31 | Evonik Degussa Gmbh | Polimery utwardzalne |
JP6909232B2 (ja) | 2016-03-31 | 2021-07-28 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッドMomentive Performance Materials Inc. | 有機ケイ素湿潤剤を含有するレシチン系スプレーアジュバント |
JP6651968B2 (ja) * | 2016-04-21 | 2020-02-19 | 日清紡ホールディングス株式会社 | ケイ素含有硫酸エステル塩 |
PL3321304T3 (pl) | 2016-11-15 | 2019-11-29 | Evonik Degussa Gmbh | Mieszaniny cyklicznych, rozgałęzionych siloksanów typu D/T i ich dalszych produktów |
CN108164693B (zh) * | 2016-12-07 | 2019-11-29 | 上海东大化学有限公司 | 一种硅改性聚醚及其制备方法、应用 |
CN106750327B (zh) * | 2016-12-29 | 2019-10-11 | 中国石油天然气股份有限公司 | 一种改性聚醚及其制备方法和应用 |
EP3415548B1 (de) | 2017-06-13 | 2020-03-25 | Evonik Operations GmbH | Verfahren zur herstellung sic-verknüpfter polyethersiloxane |
EP3415547B1 (de) | 2017-06-13 | 2020-03-25 | Evonik Operations GmbH | Verfahren zur herstellung sic-verknüpfter polyethersiloxane |
EP3438158B1 (de) | 2017-08-01 | 2020-11-25 | Evonik Operations GmbH | Herstellung von sioc-verknüpften polyethersiloxanen |
US10233200B2 (en) | 2017-08-21 | 2019-03-19 | Momentive Performance Matericals Inc. | Organomodified monosilyl compound, its preparation and applications thereof |
US10918109B2 (en) | 2017-09-25 | 2021-02-16 | Momentive Performance Materials Inc. | Lecithin-based spray adjuvant containing organosilicon wetting agents |
EP3467006B1 (de) | 2017-10-09 | 2022-11-30 | Evonik Operations GmbH | Mischungen zyklischer-verzweigter siloxane vom d/t-typ und deren folgeprodukte |
US10428229B2 (en) | 2017-12-28 | 2019-10-01 | Industrial Technology Research Institute | Aqueous coating material and method for manufacturing the same |
EP3611214A1 (de) | 2018-08-15 | 2020-02-19 | Evonik Operations GmbH | Sioc-verknüpfte, lineare polydimethylsiloxan-polyoxyalkylen-blockcopolymere |
EP3611215A1 (de) | 2018-08-15 | 2020-02-19 | Evonik Operations GmbH | Verfahren zur herstellung acetoxygruppen-tragender siloxane |
EP3663346B1 (de) | 2018-12-04 | 2023-11-15 | Evonik Operations GmbH | Reaktivsiloxane |
CN110003477B (zh) * | 2019-05-20 | 2021-09-14 | 胡海明 | 一种聚二甲基硅烷安全生产设备 |
EP3885096B1 (de) | 2020-03-27 | 2024-02-14 | Evonik Operations GmbH | Stoffliche wiederverwertung silikonisierter flächengebilde |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2039512A (en) * | 1978-12-05 | 1980-08-13 | Oreal | Surface-active polysiloxanes |
US4847397A (en) * | 1987-05-26 | 1989-07-11 | Dow Corning Kabushiki Kaisha | Method for the production of silyl group containing amine compounds |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2872434A (en) * | 1959-02-03 | mezsio | ||
US2582568A (en) * | 1947-08-26 | 1952-01-15 | Dow Corning | Silicon-containing esters |
US2640064A (en) * | 1950-06-08 | 1953-05-26 | Dow Corning | Bromoalkylsilanes and their preparation |
US2629727A (en) * | 1950-07-26 | 1953-02-24 | Dow Corning | Organosilyl alcohols |
US2983745A (en) * | 1956-07-18 | 1961-05-09 | Dow Corning | Silpropoxanes |
US2924588A (en) * | 1957-04-22 | 1960-02-09 | Dow Corning | Organosiloxane alcohols |
US3109012A (en) * | 1959-06-12 | 1963-10-29 | Goldschmidt Ag Th | Method of producing organo-silicon compounds and products therefrom |
US3161611A (en) * | 1960-07-06 | 1964-12-15 | Goldschmidt Ag Th | Aqueous solutions of hydroxypropyl silanols and their preparation |
US3159496A (en) * | 1960-08-29 | 1964-12-01 | Goldschmidt Ag Th | Process for the preparation of aqueous solutions of organosilicon compounds |
US3141898A (en) * | 1961-01-03 | 1964-07-21 | Minnesota Mining & Mfg | 2, 2-dimethyl-2-silaalkane-sulfonic acids and their salts |
BE754332A (fr) * | 1969-08-05 | 1971-02-03 | Dow Corning | Copolymeres de siloxanes a fonctionnalite carboxyle utiles comme agent d'encollage et papier encolle a l'aide de ces copolymeres |
GB1520421A (en) * | 1975-10-09 | 1978-08-09 | Dow Corning Ltd | Organosilicon compounds |
US4235638A (en) * | 1978-04-11 | 1980-11-25 | Minnesota Mining And Manufacturing Company | Sulfonato-organosilanol compounds and aqueous solutions |
US4152165A (en) * | 1978-04-11 | 1979-05-01 | Minnesota Mining And Manufacturing Company | One-part hydrophilic treatment compositions |
JPS6170551A (ja) * | 1984-09-14 | 1986-04-11 | Hitachi Ltd | レジスト現像液 |
GB8708552D0 (en) * | 1987-04-09 | 1987-05-13 | Dow Corning Ltd | Surface active silicone compound |
GB8819567D0 (en) * | 1988-08-17 | 1988-09-21 | Dow Corning Ltd | Carbosilane surfactants |
DE69015417T2 (de) * | 1989-04-25 | 1995-06-29 | Shinetsu Chemical Co | Fluorhaltiges Detergens und Verfahren zu seiner Herstellung. |
US5159095A (en) * | 1991-06-07 | 1992-10-27 | Abbott Laboratories | Substituted silyl alcohols |
US5113005A (en) * | 1991-06-07 | 1992-05-12 | Abbott Laboratories | Process for synthesis of silyl alcohols |
JPH0625615A (ja) * | 1992-04-07 | 1994-02-01 | Shin Etsu Chem Co Ltd | プライマー組成物 |
CA2129773C (en) * | 1993-09-02 | 2007-05-01 | Michael Klaus | Aromatic carboxylic acid derivatives |
-
1993
- 1993-06-24 DE DE4320920A patent/DE4320920C1/de not_active Expired - Fee Related
-
1994
- 1994-06-01 CA CA002124877A patent/CA2124877C/en not_active Expired - Fee Related
- 1994-06-01 CA CA002124876A patent/CA2124876C/en not_active Expired - Fee Related
- 1994-06-15 AU AU64752/94A patent/AU668041B2/en not_active Ceased
- 1994-06-15 DE DE59407623T patent/DE59407623D1/de not_active Expired - Fee Related
- 1994-06-15 DK DK94109144T patent/DK0630902T3/da active
- 1994-06-15 NZ NZ260771A patent/NZ260771A/en unknown
- 1994-06-15 EP EP94109144A patent/EP0630902B1/de not_active Expired - Lifetime
- 1994-06-15 ES ES94109144T patent/ES2128461T3/es not_active Expired - Lifetime
- 1994-06-15 NZ NZ260770A patent/NZ260770A/en unknown
- 1994-06-15 AU AU64753/94A patent/AU667436B2/en not_active Ceased
- 1994-06-15 EP EP94109141A patent/EP0630901B1/de not_active Expired - Lifetime
- 1994-06-15 DE DE59407622T patent/DE59407622D1/de not_active Expired - Fee Related
- 1994-06-15 ES ES94109141T patent/ES2128460T3/es not_active Expired - Lifetime
- 1994-06-15 DK DK94109141T patent/DK0630901T3/da active
- 1994-06-20 JP JP6137398A patent/JP2749520B2/ja not_active Expired - Fee Related
- 1994-06-23 BR BR9402516A patent/BR9402516A/pt not_active IP Right Cessation
- 1994-06-23 JP JP6141904A patent/JPH0733782A/ja active Pending
- 1994-06-23 BR BR9402517A patent/BR9402517A/pt not_active IP Right Cessation
- 1994-06-24 US US08/265,075 patent/US5430167A/en not_active Expired - Fee Related
- 1994-06-24 US US08/265,078 patent/US5430166A/en not_active Expired - Fee Related
- 1994-06-24 CN CN94107819A patent/CN1046527C/zh not_active Expired - Fee Related
- 1994-06-24 CN CN94107821A patent/CN1044708C/zh not_active Expired - Fee Related
- 1994-06-24 MX MX9404816A patent/MX9404816A/es not_active IP Right Cessation
- 1994-06-24 MX MX9404815A patent/MX9404815A/es not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2039512A (en) * | 1978-12-05 | 1980-08-13 | Oreal | Surface-active polysiloxanes |
US4847397A (en) * | 1987-05-26 | 1989-07-11 | Dow Corning Kabushiki Kaisha | Method for the production of silyl group containing amine compounds |
Non-Patent Citations (3)
Title |
---|
YUKAGAGU 19,NO.11,23 1970.1.1 牧宏久.堀口恭伸.菅 * |
YUKAGAGU 19,NO.11,23 1970.1.1 牧宏久.堀口恭伸.菅;YUKAGAGU 19,NO.4,51 1970.1.1 牧宏久.菅.孝明.池田 * |
YUKAGAGU 19,NO.4,51 1970.1.1 牧宏久.菅.孝明.池田 * |
Also Published As
Publication number | Publication date |
---|---|
DE4320920C1 (de) | 1994-06-16 |
DE59407622D1 (de) | 1999-02-25 |
NZ260770A (en) | 1995-12-21 |
ES2128461T3 (es) | 1999-05-16 |
DE59407623D1 (de) | 1999-02-25 |
NZ260771A (en) | 1995-12-21 |
CN1046527C (zh) | 1999-11-17 |
DK0630901T3 (da) | 1999-08-30 |
US5430167A (en) | 1995-07-04 |
CN1107477A (zh) | 1995-08-30 |
JPH0710884A (ja) | 1995-01-13 |
AU668041B2 (en) | 1996-04-18 |
MX9404816A (es) | 1995-01-31 |
AU6475294A (en) | 1995-01-05 |
ES2128460T3 (es) | 1999-05-16 |
CA2124877A1 (en) | 1994-12-25 |
EP0630902B1 (de) | 1999-01-13 |
EP0630901B1 (de) | 1999-01-13 |
AU6475394A (en) | 1995-01-05 |
EP0630901A1 (de) | 1994-12-28 |
DK0630902T3 (da) | 1999-08-30 |
CA2124877C (en) | 1999-02-02 |
CN1106413A (zh) | 1995-08-09 |
JPH0733782A (ja) | 1995-02-03 |
MX9404815A (es) | 1995-01-31 |
EP0630902A1 (de) | 1994-12-28 |
CA2124876C (en) | 1998-12-15 |
US5430166A (en) | 1995-07-04 |
AU667436B2 (en) | 1996-03-21 |
JP2749520B2 (ja) | 1998-05-13 |
CA2124876A1 (en) | 1994-12-25 |
BR9402517A (pt) | 1995-03-14 |
BR9402516A (pt) | 1995-03-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1044708C (zh) | 具有亲水基团的硅烷及其制备方法和应用 | |
CN1043895C (zh) | 具有亲水基团的硅烷及其制备方法和应用 | |
US5475127A (en) | Organosilyl and organosiloxanyl derivatives of glycerin ethers and their use | |
US5869728A (en) | Process for preparing fluoroalkyl-containing organosilicon compounds, and their use | |
US6987157B2 (en) | Certain silicone polyethers, methods for making them and uses | |
US3296291A (en) | Reaction of silanes with unsaturated olefinic compounds | |
EP0367381A2 (en) | Carbosilane surfactants | |
CA2030958C (en) | Polydimethylsiloxane terminated at one end with a branched aminoalkyl group and preparation thereof | |
JPH0267290A (ja) | 鳥かご状構造を有する親油性二重環ケイ酸誘導体、その製造方法及びその使用方法 | |
US5527935A (en) | Organopolysiloxanes having bifunctional terminal siloxane units | |
KR20100057027A (ko) | 혼합된 플루오로알킬-알킬 계면활성제 | |
EP3689944A1 (en) | Polysiloxazane compound, method for producing the same, and composition containing the same and cured product thereof | |
EP0523910B1 (en) | Organosilicon compounds | |
EP0819693B1 (de) | Cyclische Silanester und deren Solvolyseprodukte sowie Verfahren zur Herstellung der cyclischen Silanester und der Solvolyseprodukte | |
EP2528927B1 (en) | Silicon polyethers and method of producing the same | |
US4490416A (en) | Organosiloxane-oxyalkylene copolymers | |
DE2418387A1 (de) | Siliciumhaltige nitrophenylaether | |
JPH0739425B2 (ja) | アシルアミノシリコーン化合物の合成方法 | |
KR20190075180A (ko) | 아미노산 모이어티를 가진 오르가노실리콘 화합물 및 이의 제조 방법 | |
EP0392509B1 (en) | 3-(2-Oxo-1-pyrrolidinyl)-propyl-silanes and method for preparing the silane compounds | |
US2888475A (en) | Titanated alkoxy silanes | |
EP3334774B1 (en) | Bifunctional poly(alkyleneoxides) with aminoalkyl and unsaturated termini and derivatives thereof | |
EP0408219A2 (en) | Method of treating textiles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |