EP4251691A1 - Mixtures containing phosphorus compounds and use thereof - Google Patents
Mixtures containing phosphorus compounds and use thereofInfo
- Publication number
- EP4251691A1 EP4251691A1 EP21708964.8A EP21708964A EP4251691A1 EP 4251691 A1 EP4251691 A1 EP 4251691A1 EP 21708964 A EP21708964 A EP 21708964A EP 4251691 A1 EP4251691 A1 EP 4251691A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixtures
- optionally
- formula
- integer
- hydrocarbon radicals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 150000003018 phosphorus compounds Chemical class 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 125000003110 organyloxy group Chemical group 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- -1 phosphorus compound Chemical class 0.000 claims description 102
- 229930195733 hydrocarbon Natural products 0.000 claims description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 150000004756 silanes Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 125000005372 silanol group Chemical group 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 40
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000306 component Substances 0.000 description 50
- 150000003254 radicals Chemical class 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- 229920004482 WACKER® Polymers 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 11
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 9
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 6
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 4
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 3
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 3
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- UOCZMUZYGLTGHO-UHFFFAOYSA-N triethoxy(morpholin-4-ylmethyl)silane Chemical compound CCO[Si](OCC)(OCC)CN1CCOCC1 UOCZMUZYGLTGHO-UHFFFAOYSA-N 0.000 description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical compound C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 2
- IVLBLTUZCAKUCG-UHFFFAOYSA-N ethyl 3-oxobutanoate 2-methylpropan-1-olate titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CCOC(=O)[CH-]C(C)=O.CCOC(=O)[CH-]C(C)=O IVLBLTUZCAKUCG-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 description 2
- RQCNTLREGQQSNU-UHFFFAOYSA-N trimethoxy(2,2,4-trimethylpentyl)silane Chemical compound CO[Si](OC)(OC)CC(C)(C)CC(C)C RQCNTLREGQQSNU-UHFFFAOYSA-N 0.000 description 2
- LTMJJNPVAMLQGV-PWNYCUMCSA-N (-)-(2R,3R)-2,3-dihydroxybutanamide Chemical compound C[C@@H](O)[C@@H](O)C(N)=O LTMJJNPVAMLQGV-PWNYCUMCSA-N 0.000 description 1
- MASDFXZJIDNRTR-UHFFFAOYSA-N 1,3-bis(trimethylsilyl)urea Chemical compound C[Si](C)(C)NC(=O)N[Si](C)(C)C MASDFXZJIDNRTR-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- CGERYHYIVJQVLJ-UHFFFAOYSA-N 2-methylbutane Chemical compound CC[C](C)C CGERYHYIVJQVLJ-UHFFFAOYSA-N 0.000 description 1
- BFDYSJCMAFSRDH-UHFFFAOYSA-N 2-phenylethylphosphonic acid Chemical compound OP(O)(=O)CCC1=CC=CC=C1 BFDYSJCMAFSRDH-UHFFFAOYSA-N 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- HNUALPPJLMYHDK-UHFFFAOYSA-N C[CH]C Chemical compound C[CH]C HNUALPPJLMYHDK-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FGPCETMNRYMFJR-UHFFFAOYSA-L [7,7-dimethyloctanoyloxy(dimethyl)stannyl] 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCC(C)(C)C FGPCETMNRYMFJR-UHFFFAOYSA-L 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DLEPCXYNAPUMDZ-UHFFFAOYSA-N butan-2-ylphosphonic acid Chemical compound CCC(C)P(O)(O)=O DLEPCXYNAPUMDZ-UHFFFAOYSA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- SCIGVHCNNXTQDB-UHFFFAOYSA-N decyl dihydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(O)=O SCIGVHCNNXTQDB-UHFFFAOYSA-N 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- RNPXCFINMKSQPQ-UHFFFAOYSA-N dicetyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCC RNPXCFINMKSQPQ-UHFFFAOYSA-N 0.000 description 1
- QHAUASBJFFBWMY-UHFFFAOYSA-N didecyl hydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(=O)OCCCCCCCCCC QHAUASBJFFBWMY-UHFFFAOYSA-N 0.000 description 1
- JTXUVYOABGUBMX-UHFFFAOYSA-N didodecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCC JTXUVYOABGUBMX-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- HUDSKKNIXMSHSZ-UHFFFAOYSA-N dihexyl hydrogen phosphate Chemical compound CCCCCCOP(O)(=O)OCCCCCC HUDSKKNIXMSHSZ-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- CYFHLEMYBPQRGN-UHFFFAOYSA-N ditetradecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCC CYFHLEMYBPQRGN-UHFFFAOYSA-N 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass 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
- 150000002357 guanidines Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- GGKJPMAIXBETTD-UHFFFAOYSA-N heptyl dihydrogen phosphate Chemical compound CCCCCCCOP(O)(O)=O GGKJPMAIXBETTD-UHFFFAOYSA-N 0.000 description 1
- VAJFLSRDMGNZJY-UHFFFAOYSA-N heptylphosphonic acid Chemical compound CCCCCCCP(O)(O)=O VAJFLSRDMGNZJY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 description 1
- JDPSFRXPDJVJMV-UHFFFAOYSA-N hexadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCP(O)(O)=O JDPSFRXPDJVJMV-UHFFFAOYSA-N 0.000 description 1
- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 description 1
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- WUFHQGLVNNOXMP-UHFFFAOYSA-N n-(triethoxysilylmethyl)cyclohexanamine Chemical compound CCO[Si](OCC)(OCC)CNC1CCCCC1 WUFHQGLVNNOXMP-UHFFFAOYSA-N 0.000 description 1
- QRANWKHEGLJBQC-UHFFFAOYSA-N n-(trimethoxysilylmethyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CNC1CCCCC1 QRANWKHEGLJBQC-UHFFFAOYSA-N 0.000 description 1
- BWYLUCQZPVGWLL-UHFFFAOYSA-N n-butyl-n-(triethoxysilylmethyl)butan-1-amine Chemical compound CCCCN(CCCC)C[Si](OCC)(OCC)OCC BWYLUCQZPVGWLL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YOOYVODKUBZAPO-UHFFFAOYSA-N naphthalen-1-ylphosphonic acid Chemical compound C1=CC=C2C(P(O)(=O)O)=CC=CC2=C1 YOOYVODKUBZAPO-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OLGGYSFJQGDOFX-UHFFFAOYSA-N nonylphosphonic acid Chemical compound CCCCCCCCCP(O)(O)=O OLGGYSFJQGDOFX-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
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- ULIMUQCIZMJOHK-UHFFFAOYSA-N pentadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCP(O)(O)=O ULIMUQCIZMJOHK-UHFFFAOYSA-N 0.000 description 1
- NVTPMUHPCAUGCB-UHFFFAOYSA-N pentyl dihydrogen phosphate Chemical compound CCCCCOP(O)(O)=O NVTPMUHPCAUGCB-UHFFFAOYSA-N 0.000 description 1
- CKVICYBZYGZLLP-UHFFFAOYSA-N pentylphosphonic acid Chemical compound CCCCCP(O)(O)=O CKVICYBZYGZLLP-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 102220065927 rs794726936 Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- OGDSVONAYZTTDA-UHFFFAOYSA-N tert-butylphosphonic acid Chemical compound CC(C)(C)P(O)(O)=O OGDSVONAYZTTDA-UHFFFAOYSA-N 0.000 description 1
- KRIXEEBVZRZHOS-UHFFFAOYSA-N tetradecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(O)=O KRIXEEBVZRZHOS-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- KREGXBHGJXTOKZ-UHFFFAOYSA-N tridecylphosphonic acid Chemical compound CCCCCCCCCCCCCP(O)(O)=O KREGXBHGJXTOKZ-UHFFFAOYSA-N 0.000 description 1
- DHEOLHWDNNLCNQ-UHFFFAOYSA-N triethoxy(2,2,4-trimethylpentyl)silane Chemical compound CCO[Si](OCC)(OCC)CC(C)(C)CC(C)C DHEOLHWDNNLCNQ-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UWSYCPWEBZRZNJ-UHFFFAOYSA-N trimethoxy(2,4,4-trimethylpentyl)silane Chemical compound CO[Si](OC)(OC)CC(C)CC(C)(C)C UWSYCPWEBZRZNJ-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- GKIQHTGBORJXKZ-UHFFFAOYSA-N undecylphosphonic acid Chemical compound CCCCCCCCCCCP(O)(O)=O GKIQHTGBORJXKZ-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- 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
- C08G2190/00—Compositions for sealing or packing joints
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
Definitions
- the invention relates to mixtures containing phosphorus compounds, processes for their production and their use, in particular in crosslinkable compositions based on organosilicon compounds and processes for the production of organosilicon compounds containing organyloxy groups.
- One-component sealing compounds which can be stored in the absence of water and harden when exposed to water at room temperature with elimination of alcohols to form elastomers are already known. These products are used in large quantities, e.g. in the construction industry. These mixtures are based on polymers terminated by silyl groups bearing reactive substituents such as OH groups or hydrolyzable groups such as alkoxy groups. Furthermore, these sealants can contain fillers, plasticizers, crosslinkers, catalysts and various additives. Alkoxysilanes are often used as crosslinkers. To accelerate curing, these sealants require catalysts based on tin or titanium.
- Tin catalysts frequently used are, for example, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dioxide and their reaction products with alkoxysilanes.
- RTVI sealing compounds produced using alkoxysilanes have disadvantages. After just a few months, they no longer fully harden.
- Various organic phosphorus compounds are therefore proposed in EP 1397 428 B1 to significantly improve storage stability.
- the phosphorus compounds that are particularly suitable for stabilizing RTVI sealing compounds such as, for example, octlyphosphonic acid, are solids at room temperature. In operational use, however, liquids are strongly preferred, because these are just about continuously running processes are much better suited for dosing than solids.
- EP 2030 675 B1 an easy-to-handle, liquid solution of n-octylphosphonic acid in methyltrimethoxysilane is used.
- methyltrimethoxysilane has a particularly disadvantageous very low flash point. This undesirably complex safety measures are required when handling Me thyltrimethoxysilan. Furthermore, it is not always ensured that no undesired reaction products form in the case of mixtures of n-octylphosphonic acid and methyltrimethoxysilane.
- n-octylphosphonic acid is also known as a neutralizing agent in the production of polymers with hydrolyzable end groups.
- EP 3344 684 B1 describes the reaction of terminal silanol groups of linear polydimethylsiloxanes with alkoxysilanes. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene is used as the catalyst.
- the catalyst is neutralized in a second step with n-octylphosphonic acid.
- the disadvantageous variant of a solution of n-octylphosphonic acid in methyltrimethoxysilane is also used here.
- the object of the invention was to overcome the disadvantages of the Stan of the art.
- the invention relates to mixtures (M) containing (X) polyethers of the general formula
- R 2 can be the same or different and is divalent, optionally substituted hydrocarbon radicals and p is an integer from 4 to 110,
- R 5 can be the same or different and is optionally substituted hydrocarbon radicals
- R 6 can be the same or different and is optionally substituted hydrocarbon radicals, m is 0 or 1, preferably 1, and n is 0, 1 or 2, with the proviso that m+n is 1 or 2, preferably 1, is, and if necessary
- radicals R 1 are alkyl radicals such as methyl,
- the radicals R 1 are preferably a hydrogen atom or alkyl radicals having 1 to 18 carbon atoms, particularly preferably a hydrogen atom.
- divalent radicals R 2 are alkylene radicals, such as ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, butane-1 ,3-diyl, 2-methylpropane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, 2,2- dimethylpropane-1,3-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl and 2-methylheptane-1,7-diyl and 2 ,2,4-trimethylpentane-1,5-diyl radical.
- alkylene radicals such as ethane-1,2-diyl, propane-1,2-diyl, propane-1,
- the radical R 2 is preferably a divalent hydrocarbon radical having 2 to 4 carbon atoms, particularly preferably the propane-1,2-diyl radical.
- Index p is preferably an integer from 4 to 65.
- polyethers (X) used according to the invention are preferably those of the formula
- R 1 has one of the meanings given above, q is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15, s is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15; and r is an integer from 4 to 50, preferably an integer from 4 to 35.
- Examples of the compounds (X) used according to the invention are H(OCH 2 CH 2 ) 5 (OCHCH 3 CH 2 )(OCH 2 CH 2 ) 10 OH,
- polyethers (X) used according to the invention are those of the formula
- the mixtures (M) according to the invention contain polyethers (X) in amounts of preferably 40 to 90 parts by weight, especially preferably from 50 to 70 parts by weight, based in each case on 100 parts by weight of the mixture (M).
- Polyethers (X) are commercially available products or can be prepared by methods customary in organic chemistry.
- radicals R 5 are the radicals given for R 1 .
- the radical R 5 is preferably linear or branched alkyl radicals having 4 to 16 carbon atoms, aryl radicals or the vinyl radical, particularly preferably linear or branched alkyl radicals having 4 to 16 carbon atoms, in particular the n-octyl radical.
- R 6 are the radicals given for R 1 and radicals interrupted by oxygen such as R 1 -(O-CH2CH2)3-,
- the R 6 radical is preferably a linear or branched alkyl radical having 1 to 18 carbon atoms or an oxygen-interrupted alkyl radical having 10 to 68 carbon atoms.
- Examples of phosphorus compounds (Y) used according to the invention are alkylphosphonic acids such as butylphosphonic acid, s-butylphosphonic acid, i-butylphosphonic acid, tert-butylphosphonic acid, n-pentylphosphonic acid, n-hexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, n-nonylphosphonic acid, n -Decylphosphonic acid, n-undecylphosphonic acid, n-dodecylphosphonic acid, n-tridecylphosphonic acid, n-tetratedylphosphonic acid, n-pentadecylphosphonic acid, n-hexadecylphosphonic acid, Benzylphosphonic acid, 2-phenylethylphosphonic acid, arylphosphonic acids such as phenylphosphonic acid, 1-naphthylphosphonic acid,
- the phosphorus compounds (Y) used according to the invention are preferably alkylphosphonic acids having 4 to 18 carbon atoms, particularly preferably n-octylphosphonic acid.
- Phosphorus compounds (Y) are commercial products.
- n-octylphosphonic acid is available as a pure substance or as a solution in ethanol and water, e.g. under the name "Hostaphat OPS 100" (pure product) or “Hostaphat OPS 75” (solution in ethanol and water) from Clariant.
- the mixtures (M) according to the invention contain phosphorus compounds (Y) in amounts of preferably 10 to 50 parts by weight, particularly preferably 25 to 35 parts by weight, based in each case on 100 parts by weight of the mixture (M).
- the mixtures (M) according to the invention preferably contain water (Z).
- the mixtures (M) according to the invention contain water (Z) in amounts of preferably 0.5 to 3.0 mol, particularly preferably 1.0 to 2.0 mol, in particular 1.0 to 1.5 mol, in each case based on 1 mol Phosphorus compound (Y), preferably n-octylphosphonic acid.
- the mixtures (M) according to the invention can contain other components, such as alcohols, in particular ethanol.
- the mixtures (M) according to the invention preferably consist of at least 98% by weight, particularly preferably at least 99.8% by weight, in particular 100% by weight, of the components (X),
- the mixtures (M) according to the invention are colorless to slightly yellowish liquids or low-melting solids and have a melting point of preferably ⁇ 35°C, particularly preferably ⁇ 0°C, in particular ⁇ -30°C.
- mixtures (M) can be mixed with one another in any order. This mixing can take place at room temperature or at an elevated temperature of 30° C. to 150° C. and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa, or reduced pressure of 1 to 900 hPa.
- Another subject of the invention is a process for preparing the mixtures (M) according to the invention by mixing the individual components.
- polyether (X) is preferably initially taken in a suitable vessel and then the phosphorus compound (Y) is metered in with stirring. This happens before preferably at the ambient temperature.
- the mixture is then heated to a temperature of from 80 to 150° C., with stirring and under a reduced pressure of up to 20 mbar, and impurities present, such as water and alcohols, are removed by distillation. The temperature and reduced pressure are preferably maintained until no more distillate comes over. It is then cooled to room temperature and, if desired, a defined amount of water (Z) is added.
- the process according to the invention can be carried out continuously, batchwise or semicontinuously according to known processes and using known apparatus.
- the mixtures (M) according to the invention have the advantage that they can be handled as a liquid with a low risk potential without the formation of undesirable by-products.
- mixtures (M) according to the invention have the advantage that they are easy to prepare without the formation of undesirable by-products.
- the mixtures (M) according to the invention have the advantage that they are liquid, even at low temperatures, and have a low flash point.
- the mixtures (M) according to the invention have the advantage that they exhibit high storage stability and high resistance to low temperatures.
- mixtures (M) according to the invention can be used for all purposes for which phosphorus compounds can previously also be used, such as, for example, as stabilizers for compositions based on organosilicon compounds which can be crosslinked with elimination of alcohol.
- Mixtures (M) according to the invention are preferably used for the production of crosslinkable compositions based on organosilicon compounds.
- Another object of the invention are crosslinkable co compositions based on organosilicon compounds he obtainable by mixing
- R 4 may be the same or different and are monovalent, optionally substituted hydrocarbon radicals,
- R 7 can be the same or different and means monovalent, optionally substituted hydrocarbon radicals,
- R 3 can be the same or different and is monovalent, optionally substituted hydrocarbon radicals, a may be the same or different and is 0 or 1, preferably 1, and x is an integer from 30 to 2000, and
- radicals R 4 and R 7 are, independently of one another, the radicals specified for radical R 1 .
- the radicals R 4 are preferably, independently of one another, monovalent hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably a methyl, vinyl or phenyl radical, in particular the methyl radical.
- the radicals R 7 are preferably, independently of one another, alkyl radicals having 1 to 12 carbon atoms, particularly preferably methyl, ethyl, n-propyl or isopropyl radicals, in particular the methyl or ethyl radical.
- radicals R 3 are the monovalent hydrocarbon radicals specified for R 1 and hydrocarbon radicals substituted with amino groups.
- the R 3 radical is preferably a monovalent, optionally amino-substituted hydrocarbon radical having 1 to 12 carbon atoms, particularly preferably a methyl radical, ethyl radical, vinyl radical, phenyl radical, -CH2-NR 6 'R 5 ' radical or the -CH2NR 11 radical ', where R 5 ' are hydrocarbon radicals with 1 to 12 Carbon atoms, R 6 'hydrogen atom or radical R 5 ' means and R 11 'divalent hydrocarbon radicals which can be interrupted with He teroatomen means.
- the R 3 radical is particularly preferably a -CH 2 -NR 6 'R 5 ' radical or a -CH 2 NR 11 ' radical with R 5 ', R 6 ' and R 11 ' having the same meaning as mentioned above, in particular - CH 2 -N [(CH 2 ) 2 ] 2 O, -CH 2 -N(Bu) 2 or -CH 2 -NH (cHex), where Bu is n-butyl and cHex is cyclohexyl.
- radicals R 5 ' are the hydrocarbon radicals specified for R 1 .
- the radical R 5 ' is preferably the methyl, ethyl, isopropyl, n-propyl, n-butyl, cyclohexyl or phenyl radical, particularly preferably the n-butyl radical.
- hydrocarbon radicals R 6 ' are the hydrocarbon radicals specified for R 1 .
- the radical R 6 ' is preferably a hydrogen atom, the methyl, ethyl, isopropyl, n-propyl, n-butyl or cyclohexyl radical, particularly preferably the n-butyl radical.
- Examples of divalent radicals R 11 ' are the examples given for R 2 and radicals -CH 2 -CH 2 -O-CH 2 -CH 2 - and -CH 2 -CH 2 -NH-CH 2 -CH 2 -.
- the radical R 11 ' is preferably a divalent hydrocarbon radical having 4 to 6 carbon atoms which can be interrupted by heteroatoms, preferably oxygen -O- or nitrogen -NH-, particularly preferably -CH 2 -CH 2 - O- CH2 - CH2- .
- the organopolysiloxanes (A) used according to the invention are preferably (MeO) 2 Si(Ox)0(SiMe 2 0) 30-2000 S1(Ox)(OMe) 2 ,
- the organopolysiloxanes (A) used according to the invention have a viscosity of preferably from 6,000 to 350,000 mPas, particularly preferably from 20,000 to 120,000 mPas, in each case at 25.degree.
- the organopolysiloxanes (A) are commercially available products or they can be prepared by a method described below.
- the component (B) used according to the invention is preferably a mixture (M) which comprises water (Z).
- the compositions according to the invention contain component (B) in amounts of preferably 0.001 to 5 parts by weight, more preferably 0.01 to 5 parts by weight, in particular 0.1 to 1 part by weight, based in each case on 100 parts by weight of component (A).
- compositions according to the invention can contain a component (C) consisting of silanes of the formula
- R 8 can be the same or different and is monovalent, optionally substituted hydrocarbon radicals and R 9 is monovalent, optionally substituted hydrocarbon radicals.
- the radical R 8 is preferably an alkyl radical having 1 to 12 carbon atoms, particularly preferably a methyl, ethyl, n-propyl or isopropyl radical, in particular the methyl or ethyl radical.
- the radical R 9 is preferably a monovalent hydrocarbon radical having 1 to 18 carbon atoms which is optionally substituted by glycidoxy, ureido, methacryloxy or amino groups, particularly preferably alkyl radicals, the vinyl radical or the phenyl radical, in particular the methyl radical or the 2,2,4-trimethylpentyl radical.
- silanes and/or their partial hydrolyzates are used in whole or in part as component (C).
- functional groups are used, such as those with glycidoxypropyl, aminopropyl, aminoethylaminopropyl, ureidopropyl or methacryloxypropyl radicals, especially when adhesion-promoting properties are desired.
- the partial hydrolyzates (C) used if appropriate can be partial homohydrolysates, i.e. partial hydrolysates of one type of silanes of the formula (III), or partial cohydrolysates, i.e. partial hydrolysates of at least two different types of silanes of the formula (III) .
- partial hydrolyzates is understood to mean products which have arisen by hydrolysis and/or condensation.
- component (C) optionally used in the compositions according to the invention is a partial hydrolyzate of silanes of the formula (VI), those having up to 20 silicon atoms are preferred.
- component (C) optionally used according to the invention are methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, tetraethoxysilane, 2,2,4-trimethylpentyltriethoxysilane, (2,3,5, 6-Tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane, N,N-di-n-butylaminomethyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, (2,3,5,6-Tetrahydro-1,4-oxazine-4 -yl)methyltrimethoxysilane N,N-di-n-butylaminomethyltrimethoxysilane, N,
- compositions according to the invention contain component (C), the amounts involved are preferably from 0.01 to 5 parts by weight, particularly preferably from 0.01 to 2 parts by weight, in particular from 0.05 to 2 parts by weight, in each case based on 100 parts by weight component (A).
- component (C) which preferably contains at least some silanes and/or their partial hydrolyzates with functional groups.
- compositions according to the invention can now contain all substances which have also previously been used in compositions which can be crosslinked by a condensation reaction, such as, for example, curing accelerators (D), plasticizers (E) , fillers (F) and additives (G).
- Curing accelerators (D) which can be used are all curing accelerators which have hitherto been used in compositions which can be crosslinked by a condensation reaction.
- curing accelerators (D) are titanium compounds, such as tetrabutyl or tetraisopropyl titanate, or titanium chelates, such as bis(ethylacetoacetato)diisobutoxytitanium, or organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, di-n -butyltin oxide, dimethyltin diacetate, dimethyltin dilaurate, dimethyltin dineodecanoate, dimethyltin noxide, di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin oxide and reaction products of these compounds with Alkoxysilanes, such as the
- compositions according to the invention contain curing accelerators (D), the amounts involved are preferably 0.001 to 20 parts by weight, particularly preferably 0.001 to 1 part by weight, based in each case on 100 parts by weight of component (A).
- plasticizers (E) which may be used are dimethylpolysiloxanes which are liquid at room temperature and end-capped by trimethylsiloxy groups, in particular with viscosities at 25° C. in the range between 5 and 1000 mPas, and high-boiling hydrocarbons, such as paraffin oils or mineral oils consisting of naphthenic and paraffinic units.
- compositions according to the invention contain component (E), the amounts involved are preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, based in each case on 100 parts by weight of siloxanes (A).
- the compositions according to the invention preferably contain no plasticizer (E).
- the fillers (F) optionally used in the compositions according to the invention can be any previously known fillers.
- fillers (F) are non-reinforcing fillers (F), ie fillers with a BET surface area of up to 20 m 2 /g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders such as aluminum, titanium -, Iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders such as polyacrylonitrile powder; reinforcing fillers, ie fillers with a BET surface area of more than 20 m 2 /g, such as precipitated chalk and carbon black, such as furnace and acetylene black; Silicic acid, such as pyrogenically produced silicic acid and precipitated silicic acid; fibrous fillers such as plastic fibers.
- BET surface area such as quartz, diatomaceous earth, calcium silicate, zirconium silicate,
- the optionally used fillers (F) are preferably calcium carbonate or silicic acid, particularly preferably silicic acid or a mixture of silicic acid and calcium carbonate.
- Preferred types of calcium carbonate (F) are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or salts thereof.
- the preferred silica is preferably fumed silica.
- compositions according to the invention contain fillers (F), the amounts involved are preferably 10 to 150 parts by weight, particularly preferably 10 to 130 parts by weight, in particular 10 to 100 parts by weight, based in each case on 100 parts by weight of organopolysiloxanes (A).
- the compositions according to the invention preferably contain filler (F).
- additives (G) are pigments, dyes, fragrances, oxidation inhibitors, agents for influencing the electrical properties, such as conductive carbon black, flame retardants, light stabilizers, biocides such as fungicides, bactericides and acaricides, cell-generating agents, for example azodicarbonamide , Heat stabilizers, scavengers, such as Si-N-containing silazanes or silylamides, for example N,N'-bis-trimethylsilylurea or hexamethyldisilazane, cocatalysts, thixotropic agents, such as polyethylene glycol end-terminated on one or both sides or hydrogenated castor oil , Agents to further regulate the modulus such as polydimethylsiloxanes with an OH end group, as well as any siloxanes that are different from components (A), (B) and (C).
- additives (G) are pigments, dyes, fragrances, oxidation inhibitors, agents for influencing
- thixotropic agents (G) can be dispensed with.
- compositions according to the invention can each be one type of such a component or a mixture of at least two different types of such components.
- compositions according to the invention are preferably those which
- compositions according to the invention are particularly preferably those which
- silanes of the formula (VI) and/or their partial hydrolyzates optionally (D) curing accelerators, optionally (E) plasticizers, optionally (F) fillers and optionally (G) additives.
- compositions according to the invention are those that are identical to each other.
- compositions according to the invention preferably contain no further constituents.
- compositions according to the invention are preferably viscous to pasty masses.
- compositions according to the invention can be mixed together in any order. This mixing can take place at room temperature and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa.
- this mixing can also be carried out at higher temperatures, e.g., at temperatures in the range of from 35 to 135°C.
- this mixing can also be carried out at higher temperatures, e.g., at temperatures in the range of from 35 to 135°C.
- the mixing according to the invention preferably takes place with the greatest possible exclusion of water from the atmosphere.
- All raw materials with the exception of (M) have a water content of preferably less than 10000 mg/kg, preferably less than 5000 mg/kg, in particular less than 1000 mg/kg.
- Dry air or protective gas such as nitrogen is preferably used as a blanket during the mixing process, with the respective gas having a moisture content of preferably less than 10,000 pg/kg, preferably less than 1000 pg/kg, in particular less than 500 pg/kg.
- the pastes are filled into commercially available moisture-proof containers, such as cartridges, tubular bags, buckets and barrels.
- the components (A), optionally (C) and (E) are first mixed together, then optionally fillers (F) are added and finally (B) and optionally further components (D) and (G) are added, the temperature during mixing preferably not exceeding 60°C.
- Another object of the invention is a process for preparing the compositions according to the invention by mixing the individual components.
- the process according to the invention can be carried out continuously, batchwise or semicontinuously according to known processes and using known apparatus.
- compositions according to the invention or those produced according to the invention can be stored in the absence of moisture and can be crosslinked if moisture is present.
- compositions according to the invention are preferably crosslinked at room temperature. If desired, it can also be carried out at temperatures higher or lower than room temperature, e.g. at -5° to 15°C or at 30°C to 50°C and/or using concentrations of water that exceed the normal water content of air will.
- the crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa.
- a further subject of the present invention are moldings produced by crosslinking the compositions according to the invention.
- compositions according to the invention can be used for all purposes for which compositions which can be stored in the absence of water and which crosslink to form elastomers at room temperature when exposed to water can be used.
- compositions of the invention are therefore excellent, for example, as a sealing compound for joints, including vertical joints, and similar voids of z 10 to 40 mm clear width, e.g. of buildings, land vehicles, watercraft and aircraft, or as adhesives or cementing compounds, e.g. in window construction or in the manufacture of showcases, and for example for the production of protective coatings, including those for the constant exposure to Surfaces exposed to freshwater or seawater or coatings that prevent sliding or rubber-elastic molded bodies.
- the masses according to the invention have the advantage that they are easy to produce and are characterized by a very high storage stability.
- the mixtures (M) according to the invention can furthermore preferably be used as neutralizing agents in processes for preparing polymers with hydrolyzable end groups.
- Another subject of the invention is a process for preparing organyloxy-containing organosilicon compounds, characterized in that in a 1st step at least one silanol group-containing organosilicon compound (a) with at least two organyloxy-containing compound (b) in the presence of strongly basic Catalysts (c) are reacted and, in a 2nd step, after reaction of the hydroxyl groups of component (a) with the compounds (b) containing organyloxy groups, the mixture (M) according to the invention is added.
- the strongly basic catalysts (c) can be lithium compounds, such as lithium alkoxylates or lithium hydroxide, and also amidines or guanidines, cyclic guanidines being preferred as component (c), particularly preferably 1,5 ,7-Triazabicyclo[4.4.0]dec-5-ene.
- organosilicon compound (a) containing at least one silanol group is reacted with compound (b) containing at least two organyloxy groups in the presence of 1,5,7-triazabicyclo[4.4.0]dec- 5-ene (c) and, in a 2nd step, mixture (M) according to the invention was added.
- Component (a) used according to the invention can be any previously known organosilicon compound having at least one silanol group.
- the organosilicon compound (a) is preferably an organosilicon compound having at least two silanol groups.
- the organosilicon compound (a) is preferably an essentially linear organopolysiloxane.
- the organosilicon compounds (a) used according to the invention have a viscosity of preferably 10 2 to 10 8 mPas, particularly preferably 1,000 to 350,000 mPas, in each case at 25.degree.
- organosilicon compound (a) used according to the invention are organosilicon compound (a) used according to the invention.
- Component (a) are commercially available products or can be produced by methods customary in chemistry.
- Component (b) used according to the invention can be any previously known compound having at least two organyloxy groups, preferably siloxanes or silanes.
- Component (b) is particularly preferably a silane of the formula (VI) and/or its partial hydrolyzates.
- Examples of compound (b) used according to the invention are methyltrimethoxysilane, dimethyldimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, methylvinyldimethoxysilane, methyltriethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane and tert-butyltrimethoxysilane, and their partial hydrolyzates, where Methyltrimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, methylvinyldimethoxysilane, methyltriethoxysilane, tetraethoxysilane and n-butyltrimethoxysilane are preferred, and methyltrimethoxysilane, tetramethoxysilane, vinyl
- Component (b) are commercially available products or can be produced by methods customary in chemistry. In the process according to the invention, component (b) is preferably used in a 1-fold to 100-fold excess, particularly preferably in a 2-fold to 50-fold molar excess, based in each case on the molar amount of Si—OH groups in the compound (a). .
- catalyst (c) is used in amounts of preferably 5 to 10,000 ppm by weight, particularly preferably 100 to 3000 ppm by weight, based in each case on the total amount of component (a) and (b).
- the individual compo nents can be mixed with one another in any order and in a previously known manner. Premixes can also be made from some components, such as a mixture of components (b) and (c), which are then mixed with the other components. Individual components can also be present or added right at the beginning or during the mixing process. For example, part of component (b) or preparation (c) can also be added 1 to 60 minutes after the other components have been mixed.
- the components used in the process according to the invention can each be one type of such a component or a mixture of at least two types of a respective component.
- the process according to the invention is preferably carried out without additional heating at ambient temperatures or at the temperatures which result when the individual components are mixed.
- the temperatures involved are preferably from 10 to 60.degree. C., particularly preferably from 15 to 40.degree.
- the process according to the invention is preferably carried out at the pressure of the surrounding atmosphere, ie from 900 to 1100 hPa; However, it is also possible to work at overpressure, such as at pressures between 1100 and 3000 hPa absolute pressure, in particular with continuous operation, if, for example, these pressures in closed systems are due to the pressure during pumping and the vapor pressure of the materials used at elevated temperatures result.
- the process according to the invention is preferably carried out in the absence of moisture, such as in dried air or nitrogen.
- the process according to the invention can be carried out under an inert gas such as nitrogen.
- the reaction mixture can be devolatilized, the devolatilization being carried out by means of a vacuum in the same apparatus or in a downstream apparatus, with or without inert gas being fed in, at room temperatures or elevated temperatures.
- the volatile components are preferably alcohols, such as methanol or ethanol.
- the process according to the invention can be carried out continuously or batchwise.
- a large number of organosilicon compounds containing organyloxy groups can advantageously be prepared by the process according to the invention.
- the process according to the invention has the advantage that organosilicon compounds containing organyloxy groups can be prepared in a simple manner.
- all viscosity data relate to a temperature of 25°C. Unless otherwise stated, the examples below are carried out at a pressure of the surrounding atmosphere, i.e. around 1000 hPa, and at room temperature, i.e. around 23° C., or at a temperature which arises when the reactants are combined at room temperature without additional heating or cooling is set and the relative humidity is about 50%. Furthermore, unless otherwise stated, all parts and percentages are by weight.
- the dynamic viscosity of the organosilicon compounds is measured according to DIN 53019.
- the procedure was preferably as follows: unless otherwise stated, the viscosity is measured at 25° C. using a “Physica MCR 300” rotational rheometer from Anton Paar.
- a coaxial cylinder measuring system (CC 27) with an annular measuring gap of 1.13 mm is used for viscosities from 1 to 200 mPa -s and a cone-plate measuring system (Searle System with measuring cone CP 50-1) used.
- the shear rate is adjusted to the polymer viscosity (1 to 99 mPa -s at 100 s 1 ; 100 to 999 mPa -s at 200 s 1 ; 1000 to 2999 mPa -s at 120 s 1 ; 3000 to
- the number-average molar mass M n is determined by means of size exclusion chromatography (SEC) against a polystyrene standard, in THF, at 60° C., flow rate 1.2 ml/min and detection with RI (refractive index detector) on a Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA determined with an injection volume of 100 m ⁇ .
- SEC size exclusion chromatography
- PPG 425 Polypropylene glycol with an average molecular weight M n of 425 g/mol;
- PPG 1000 polypropylene glycol with an average molecular weight M n of 1000 g/mol;
- PPG 400 polypropylene glycol with an average molecular weight M n of 400 g/mol;
- OPS 75 n-octylphosphonic acid, 75% by weight in water and ethanol (commercially available, for example, under the name "Hostaphat OPS 75" from Clariant).
- Example 1 The procedure described in Example 1 was repeated using the amounts of starting materials given in Table 1.
- Example 7 The procedure described in Example 7 was repeated with the modification that PPG 425 was used instead of PPG 400. No differences were found. In particular, the melting point was also less than -30°C.
- a pyrogenic silica with a BET specific surface area of 150 m 2 /g (commercially available under the name HDK® V15 from Wacker Chemie AG, D-Munich) were mixed in and completely homogenized at a pressure of 50 hPa .
- 1 g of the mixture produced in Example 1 and 2 g of a reaction product of dibutyltin diacetate and tetraethoxysilane (commercially available under the name "Katalysator 41" from Wacker Chemie AG, D-Munich) was added and the mixture was homogenized again for 5 minutes at a pressure of about 50 hPa (absolute).
- the RTVI mass obtained in this way was filled into moisture-proof commercially available polyethylene cartridges and stored at room temperature for 24 h and another sample at 70° C. for 7 days. Thereafter, 2 mm thick plates were spread out from each of the samples stored in this way and stored for 7 days at 23° C. and 50% relative atmospheric humidity. Test specimens in accordance with DIN 53504 of form S2 were punched out of the materials cured in the process and the mechanical parameters were measured. The results can be found in Table 2.
- Example 9 was repeated with the modification that instead of 1 g of the mixture according to example 11.57 g of a mixture according to example 7 were added.
- 300 g of the product produced according to Example 11 were mixed with 130 g of an a,w-bis(trimethylsiloxy)polydimethylsiloxane with a viscosity of 1000 mPa -s (commercially available under the name "Softener 1000" from Wacker Chemie AG, D-Munich ), 5 g N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (commercially available under the name GENIOSIL® GF 91 from Wacker Chemie AG, D-Munich), 2 g vinyltrimethoxysilane (commercially available under the name GENIOSIL® XL 10 at Wacker Chemie AG, D-Munich) in a planetary mixer and mixed for a period of 30 minutes.
- Softener 1000 commercially available under the name "Softener 1000" from Wacker Chemie AG, D-Munich
- the RTVI mass obtained in this way was filled into moisture-proof commercially available polyethylene cartridges and stored at room temperature for 24 h and another sample at 70° C. for 7 days. Thereafter, 2 mm thick plates were spread out from each of the samples stored in this way and stored for 7 days at 23° C. and 50% relative atmospheric humidity. Test specimens in accordance with DIN 53504 of form S2 were punched out of the materials cured in the process and the mechanical parameters were measured.
- This mixture was devolatilized at a reduced pressure of 50 mbar at 120° C. on a rotary evaporator.
- the composition of the mixture was determined by means of 29-Si NMR spectroscopy.
- the mixture contained 1.4% by weight of iOctSi(OMe)3, 0.4% by weight of Me2Si(OMe)2 and 98.2% by weight of an oligomer mixture with the average composition of [iOctSi(OMe)2O1 / 2 ]o,os[iO ⁇ ctSi(OMe)O2 / 2]0.15[iOctSiO3 / 2]0.05 [Me2S1O2 / 2]0.43[Me2Si(OMe)O1 / 2]0.29
- the molecular weights determined by means of gel permeation chromatography were 929 g/mol (Mw—weight average) and 635 (Mn—number average).
- the polydispersity (Mw/Mn) was 1.46.
- a mixture of 660 g of a,w-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPas and 220 g of a,w-dihydroxypolydimethylsiloxane with a viscosity of 20,000 mPas were mixed with 30.44 g of a solution of 0.04 g 1, 5,7-Triazabicyclo[4.4.0]dec-5-ene in 30.4 g (2,3,5,6-Tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane for 5 minutes at 200 rpm /min stirred.
- the mixture is then filled into commercially available cartridges and stored away from moisture. 24 hours after the preparation of the mixtures, 2 mm thick plates were drawn out of these mixtures and, after curing for 7 days at 23°C and 50% relative humidity, dumbbell-shaped test specimens of type 2 according to ISO 37, 6th edition 2017-11, were produced .
- the skin formation times were in the usual range between 15 and 25 minutes.
- Viscosity after 2 hours 190.0 Pa.
- Viscosity after 22 hours 162.5 Pa.s
- Example 17 (not according to the invention)
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Abstract
The invention relates to mixtures (M) containing phosphorus compounds, comprising (X) polyethers of the general formula R1-(O-R2)p-O-R1 (I), (Y) phosphorus compounds of the formula O=PR5
m(OR6)n(OH)3-(m+n) (II) and optionally (Z) water, wherein the radicals and indices have the meanings specified in claim 1, to a process for the preparation thereof and their use, in particular in cross-linkable compositions on the basis of organosilicon compounds, and to a process for preparing organosilicon compounds comprising organyloxy groups.
Description
Phosphorverbindung enthaltende Mischungen und deren Verwendung Mixtures containing phosphorus compounds and their use
Die Erfindung betrifft Phosphorverbindung enthaltende Mi schungen, Verfahren zu deren Herstellung und deren Verwendung, insbesondere in vernetzbaren Zusammensetzungen auf der Basis von Organosiliciumverbindungen und Verfahren zur Herstellung von Organyloxygruppen aufweisenden Organosiliciumverbindungen. The invention relates to mixtures containing phosphorus compounds, processes for their production and their use, in particular in crosslinkable compositions based on organosilicon compounds and processes for the production of organosilicon compounds containing organyloxy groups.
Unter Ausschluss von Wasser lagerfähige, bei Zutritt von Wasser bei Raumtemperatur unter Abspaltung von Alkoholen zu Elastome ren aushärtende Einkomponenten-Dichtmassen sind bereits be kannt. Diese Produkte werden in großen Mengen z.B. in der Bau industrie eingesetzt. Die Basis dieser Mischungen sind Poly mere, die durch Silylgruppen terminiert sind, die reaktive Sub stituenten, wie OH-Gruppen oder hydrolysierbare Gruppen, wie z.B. Alkoxygruppen, tragen. Des Weiteren können diese Dichtmas sen Füllstoffe, Weichmacher, Vernetzer, Katalysatoren sowie verschiedene Additive enthalten. Oft werden Alkoxysilane als Vernetzer verwendet. Diese Dichtmassen benötigen zur Beschleu nigung der Aushärtung Katalysatoren auf Basis von Zinn oder Ti tan. One-component sealing compounds which can be stored in the absence of water and harden when exposed to water at room temperature with elimination of alcohols to form elastomers are already known. These products are used in large quantities, e.g. in the construction industry. These mixtures are based on polymers terminated by silyl groups bearing reactive substituents such as OH groups or hydrolyzable groups such as alkoxy groups. Furthermore, these sealants can contain fillers, plasticizers, crosslinkers, catalysts and various additives. Alkoxysilanes are often used as crosslinkers. To accelerate curing, these sealants require catalysts based on tin or titanium.
Häufig verwendete Zinnkatalysatoren sind zum Beispiel Dibutyl- zinndilaurat, Dibutylzinndiacetat, Dioctylzinndioxid und deren Umsetzungsprodukte mit Alkoxysilanen. Unter Verwendung von Al- koxysilanen hergestellte RTVl-Dichtmassen haben jedoch Nach teile. Bereits nach wenigen Monaten härten sie nicht mehr voll ständig aus. Es werden deshalb in EP 1397 428 Bl zur deutli chen Verbesserung der Lagerstabilität verschiedene organische Phosphorverbindungen vorgeschlagen. Leider sind jedoch die für die Stabilisierung von RTVl-Dichtmassen besonders geeigneten Phosphorverbindungen wie z.B. Octlyphosphonsäure bei Raumtempe ratur Feststoffe. In der betrieblichen Anwendung sind aber Flüssigkeiten stark bevorzugt, denn diese sind gerade bei
kontinuierlich ablaufenden Verfahren wesentlich besser für die Dosierung geeignet als Feststoffe. So wird z.B. in EP 2030 675 Bl eine gut handhabbare, flüssige Lösung von n-Octylphosphon- säure in Methyltrimethoxysilan angewendet. Tin catalysts frequently used are, for example, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dioxide and their reaction products with alkoxysilanes. However, RTVI sealing compounds produced using alkoxysilanes have disadvantages. After just a few months, they no longer fully harden. Various organic phosphorus compounds are therefore proposed in EP 1397 428 B1 to significantly improve storage stability. Unfortunately, however, the phosphorus compounds that are particularly suitable for stabilizing RTVI sealing compounds, such as, for example, octlyphosphonic acid, are solids at room temperature. In operational use, however, liquids are strongly preferred, because these are just about continuously running processes are much better suited for dosing than solids. For example, in EP 2030 675 B1, an easy-to-handle, liquid solution of n-octylphosphonic acid in methyltrimethoxysilane is used.
Methyltrimethoxysilan weist jedoch besonders nachteilig einen sehr niedrigen Flammpunkt auf. Damit sind beim Umgang mit Me thyltrimethoxysilan unerwünscht aufwendige Sicherheitsmaßnahmen erforderlich. Weiterhin ist nicht immer sichergestellt, dass sich bei Mischungen aus n-Octylphosphonsäure und Mehyltrime- thoxysilan keine unerwünschten Umsetzungsprodukte bilden. However, methyltrimethoxysilane has a particularly disadvantageous very low flash point. This undesirably complex safety measures are required when handling Me thyltrimethoxysilan. Furthermore, it is not always ensured that no undesired reaction products form in the case of mixtures of n-octylphosphonic acid and methyltrimethoxysilane.
Des Weiteren ist die Verwendung von n-Octylphosphonsäure auch als Neutralisationsmittel bei der Herstellung von Polymeren mit hydrolysierbaren Endgruppen bekannt. EP 3344 684 Bl beschreibt die Reaktion endständiger Silanolgruppen von linearen Polydime- thylsiloxanen mit Alkoxysilanen. Verwendet wird 1,5,7-Triazabi- cyclo [4.4.0]dec-5-en als Katalysator. In den Beispielen wird nach der Reaktion der Katalysator in einem zweiten Schritt mit n-Octylphosphonsäure neutralisiert. Verwendet wird auch hier die nachteilige Variante einer Lösung von n-Octylphosphonsäure in Methyltrimethoxysilan. Furthermore, the use of n-octylphosphonic acid is also known as a neutralizing agent in the production of polymers with hydrolyzable end groups. EP 3344 684 B1 describes the reaction of terminal silanol groups of linear polydimethylsiloxanes with alkoxysilanes. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene is used as the catalyst. In the examples, after the reaction, the catalyst is neutralized in a second step with n-octylphosphonic acid. The disadvantageous variant of a solution of n-octylphosphonic acid in methyltrimethoxysilane is also used here.
Die Aufgabe der Erfindung bestand darin die Nachteile des Stan des der Technik zu überwinden. The object of the invention was to overcome the disadvantages of the Stan of the art.
Gegenstand der Erfindung sind Mischungen (M) enthaltend (X) Polyether der allgemeinen Formel The invention relates to mixtures (M) containing (X) polyethers of the general formula
R1-(O-R2)p-O-R1 (I), wobei
R1 gleich oder verschieden sein kann und Wasserstoffatom oder Kohlenwasserstoffreste darstellt, R 1 -(OR 2 ) p -OR 1 (I), wherein R 1 can be the same or different and represents hydrogen atom or hydrocarbon radicals,
R2 gleich oder verschieden sein kann und zweiwertige, gegebe nenfalls substituierte Kohlenwasserstoffreste bedeutet und p eine ganze Zahl von 4 bis 110 ist, R 2 can be the same or different and is divalent, optionally substituted hydrocarbon radicals and p is an integer from 4 to 110,
(Y) Phosphorverbindungen der Formel (Y) phosphorus compounds of the formula
0=PR5 m(0R6)n(0H)3-(m+n) (II), wobei O=PR 5 m (OR 6 ) n (OH) 3-(m+n) (II), where
R5 gleich oder verschieden sein kann und gegebenenfalls substi tuierte Kohlenwasserstoffreste bedeutet, R 5 can be the same or different and is optionally substituted hydrocarbon radicals,
R6 gleich oder verschieden sein kann und gegebenenfalls substi tuierte Kohlenwasserstoffreste bedeutet, m gleich 0 oder 1, bevorzugt 1, ist und n gleich 0, 1 oder 2 ist, mit der Maßgabe, dass m+n gleich 1 oder 2, bevorzugt 1, ist, und gegebenenfalls R 6 can be the same or different and is optionally substituted hydrocarbon radicals, m is 0 or 1, preferably 1, and n is 0, 1 or 2, with the proviso that m+n is 1 or 2, preferably 1, is, and if necessary
(Z) Wasser. (Z) water.
Beispiele für Reste R1 sind Alkylreste, wie der Methyl-,Examples of radicals R 1 are alkyl radicals such as methyl,
Ethyl-, n-Propyl-, iso-Propyl-, 1-n-Butyl-, 2-n-Butyl-, iso- Butyl-, tert.-Butyl-, n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert.-Pentylrest; Hexylreste, wie der n-Hexylrest; Heptylreste, wie der n-Heptylrest; Octylreste, wie der n-Octylrest und iso- Octylreste, wie der 2,2,4-Trimethylpentylrest; Nonylreste, wie der n-Nonylrest; Decylreste, wie der n-Decylrest; Dodecylreste, wie der n-Dodecylrest; Octadecylreste, wie der n-Octadecylrest; Cycloalkylreste, wie der Cyclopentyl-, Cyclohexyl-, Cyclo- heptylrest und Methylcyclohexylreste; Alkenylreste, wie der Vi nyl-, 1-Propenyl- und der 2-Propenylrest; Arylreste, wie der
Phenyl-, Naphthyl-, Anthryl- und Phenanthrylrest; Alkarylreste, wie o-, m-, p-Tolylreste; Xylylreste und Ethylphenylreste; und Aralkylreste, wie der Benzylrest, der der a- und der ß-Phe- nylethylrest . ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neo- pentyl, tert-pentyl radical; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; octadecyl radicals, such as the n-octadecyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; alkenyl radicals, such as the vinyl, 1-propenyl and 2-propenyl radical; aryl residues, like that phenyl, naphthyl, anthryl and phenanthryl; alkaryl radicals such as o-, m-, p-tolyl radicals; xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.
Bevorzugt handelt es sich bei den Resten R1 um Wasserstoffatom oder Alkylreste mit 1 bis 18 Kohlenstoffatomen, besonders be vorzugt um Wasserstoffatom. The radicals R 1 are preferably a hydrogen atom or alkyl radicals having 1 to 18 carbon atoms, particularly preferably a hydrogen atom.
Beispiele für zweiwertige Reste R2 sind Alkylenreste, wie der Ethan-1,2-diyl-, Propan-1,2-diyl-, Propan-1,3-diyl-, Butan-1,4- diyl-, Butan-1,3-diyl-, 2-Methylpropan-l,3-diyl-, Pentan-1,5- diyl-, Pentan-1,4-diyl-, 2-Methylbutan-l,4-diyl-, 2,2-Dimethyl- propan-1,3-diyl-, Hexan-1,6-diyl-, Heptan-1,7-diyl-, Octan-1,8- diyl- und 2-Methylheptan-l,7-diyl- und 2,2,4-Trimethylpentan- 1,5-diylrest . Examples of divalent radicals R 2 are alkylene radicals, such as ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, butane-1 ,3-diyl, 2-methylpropane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, 2,2- dimethylpropane-1,3-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl and 2-methylheptane-1,7-diyl and 2 ,2,4-trimethylpentane-1,5-diyl radical.
Bevorzugt handelt es sich bei Rest R2 um zweiwertige Kohlenwas serstoffreste mit 2 bis 4 Kohlenstoffatomen, besonders bevor zugt um den Propan-1,2-diylrest. The radical R 2 is preferably a divalent hydrocarbon radical having 2 to 4 carbon atoms, particularly preferably the propane-1,2-diyl radical.
Bevorzugt bedeutet Index p eine ganze Zahl von 4 bis 65. Index p is preferably an integer from 4 to 65.
Bevorzugt handelt es sich bei den erfindungsgemäß eingesetzten Polyethern (X) um solche der Formel The polyethers (X) used according to the invention are preferably those of the formula
R1 (OCH2CH2)q (OCHCH3CH2)r (OCH2CH2)sOR1 (III), wobei R 1 (OCH 2 CH 2 ) q (OCHCH 3 CH 2 ) r (OCH 2 CH 2 ) s OR 1 (III), wherein
R1 eine der obengenannten Bedeutungen hat, q 0 oder eine ganze Zahl von 1 bis 30, bevorzugt 0 oder eine ganze Zahl von 1 bis 15, ist,
s 0 oder eine ganze Zahl von 1 bis 30, bevorzugt 0 oder eine ganze Zahl von 1 bis 15, ist sowie r eine ganze Zahl von 4 bis 50, bevorzugt eine ganze Zahl von 4 bis 35, ist. R 1 has one of the meanings given above, q is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15, s is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15; and r is an integer from 4 to 50, preferably an integer from 4 to 35.
Beispiele für die erfindungsgemäß eingesetzten Verbindungen (X) sind H (OCH2CH2)5 (OCHCH3CH2)(OCH2CH2)10OH, Examples of the compounds (X) used according to the invention are H(OCH 2 CH 2 ) 5 (OCHCH 3 CH 2 )(OCH 2 CH 2 ) 10 OH,
H (OCH2CH2)6 (OCHCH3CH2)(OCH2CH2)7OH, H( OCH2CH2 ) 6 ( OCHCH3CH2 ) ( OCH2CH2 ) 7OH ,
H (OCH2CH2)5 (OCHCH3CH2)(OCH2CH2)20OH, H( OCH2CH2 ) 5 ( OCHCH3CH2 ) ( OCH2CH2 ) 20OH ,
H (OCH2CH2)7 (OCHCH3CH2)(OCH2CH2)7OH, H( OCH2CH2 ) 7 ( OCHCH3CH2 ) ( OCH2CH2 ) 7OH ,
H (OCH2CH2)2 (OCHCH3CH2)(OCH2CH2)12OH, H( OCH2CH2 ) 2 ( OCHCH3CH2 ) ( OCH2CH2 ) 12OH ,
H (OCH2CH2)5(OCHCH3CH2)2(OCH2CH2)10OH, H(OCH2CH2)5(OCHCH3CH2)2(OCH2CH2) 10OH ,
H (OCH2CH2)6 (OCHCH3CH2)2(OCH2CH2)6OH, H(OCH2CH2) 6 (OCHCH3CH2)2(OCH2CH2) 6OH ,
CH3 (OCH2CH2)5 (OCHCH3CH2)(OCH2CH2)10OCH3, CH3 ( OCH2CH2 ) 5 ( OCHCH3CH2 ) ( OCH2CH2 ) 10OCH3 ,
CH3 (OCH2CH2)6 (OCHCH3CH2)(OCH2CH2)7OCH3, CH3 ( OCH2CH2 ) 6 ( OCHCH3CH2 ) ( OCH2CH2 ) 7OCH3 ,
CH3 (OCH2CH2)5 (OCHCH3CH2)(OCH2CH2)20OCH3, CH3 ( OCH2CH2 ) 5 ( OCHCH3CH2 ) ( OCH2CH2 ) 20OCH3 ,
CH3 (OCH2CH2)7 (OCHCH3CH2)(OCH2CH2)7OH, CH3 ( OCH2CH2 ) 7 ( OCHCH3CH2 ) ( OCH2CH2 ) 7OH ,
CH3 (OCH2CH2)2 (OCHCH3CH2)(OCH2CH2)12OH, CH3 ( OCH2CH2 ) 2 ( OCHCH3CH2 ) ( OCH2CH2 ) 12OH ,
CH3 (OCH2CH2)5 (OCHCH3CH2)2 (OCH2CH2)10OH und CH3 (OCH2CH2)6 (OCHCH3CH2)2(OCH2CH2)6OH, wobei H (OCHCH3CH2)pOH, CH3 (OCHCH3CH2)POH oder CH3 (OCHCH3CH2)POCH3 besonders bevorzugt sind. CH3( OCH2CH2 ) 5 ( OCHCH3CH2 ) 2 ( OCH2CH2 ) 10OH and CH3( OCH2CH2 ) 6 ( OCHCH3CH2 ) 2 ( OCH2CH2 ) 6OH , where H( OCHCH3CH2 ) p OH, CH 3 (OCHCH 3 CH 2 ) P OH or CH 3 (OCHCH 3 CH 2 ) P OCH 3 are particularly preferred.
Insbesondere handelt es sich bei den erfindungsgemäß eingesetz ten Polyethern (X) um solche der Formel In particular, the polyethers (X) used according to the invention are those of the formula
H (OCHCH3CH2)rOH (IV) mit r gleich der oben angegebenen Bedeutung. H(OCHCH 3 CH 2 ) r OH (IV) where r is as defined above.
Die erfindungsgemäßen Mischungen (M) enthalten Polyether (X) in Mengen von bevorzugt 40 bis 90 Gewichtsteilen, besonders
bevorzugt von 50 bis 70 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile der Mischung (M). The mixtures (M) according to the invention contain polyethers (X) in amounts of preferably 40 to 90 parts by weight, especially preferably from 50 to 70 parts by weight, based in each case on 100 parts by weight of the mixture (M).
Polyether (X) sind handelsübliche Produkte bzw. können nach in der organischen Chemie gängigen Methoden hergestellt werden. Polyethers (X) are commercially available products or can be prepared by methods customary in organic chemistry.
Beispiele für Reste R5 sind die für R1 angegebenen Reste. Examples of radicals R 5 are the radicals given for R 1 .
Bevorzugt handelt es sich bei Rest R5 um lineare oder ver zweigte Alkylreste mit 4 bis 16 Kohlenstoffatomen, Arylreste o- der den Vinylrest, besonders bevorzugt um lineare oder ver zweigte Alkylreste mit 4 bis 16 Kohlenstoffatomen, insbesondere um den n-Octylrest. The radical R 5 is preferably linear or branched alkyl radicals having 4 to 16 carbon atoms, aryl radicals or the vinyl radical, particularly preferably linear or branched alkyl radicals having 4 to 16 carbon atoms, in particular the n-octyl radical.
Beispiele für R6 sind die für R1 angegebenen Reste und durch Sauerstoff unterbrochene Reste wie R1-(O-CH2CH2)3-, Examples of R 6 are the radicals given for R 1 and radicals interrupted by oxygen such as R 1 -(O-CH2CH2)3-,
R1-(O-CH2CH2)4-, R1-(O-CH2CH2)5- und R1-(O-CH2CH2)6-, n-Ci2H25-(O-CH2CH2)z-, n-Ci4H29-(O-CH2CH2)z-, n-Ci6H33-(0- CH2CH2)Z _ und n-Ci8H37-(O-CH2CH2)z_ mit z gleich 4 bis 25. R 1 -(O-CH2CH2)4-, R 1 -(O-CH2CH2)5- and R 1 -(O-CH2CH2) 6 -, n-Ci 2 H 25 -(O-CH2CH2)z-, n- Ci 4 H 29 -(O-CH2CH2)z-, n-Ci 6 H 33 -( 0 -CH2CH2) Z _ and n-Ci 8 H 37 -(O-CH2CH2)z _ with z equal to 4 to 25 .
Bevorzugt handelt es sich bei Rest R6 um lineare oder ver zweigte Alkylreste mit 1 bis 18 Kohlenstoffatomen oder um durch Sauerstoff unterbrochene Alkylreste mit 10 bis 68 Kohlenstoff atomen. The R 6 radical is preferably a linear or branched alkyl radical having 1 to 18 carbon atoms or an oxygen-interrupted alkyl radical having 10 to 68 carbon atoms.
Beispiele für erfindungsgemäß eingesetzte Phosphorverbindungen (Y) sind Alkylphosphonsäuren wie Butylphosphonsäure, s-Butylphosphonsäure, i-Butylphosphonsäure, tert.-Butylphos phonsäure, n-Pentylphosphonsäure, n-Hexylphosphonsäure, n- Heptylphosphonsäure, n-Octylphosphonsäure, n-Nonylphosphon- säure, n-Decylphosphonsäure, n-Undecylphosphonsäure, n-Dode- cylphosphonsäure, n-Tridecylphosphonsäure, n-Tetratedylphos- phonsäure, n-Pentadecylphosphonsäure, n-Hexadecylphosphonsäure,
Benzylphosphonsäure, 2-Phenylethylphosphonsäure, Arylphosphon- säuren wie Phenylphosphonsäure, 1-Naphthylphosphonsäure, Phos phorsäuremonoester wie Methylphosphat, Ethylphosphat, n-Propyl- phosphat, i-Propylphosphat, n-Butylphosphat, n-Pentylphosphat, n-Hexylphosphat, n-Heptylphosphat, n-Octylphosphat, 2-Ethylhe- xylphosphat, n-Decylphosphat, n-Dodecylphosphat, n-Tetradecylphosphat, n-Hexadecylphosphat, Phosphorsäurediester wie Dimethylphosphat, Diethylphosphat, Di-n-Butylphosphat, Di- n-Hexylphosphat, Di-n-Octylphosphat, Di-2-Ethylhexylphosphat, Di-n-Decylphosphat, Di-n-Dodecylphosphat, Di-n-Tetradecylphos- phat, Di-n-Hexadecylphosphat, Polyoxyethylenalkylphosphate wie Polyoxyethylenlaurylphosphat , Polyoxyethylencetylphosphat, Po- lyoxyethylenstearylphosphat , jeweils mit 4 bis 25 Oxyethylen- einheiten. Examples of phosphorus compounds (Y) used according to the invention are alkylphosphonic acids such as butylphosphonic acid, s-butylphosphonic acid, i-butylphosphonic acid, tert-butylphosphonic acid, n-pentylphosphonic acid, n-hexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, n-nonylphosphonic acid, n -Decylphosphonic acid, n-undecylphosphonic acid, n-dodecylphosphonic acid, n-tridecylphosphonic acid, n-tetratedylphosphonic acid, n-pentadecylphosphonic acid, n-hexadecylphosphonic acid, Benzylphosphonic acid, 2-phenylethylphosphonic acid, arylphosphonic acids such as phenylphosphonic acid, 1-naphthylphosphonic acid, phosphoric acid monoesters such as methyl phosphate, ethyl phosphate, n-propyl phosphate, i-propyl phosphate, n-butyl phosphate, n-pentyl phosphate, n-hexyl phosphate, n-heptyl phosphate, n -octyl phosphate, 2-ethylhexyl phosphate, n-decyl phosphate, n-dodecyl phosphate, n-tetradecyl phosphate, n-hexadecyl phosphate, phosphoric acid diesters such as dimethyl phosphate, diethyl phosphate, di-n-butyl phosphate, di-n-hexyl phosphate, di-n-octyl phosphate, di -2-Ethylhexyl phosphate, di-n-decyl phosphate, di-n-dodecyl phosphate, di-n-tetradecyl phosphate, di-n-hexadecyl phosphate, polyoxyethylene alkyl phosphates such as polyoxyethylene lauryl phosphate, polyoxyethylene cetyl phosphate, polyoxyethylene stearyl phosphate, each with 4 to 25 oxyethylene units.
Bevorzugt handelt es sich bei den erfindungsgemäß eingesetzten Phosphorverbindungen (Y) um Alkylphosphonsäuren mit 4 bis 18 Kohlenstoffatomen, besonders bevorzugt um n-Octylphosphonsäure. The phosphorus compounds (Y) used according to the invention are preferably alkylphosphonic acids having 4 to 18 carbon atoms, particularly preferably n-octylphosphonic acid.
Phosphorverbindungen (Y) sind handelsübliche Produkte. Bei spielsweise ist n-Octylphosphonsäure als reiner Stoff erhält lich oder auch als Lösung in Ethanol und Wasser, z.B. unter der Bezeichnung „Hostaphat OPS 100" (reines Produkt) oder „Hostaphat OPS 75" (Lösung in Ethanol und Wasser) bei Clariant. Phosphorus compounds (Y) are commercial products. For example, n-octylphosphonic acid is available as a pure substance or as a solution in ethanol and water, e.g. under the name "Hostaphat OPS 100" (pure product) or "Hostaphat OPS 75" (solution in ethanol and water) from Clariant.
Die erfindungsgemäßen Mischungen (M) enthalten Phosphorverbin dungen (Y) in Mengen von bevorzugt 10 bis 50 Gewichtsteilen, besonders bevorzugt von 25 bis 35 Gewichtsteilen, jeweils bezo gen auf 100 Gewichtsteile der Mischung (M). The mixtures (M) according to the invention contain phosphorus compounds (Y) in amounts of preferably 10 to 50 parts by weight, particularly preferably 25 to 35 parts by weight, based in each case on 100 parts by weight of the mixture (M).
Die erfindungsgemäßen Mischungen (M) enthalten bevorzugt Wasser (Z).
Die erfindungsgemäßen Mischungen (M) enthalten Wasser (Z) in Mengen von bevorzugt 0,5 bis 3,0 mol, besonders bevorzugt 1,0 bis 2,0 mol, insbesondere 1,0 bis 1,5 mol, jeweils bezogen auf 1 mol Phosphorverbindung (Y), bevorzugt n-Octylphosphonsäure. The mixtures (M) according to the invention preferably contain water (Z). The mixtures (M) according to the invention contain water (Z) in amounts of preferably 0.5 to 3.0 mol, particularly preferably 1.0 to 2.0 mol, in particular 1.0 to 1.5 mol, in each case based on 1 mol Phosphorus compound (Y), preferably n-octylphosphonic acid.
Zusätzlich zu den Komponenten (X), (Y) und (Z) können die er findungsgemäßen Mischungen (M) weitere Bestandteile enthalten, wie z.B. Alkohole, insbesondere Ethanol. In addition to the components (X), (Y) and (Z), the mixtures (M) according to the invention can contain other components, such as alcohols, in particular ethanol.
Vorzugsweise bestehen die erfindungsgemäßen Mischungen (M) zu mindestens 98 Gew.-%, besonders bevorzugt zu mindestens 99,8 Gew.-%, insbesondere zu 100 Gew.-%, aus den Komponenten (X),The mixtures (M) according to the invention preferably consist of at least 98% by weight, particularly preferably at least 99.8% by weight, in particular 100% by weight, of the components (X),
(Y) und (Z). (Y) and (Z).
Die erfindungsgemäßen Mischungen (M) sind farblose bis leicht gelbliche Flüssigkeiten oder niedrigschmelzende Feststoffe und haben einen Schmelzpunkt von bevorzugt < 35°C, besonders bevor zugt < 0°C, insbesondere < -30°C. The mixtures (M) according to the invention are colorless to slightly yellowish liquids or low-melting solids and have a melting point of preferably <35°C, particularly preferably <0°C, in particular <-30°C.
Zur Bereitung der erfindungsgemäßen Mischungen (M) können alle Bestandteile in beliebiger Reihenfolge miteinander vermischt werden. Dieses Vermischen kann bei Raumtemperatur oder erhöhter Temperatur von 30°C bis 150°C und dem Druck der umgebenden At mosphäre, also etwa 900 bis 1100 hPa, oder vermindertem Druck von 1 bis 900 hPa erfolgen. To prepare the mixtures (M) according to the invention, all the constituents can be mixed with one another in any order. This mixing can take place at room temperature or at an elevated temperature of 30° C. to 150° C. and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa, or reduced pressure of 1 to 900 hPa.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Mischungen (M) durch Ver mischen der einzelnen Bestandteile. Another subject of the invention is a process for preparing the mixtures (M) according to the invention by mixing the individual components.
Bei dem erfindungsgemäßen Verfahren wird bevorzugt Polyether (X) in einem geeigneten Gefäß vorgelegt und danach die Phos phorverbindung (Y) unter Rühren zudosiert. Dies geschieht vor-
zugsweise bei der Temperatur der Umgebung. Bevorzugt wird an schließend unter Rühren und bei vermindertem Druck von bis zu 20 mbar auf eine Temperatur von 80 bis 150°C erwärmt und ent haltene Verunreinigungen, wie Wasser und Alkohole, durch Destillation entfernt. Temperatur und verminderter Druck werden vorzugsweise solange aufrechterhalten, bis kein Destillat mehr übergeht. Anschließend wird auf Raumtemperatur abgekühlt und, falls erwünscht, eine definierte Menge Wasser (Z) zugegeben. In the process according to the invention, polyether (X) is preferably initially taken in a suitable vessel and then the phosphorus compound (Y) is metered in with stirring. This happens before preferably at the ambient temperature. Preferably, the mixture is then heated to a temperature of from 80 to 150° C., with stirring and under a reduced pressure of up to 20 mbar, and impurities present, such as water and alcohols, are removed by distillation. The temperature and reduced pressure are preferably maintained until no more distillate comes over. It is then cooled to room temperature and, if desired, a defined amount of water (Z) is added.
Das erfindungsgemäße Verfahren kann kontinuierlich, diskontinu ierlich oder semikontinuierlich nach bekannten Verfahren und unter Verwendung von bekannten Apparaturen erfolgen. The process according to the invention can be carried out continuously, batchwise or semicontinuously according to known processes and using known apparatus.
Es war nicht zu erwarten, dass sich die Phosphorverbindungen (Y) in Polyethern (X) ohne sichtbare Rückstände bis zu einer Konzentration von 50 Gew.-% auflösen lassen. Für die Verwend barkeit in der Praxis ist es notwendig, dass auch bei tiefen Temperaturen die n-Octylphosphonsäure aus der Mischung nicht auskristallisiert. Besonders überraschend war, dass der Zusatz von definierten Mengen an Wasser (Z) die Stabilität der Mi schung (M) selbst bis zu Temperaturen von -30°C nochmals deut lich verbessern. It was not to be expected that the phosphorus compounds (Y) could be dissolved in polyethers (X) without visible residues up to a concentration of 50% by weight. In order to be able to use it in practice, it is necessary that the n-octylphosphonic acid does not crystallize out of the mixture, even at low temperatures. It was particularly surprising that the addition of defined amounts of water (Z) again significantly improved the stability of the mixture (M) even down to temperatures of -30.degree.
Die erfindungsgemäßen Mischungen (M) haben den Vorteil, dass mit ihnen eine Handhabung als Flüssigkeit mit geringem Gefah renpotential ohne die Bildung unerwünschter Nebenprodukte er möglicht wird. The mixtures (M) according to the invention have the advantage that they can be handled as a liquid with a low risk potential without the formation of undesirable by-products.
Des Weiteren haben die erfindungsgemäßen Mischungen (M) den Vorteil, dass sie leicht herstellbar sind ohne Bildung uner wünschter Nebenprodukte.
Die erfindungsgemäßen Mischungen (M) haben den Vorteil, dass sie flüssig sind, auch bei niedrigen Temperaturen, und einen niedrigen Flammpunkt aufweisen. Furthermore, the mixtures (M) according to the invention have the advantage that they are easy to prepare without the formation of undesirable by-products. The mixtures (M) according to the invention have the advantage that they are liquid, even at low temperatures, and have a low flash point.
Die erfindungsgemäßen Mischungen (M) haben den Vorteil, dass sie eine hohe Lagerstabilität zeigen und eine hohe Beständig keit gegen tiefe Temperaturen haben. The mixtures (M) according to the invention have the advantage that they exhibit high storage stability and high resistance to low temperatures.
Die erfindungsgemäßen Mischungen (M) können für alle Verwen dungszwecke eingesetzt werden, für die auch bisher Phosphorver bindungen eingesetzt werden können, wie z.B. als Stabilisatoren für unter Alkoholabspaltung vernetzbare Zusammensetzungen auf der Basis von Organosiliciumverbindungen. The mixtures (M) according to the invention can be used for all purposes for which phosphorus compounds can previously also be used, such as, for example, as stabilizers for compositions based on organosilicon compounds which can be crosslinked with elimination of alcohol.
Bevorzugt werden erfindungsgemäße Mischungen (M) zur Herstel lung von vernetzbaren Zusammensetzungen auf der Basis von Orga nosiliciumverbindungen verwendet. Mixtures (M) according to the invention are preferably used for the production of crosslinkable compositions based on organosilicon compounds.
Ein weiterer Gegenstand der Erfindung sind vernetzbare Zusam mensetzungen auf der Basis von Organosiliciumverbindungen er hältlich durch Vermischen von Another object of the invention are crosslinkable co compositions based on organosilicon compounds he obtainable by mixing
(A) Organopolysiloxane der Formel (A) Organopolysiloxanes of the formula
(R70)3-aSlR3 aO (S1R4 20)nSiR3 x (OR7)3-a (V), wobei (R 7 0) 3-a SlR 3 a O (S1R 4 2 0) n SiR 3 x (OR 7 ) 3-a (V), where
R4 gleich oder verschieden sein kann und einwertige, gegebenen falls substituierte Kohlenwasserstoffreste bedeutet, R 4 may be the same or different and are monovalent, optionally substituted hydrocarbon radicals,
R7 gleich oder verschieden sein kann und einwertige, gegebenen falls substituierte Kohlenwasserstoffreste bedeutet, R 7 can be the same or different and means monovalent, optionally substituted hydrocarbon radicals,
R3 gleich oder verschieden sein kann und einwertige, gegebenen falls substituierte Kohlenwasserstoffreste bedeutet,
a gleich oder verschieden sein kann und 0 oder 1, bevorzugt 1, ist und x eine ganze Zahl von 30 bis 2000 ist, und R 3 can be the same or different and is monovalent, optionally substituted hydrocarbon radicals, a may be the same or different and is 0 or 1, preferably 1, and x is an integer from 30 to 2000, and
(B) Mischungen (M) enthaltend (B) containing mixtures (M).
(X) Polyether der allgemeinen Formel (I), (X) polyethers of general formula (I),
(Y) Phosphorverbindungen der Formel (II) und gegebenenfalls (Y) phosphorus compounds of formula (II) and optionally
(Z) Wasser. (Z) water.
Beispiele für Reste R4 und R7 sind unabhängig voneinander die für Rest R1 angegebenen Reste. Examples of radicals R 4 and R 7 are, independently of one another, the radicals specified for radical R 1 .
Bevorzugt handelt es sich bei den Resten R4 unabhängig vonei nander um einwertige Kohlenwasserstoffreste mit 1 bis 18 Koh lenstoffatomen, besonders bevorzugt um Methyl-, Vinyl- oder Phenylrest, insbesondere um den Methylrest. The radicals R 4 are preferably, independently of one another, monovalent hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably a methyl, vinyl or phenyl radical, in particular the methyl radical.
Bevorzugt handelt es sich bei den Resten R7 unabhängig vonei nander um Alkylreste mit 1 bis 12 Kohlenstoffatomen, besonders bevorzugt um Methyl-, Ethyl-, n-Propyl- oder iso-Propylreste, insbesondere um den Methyl- oder den Ethylrest. The radicals R 7 are preferably, independently of one another, alkyl radicals having 1 to 12 carbon atoms, particularly preferably methyl, ethyl, n-propyl or isopropyl radicals, in particular the methyl or ethyl radical.
Beispiele für Reste R3 sind die für R1 angegebenen einwertigen Kohlenwasserstoffreste sowie mit Aminogruppen substituierte Kohlenwasserstoffreste . Examples of radicals R 3 are the monovalent hydrocarbon radicals specified for R 1 and hydrocarbon radicals substituted with amino groups.
Bevorzugt handelt es sich bei Rest R3 um einwertige, gegebenen falls mit Aminogruppen substituierte Kohlenwasserstoffreste mit 1 bis 12 Kohlenstoffatomen, besonders bevorzugt um Methylrest, Ethylrest, Vinylrest, Phenylrest, Rest -CH2-NR6'R5' oder den Rest -CH2NR11', wobei R5' Kohlenwasserstoffreste mit 1 bis 12
Kohlenstoffatomen bedeutet, R6'Wasserstoffatom oder Rest R5' be deutet und R11'zweiwertige Kohlenwasserstoffreste, die mit He teroatomen unterbrochen sein können, bedeutet. The R 3 radical is preferably a monovalent, optionally amino-substituted hydrocarbon radical having 1 to 12 carbon atoms, particularly preferably a methyl radical, ethyl radical, vinyl radical, phenyl radical, -CH2-NR 6 'R 5 ' radical or the -CH2NR 11 radical ', where R 5 ' are hydrocarbon radicals with 1 to 12 Carbon atoms, R 6 'hydrogen atom or radical R 5 ' means and R 11 'divalent hydrocarbon radicals which can be interrupted with He teroatomen means.
Besonders bevorzugt handelt es sich bei Rest R3 um Rest -CH2- NR6'R5' oder Rest -CH2NR11'mit R5', R6' und R11' gleich der oben genannten Bedeutung, insbesondere um -CH2-N [(CH2)2]2O, -CH2- N (Bu)2 oder -CH2-NH (cHex), wobei Bu n-Butylrest und cHex Cyclo- hexylrest bedeutet. The R 3 radical is particularly preferably a -CH 2 -NR 6 'R 5 ' radical or a -CH 2 NR 11 ' radical with R 5 ', R 6 ' and R 11 ' having the same meaning as mentioned above, in particular - CH 2 -N [(CH 2 ) 2 ] 2 O, -CH 2 -N(Bu) 2 or -CH 2 -NH (cHex), where Bu is n-butyl and cHex is cyclohexyl.
Beispiele für Reste R5'sind die für R1 angegebenen Kohlenwas serstoffreste . Examples of radicals R 5 'are the hydrocarbon radicals specified for R 1 .
Bevorzugt handelt es sich bei Rest R5'um den Methyl-, Ethyl-, iso-Propyl-, n-Propyl-, n-Butyl-, cyclo-Hexyl- oder Phenylrest, besonders bevorzugt um den n-Butylrest. The radical R 5 'is preferably the methyl, ethyl, isopropyl, n-propyl, n-butyl, cyclohexyl or phenyl radical, particularly preferably the n-butyl radical.
Beispiele für Kohlenwasserstoffreste R6'sind die für R1 angege benen Kohlenwasserstoffreste. Examples of hydrocarbon radicals R 6 'are the hydrocarbon radicals specified for R 1 .
Bevorzugt handelt es sich bei Rest R6'um Wasserstoffatom, den Methyl-, Ethyl-, iso-Propyl-, n-Propyl-, n-Butyl- oder cyclo- Hexylrest, besonders bevorzugt um den n-Butylrest. The radical R 6 'is preferably a hydrogen atom, the methyl, ethyl, isopropyl, n-propyl, n-butyl or cyclohexyl radical, particularly preferably the n-butyl radical.
Beispiele für zweiwertige Reste R11'sind die für R2 angegebenen Beispiele sowie Reste -CH2-CH2-O-CH2-CH2- und -CH2-CH2-NH-CH2-CH2-. Examples of divalent radicals R 11 'are the examples given for R 2 and radicals -CH 2 -CH 2 -O-CH 2 -CH 2 - and -CH 2 -CH 2 -NH-CH 2 -CH 2 -.
Bevorzugt handelt es sich bei Rest R11'um zweiwertige Kohlen wasserstoffreste mit 4 bis 6 Kohlenstoffatomen, die mit Hete roatomen, bevorzugt Sauerstoff -0- oder Stickstoff -NH-, unter brochen sein können, besonders bevorzugt um -CH2-CH2-O-CH2-CH2-.
Bevorzugt handelt es sich bei den erfindungsgemäß eingesetzten Organopolysiloxanen (A) um (MeO)2Si(Ox)0(SiMe20)30-2000S1(Ox)(OMe)2, The radical R 11 'is preferably a divalent hydrocarbon radical having 4 to 6 carbon atoms which can be interrupted by heteroatoms, preferably oxygen -O- or nitrogen -NH-, particularly preferably -CH 2 -CH 2 - O- CH2 - CH2- . The organopolysiloxanes (A) used according to the invention are preferably (MeO) 2 Si(Ox)0(SiMe 2 0) 30-2000 S1(Ox)(OMe) 2 ,
(MeO)2Si(DBA)0(SiMe20)30-2000S1(DBA)(OMe)2, (MeO) 2Si (DBA)0(SiMe20)30-2000S1(DBA)(OMe )2 ,
(MeO)2Si(cHx)0(SiMe20)30-2000S1(cHx)(OMe)2, (MeO) 2 Si(cHx)0(SiMe 2 0)30-2000S1(cHx)(OMe) 2 ,
(MeO)2Si(R3)0(SiMe20)700S1(R3)(OMe)2, (MeO) 2 Si(R 3 )0(SiMe 2 0)700S1(R 3 )(OMe) 2 ,
(EtO)2Si(Ox)0(SiMe20)30-2000S1(Ox)(OEt)2, (EtO) 2 Si(Ox)0(SiMe 2 0)30-2000S1(Ox)(OEt) 2 ,
(EtO)2Si(DBA)0(SiMe20)30-2000S1(DBA)(OEt)2, (EtO) 2 Si(DBA)0(SiMe 2 0)30-2000S1(DBA)(OEt) 2 ,
(EtO)2Si(cHx)0(SiMe20)30-2000S1(cHx)(OEt)2 oder (EtO)2Si(R3)0(SiMe20)700S1(R3)(OEt)2, besonders bevorzugt um (EtO) 2 Si(cHx)0(SiMe 2 0)30-2000S1(cHx)(OEt) 2 or (EtO) 2 Si(R 3 )0(SiMe 2 0)700S1(R 3 )(OEt) 2 , particularly preferably around
(EtO)2Si(Ox)0(SiMe20)30-2000S1(Ox)(OEt)2, (EtO) 2 Si(Ox)0(SiMe 2 0)30-2000S1(Ox)(OEt) 2 ,
(EtO)2Si(DBA)0(SiMe20)30-2000S1(DBA)(OEt)2 oder (EtO)2Si(cHx)0(SiMe20)30-2000S1(cHx)(OEt)2, insbesondere um (EtO)2Si(Ox)0(SiMe20)30-2000S1(Ox)(OEt)2, worin Me gleich Methylrest, Et gleich Ethylrest, Ox gleich -CH2-N [(CH2) 2]20, DBA gleich -CH2-N (nBu)2, cHx gleich -CH2-NH (cHex), Bu gleich n-Butylrest und cHex gleich Cyclohexylrest ist sowie R3 Me, Et, Vinylrest, Phenylrest, DBA, Ox oder cHx bedeutet, wobei die Reste R3 innerhalb der einzel nen Verbindungen eine identische Bedeutung haben. (EtO) 2 Si(DBA)0(SiMe 2 0)30-2000S1(DBA)(OEt) 2 or (EtO) 2 Si(cHx)0(SiMe 2 0)30-2000S1(cHx)(OEt) 2 , in particular (EtO) 2 Si(Ox)0(SiMe 2 0)30-2000S1(Ox)(OEt) 2 where Me is methyl radical, Et is ethyl radical, Ox is -CH 2 -N [(CH 2) 2 ] 2 0, DBA is -CH 2 -N(nBu) 2 , cHx is -CH 2 -NH (cHex), Bu is n-butyl and cHex is cyclohexyl, and R 3 is Me, Et, vinyl, phenyl, DBA, Ox or cHx, where the R 3 radicals within the individual compounds have an identical meaning.
Die erfindungsgemäß eingesetzten Organopolysiloxane (A) haben eine Viskosität von bevorzugt 6000 bis 350000 mPas, besonders bevorzugt von 20000 bis 120000 mPas, jeweils bei 25°C. The organopolysiloxanes (A) used according to the invention have a viscosity of preferably from 6,000 to 350,000 mPas, particularly preferably from 20,000 to 120,000 mPas, in each case at 25.degree.
Bei den Organopolysiloxanen (A) handelt es sich um handelsübli che Produkte bzw. können sie nach einer unten beschriebenen Me thode hergestellt werden. The organopolysiloxanes (A) are commercially available products or they can be prepared by a method described below.
Bevorzugt handelt es sich bei der erfindungsgemäß eingesetzten Komponente (B) um Mischungen (M), die Wasser (Z) enthalten.
Die erfindungsgemäßen Zusammensetzungen enthalten Komponente (B) in Mengen von bevorzugt 0,001 bis 5 Gewichtsteilen, beson ders bevorzugt von 0,01 bis 5 Gewichtsteilen, insbesondere von 0,1 bis 1 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Komponente (A). The component (B) used according to the invention is preferably a mixture (M) which comprises water (Z). The compositions according to the invention contain component (B) in amounts of preferably 0.001 to 5 parts by weight, more preferably 0.01 to 5 parts by weight, in particular 0.1 to 1 part by weight, based in each case on 100 parts by weight of component (A).
Die erfindungsgemäßen Zusammensetzungen können neben den Silo xanen (A) und (B) eine Komponente (C) bestehend aus Silanen der Formel In addition to the siloxanes (A) and (B), the compositions according to the invention can contain a component (C) consisting of silanes of the formula
(R80)4-bSiR9 b (VI) und/oder deren Teilhydrolysaten enthalten, wobei b gleich 0, 1 oder 2, bevorzugt 0 oder 1, ist, (R 8 0) 4-b SiR 9 b (VI) and/or their partial hydrolyzates, where b is 0, 1 or 2, preferably 0 or 1,
R8 gleich oder verschieden sein kann und einwertige, gegebenen falls substituierte Kohlenwasserstoffreste bedeutet und R9 einwertige, gegebenenfalls substituierte Kohlenwasserstoff reste bedeutet. R 8 can be the same or different and is monovalent, optionally substituted hydrocarbon radicals and R 9 is monovalent, optionally substituted hydrocarbon radicals.
Bevorzugt handelt es sich bei Rest R8 um Alkylreste mit 1 bis 12 Kohlenstoffatomen, besonders bevorzugt um Methyl-, Ethyl-, n-Propyl- oder iso-Propylreste, insbesondere um den Methyl- o- der den Ethylrest. The radical R 8 is preferably an alkyl radical having 1 to 12 carbon atoms, particularly preferably a methyl, ethyl, n-propyl or isopropyl radical, in particular the methyl or ethyl radical.
Bevorzugt handelt es sich bei Rest R9 um einwertige, gegebenen falls mit Glycidoxy-, Ureido-, Methacryloxy- oder Aminogruppen substituierte Kohlenwasserstoffreste mit 1 bis 18 Kohlenstoff atomen, besonders bevorzugt um Alkylreste, den Vinyl- oder den Phenylrest, insbesondere um den Methylrest oder den 2,2,4-Tri- methylpentylrest . The radical R 9 is preferably a monovalent hydrocarbon radical having 1 to 18 carbon atoms which is optionally substituted by glycidoxy, ureido, methacryloxy or amino groups, particularly preferably alkyl radicals, the vinyl radical or the phenyl radical, in particular the methyl radical or the 2,2,4-trimethylpentyl radical.
In einer bevorzugten Ausführungsform werden als Komponente (C) ganz oder zum Teil Silane und/oder deren Teilhydrolysate mit
funktionellen Gruppen eingesetzt, wie beispielsweise solche mit Glycidoxypropyl-, Aminopropyl-, Aminoethylaminpropyl-, Ureidop- ropyl- oder Methacryloxypropylresten, insbesondere dann, wenn haftvermittelnde Eigenschaften erwünscht werden. In a preferred embodiment, silanes and/or their partial hydrolyzates are used in whole or in part as component (C). functional groups are used, such as those with glycidoxypropyl, aminopropyl, aminoethylaminopropyl, ureidopropyl or methacryloxypropyl radicals, especially when adhesion-promoting properties are desired.
Bei den gegebenenfalls eingesetzten Teilhydrolysaten (C) kann es sich um Teilhomohydrolysate handeln, d.h. Teilhydrolysate von einer Art von Silanen der Formel (III), wie auch um Teil- cohydrolysate, d.h. Teilhydrolysate von mindestens zwei ver schiedenen Arten von Silanen der Formel (III). The partial hydrolyzates (C) used if appropriate can be partial homohydrolysates, i.e. partial hydrolysates of one type of silanes of the formula (III), or partial cohydrolysates, i.e. partial hydrolysates of at least two different types of silanes of the formula (III) .
Unter dem Begriff Teilhydrolysate sind im Sinne der Erfindung Produkte zu verstehen, die durch Hydrolyse und/oder Kondensa tion entstanden sind. For the purposes of the invention, the term partial hydrolyzates is understood to mean products which have arisen by hydrolysis and/or condensation.
Handelt es sich bei der in den erfindungsgemäßen Massen gegebe nenfalls eingesetzten Komponente (C) um Teilhydrolysate von Si lanen der Formel (VI), so sind solche mit bis zu 20 Silicium atomen bevorzugt. If the component (C) optionally used in the compositions according to the invention is a partial hydrolyzate of silanes of the formula (VI), those having up to 20 silicon atoms are preferred.
Beispiele für erfindungsgemäß gegebenenfalls eingesetzte Kompo nente (C) sind Methyltrimethoxysilan, Vinyltrimethoxysilan, Phenyltrimethoxysilan, 2,2,4-Trimethylpentyltrimethoxysilan, Methyltriethoxysilan, Vinyltriethoxysilan, Phenyltriethoxy- silan, Tetraethoxysilan, 2,2,4-Trimethylpentyltriethoxysilan, (2,3,5,6-Tetrahydro-l,4-oxazin-4-yl)methyltriethoxysilan, N,N- Di-n-butylaminomethyltriethoxysilan, N-Cyclohexylamionomethyl- triethoxysilan, (2,3,5,6-Tetrahydro-l,4-oxazin-4-yl)methyltri methoxysilan N,N-Di-n-butylaminomethyltrimethoxysilan, N-Cyclo- hexylamionomethyltrimethoxysilan, wobei Methyltrimethoxysilan, Vinyltriethoxysilan, Tetraethoxysilan, 2,2,4-Trimethylpentyl- trimethoxysilan, (2,3,5,6-Tetrahydro-l,4-oxazin-4-yl)methyl triethoxysilan bevorzugt sind.
Bei Komponente (C) handelt es sich um handelsübliche Produkte bzw. können sie nach in der Siliciumchemie gängigen Methoden hergestellt werden. Examples of component (C) optionally used according to the invention are methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, tetraethoxysilane, 2,2,4-trimethylpentyltriethoxysilane, (2,3,5, 6-Tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane, N,N-di-n-butylaminomethyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, (2,3,5,6-Tetrahydro-1,4-oxazine-4 -yl)methyltrimethoxysilane N,N-di-n-butylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltrimethoxysilane, where methyltrimethoxysilane, vinyltriethoxysilane, tetraethoxysilane, 2,2,4-trimethylpentyltrimethoxysilane, (2,3,5,6-tetrahydro-l ,4-oxazin-4-yl)methyltriethoxysilane are preferred. Component (C) is a commercially available product or it can be prepared by methods customary in silicon chemistry.
Falls die erfindungsgemäßen Zusammensetzungen Komponente (C) enthalten, handelt es sich um Mengen von bevorzugt 0,01 bis 5 Gewichtsteilen, besonders bevorzugt von 0,01 bis 2 Gewichtstei len, insbesondere von 0,05 bis 2 Gewichtsteilen, jeweils bezo gen auf 100 Gewichtsteile Komponente (A). Die erfindungsgemäßen Zusammensetzungen enthalten bevorzugt Komponente (C), wobei diese bevorzugt zumindest zum Teil Silane und/oder deren Teil- hydrolysate mit funktionellen Gruppen enthält. If the compositions according to the invention contain component (C), the amounts involved are preferably from 0.01 to 5 parts by weight, particularly preferably from 0.01 to 2 parts by weight, in particular from 0.05 to 2 parts by weight, in each case based on 100 parts by weight component (A). The compositions according to the invention preferably contain component (C), which preferably contains at least some silanes and/or their partial hydrolyzates with functional groups.
Zusätzlich zu den Komponenten (A), (B) und gegebenenfalls (C) können die erfindungsgemäßen Zusammensetzungen nun alle Stoffe enthalten, die auch bisher in durch Kondensationsreaktion ver netzbaren Massen eingesetzt worden sind, wie z.B. Härtungsbe schleuniger (D), Weichmacher (E), Füllstoffe (F) und Additive (G). In addition to the components (A), (B) and optionally (C), the compositions according to the invention can now contain all substances which have also previously been used in compositions which can be crosslinked by a condensation reaction, such as, for example, curing accelerators (D), plasticizers (E) , fillers (F) and additives (G).
Als Härtungsbeschleuniger (D) können alle Härtungsbeschleuni ger, die auch bisher in durch Kondensationsreaktion vernetzbare Massen eingesetzt werden, verwendet werden. Beispiele für Här tungsbeschleuniger (D) sind Titanverbindungen, wie beispiels weise Tetrabutyl- oder Tetraisopropyltitanat, oder Titan- chelate, wie Bis(ethylacetoacetato)diisobutoxytitanium, oder organische Zinnverbindungen, wie Di-n-butylzinndilaurat und Di- n-butylzinndiacetat, Di-n-butylzinnoxid, Dimethylzinndiacetat, Dimethylzinndilaurat , Dimethylzinndineodecanoate, Dimethylzin- noxid, Di-n-octylzinndiacetat, Di-n-octylzinndilaurat, Di-n-oc- tylzinnoxid sowie Umsetzungsprodukte dieser Verbindungen mit
Alkoxysilanen, wie das Umsetzungsprodukt von Di-n-butylzinndi- acetat mit Tetraethoxysilan, wobei Di-n-octylzinndiacetat, Di-n-octylzinndilaurat, Di-n- octylzinnoxid, Umsetzungsprodukte des Di-n-butylzinndilaurats, Di-n-butylzinndiacetats oder Di-n-octylzinnoxids mit Tetra ethoxysilan, Tetrabutyltitanat, Tetraisopropyltitanat oder Bis (ethylacetoacetato)diisobutoxytitanium bevorzugt sind und Di-n-octylzinndiacetat, Di-n-octylzinndilaurat, Di-n-octylzin- noxid oder Umsetzungsprodukte des Di-n-butylzinndilaurats, Di- n-butylzinndiacetats oder Di-n-octylzinnoxids mit Tetraethoxy silan besonders bevorzugt sind. Curing accelerators (D) which can be used are all curing accelerators which have hitherto been used in compositions which can be crosslinked by a condensation reaction. Examples of curing accelerators (D) are titanium compounds, such as tetrabutyl or tetraisopropyl titanate, or titanium chelates, such as bis(ethylacetoacetato)diisobutoxytitanium, or organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, di-n -butyltin oxide, dimethyltin diacetate, dimethyltin dilaurate, dimethyltin dineodecanoate, dimethyltin noxide, di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin oxide and reaction products of these compounds with Alkoxysilanes, such as the reaction product of di-n-butyltin diacetate with tetraethoxysilane, with di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin oxide, reaction products of di-n-butyltin dilaurate, di-n-butyltin diacetate or di -n-octyltin oxide with tetra ethoxysilane, tetrabutyl titanate, tetraisopropyl titanate or bis(ethylacetoacetato)diisobutoxytitanium are preferred and di-n-octyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin- noxide or reaction products of di-n-butyltin dilaurate, di- n-butyltin diacetate or di-n-octyltin oxide with tetraethoxysilane are particularly preferred.
Falls die erfindungsgemäßen Massen Härtungsbeschleuniger (D) enthalten, handelt es sich um Mengen von vorzugsweise 0,001 bis 20 Gewichtsteilen, besonders bevorzugt 0,001 bis 1 Gewichts teilen, jeweils bezogen auf 100 Gewichtsteile Bestandteil (A). If the compositions according to the invention contain curing accelerators (D), the amounts involved are preferably 0.001 to 20 parts by weight, particularly preferably 0.001 to 1 part by weight, based in each case on 100 parts by weight of component (A).
Beispiele für gegebenenfalls eingesetzte Weichmacher (E) sind bei Raumtemperatur flüssige, durch Trimethylsiloxygruppen end blockierte Dimethylpolysiloxane, insbesondere mit Viskositäten bei 25°C im Bereich zwischen 5 und 1000 mPas, sowie hochsie dende Kohlenwasserstoffe, wie zum Beispiel Paraffinöle oder Mi neralöle bestehend aus naphthenischen und paraffinischen Ein heiten. Examples of plasticizers (E) which may be used are dimethylpolysiloxanes which are liquid at room temperature and end-capped by trimethylsiloxy groups, in particular with viscosities at 25° C. in the range between 5 and 1000 mPas, and high-boiling hydrocarbons, such as paraffin oils or mineral oils consisting of naphthenic and paraffinic units.
Falls die erfindungsgemäßen Massen Komponente (E) enthalten, handelt es sich um Mengen von vorzugsweise 5 bis 30 Gewichts teilen, bevorzugt 5 bis 25 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Siloxane (A). Bevorzugt enthalten die erfin dungsgemäßen Zusammensetzungen keinen Weichmacher (E).
Bei den in den erfindungsgemäßen Massen gegebenenfalls einge setzten Füllstoffen (F) kann es sich um beliebige, bisher be kannte Füllstoffe handeln. If the compositions according to the invention contain component (E), the amounts involved are preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, based in each case on 100 parts by weight of siloxanes (A). The compositions according to the invention preferably contain no plasticizer (E). The fillers (F) optionally used in the compositions according to the invention can be any previously known fillers.
Beispiele für gegebenenfalls eingesetzte Füllstoffe (F) sind nicht verstärkende Füllstoffe (F), also Füllstoffe mit einer BET-Oberflache von bis zu 20 m2/g, wie Quarz, Diatomeenerde, Calciumsilikat, Zirkoniumsilikat, Zeolithe, Metalloxidpulver, wie Aluminium-, Titan-, Eisen- oder Zinkoxide bzw. deren Mischoxide, Bariumsulfat, Calciumcarbonat, Gips, Silicium nitrid, Siliciumcarbid, Bornitrid, Glas- und Kunststoffpulver, wie Polyacrylnitrilpulver; verstärkende Füllstoffe, also Füll stoffe mit einer BET-Oberfläche von mehr als 20 m2/g, wie ge fällte Kreide und Ruß, wie Furnace- und Acetylenruß; Kiesel säure, wie pyrogen hergestellte Kieselsäure und gefällte Kie selsäure; faserförmige Füllstoffe, wie Kunststofffasern. Examples of optionally used fillers (F) are non-reinforcing fillers (F), ie fillers with a BET surface area of up to 20 m 2 /g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders such as aluminum, titanium -, Iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders such as polyacrylonitrile powder; reinforcing fillers, ie fillers with a BET surface area of more than 20 m 2 /g, such as precipitated chalk and carbon black, such as furnace and acetylene black; Silicic acid, such as pyrogenically produced silicic acid and precipitated silicic acid; fibrous fillers such as plastic fibers.
Bevorzugt handelt es sich bei den gegebenenfalls eingesetzten Füllstoffen (F) um Calciumcarbonat oder Kieselsäure, besonders bevorzugt um Kieselsäure oder ein Gemisch aus Kieselsäure und Calciumcarbonat . The optionally used fillers (F) are preferably calcium carbonate or silicic acid, particularly preferably silicic acid or a mixture of silicic acid and calcium carbonate.
Bevorzugte Calciumcarbonat-Typen (F) sind gemahlen oder gefällt und gegebenenfalls oberflächenbehandelt mit Fettsäuren wie Ste arinsäure oder deren Salze. Bei der bevorzugten Kieselsäure handelt es sich bevorzugt um pyrogene Kieselsäure. Preferred types of calcium carbonate (F) are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or salts thereof. The preferred silica is preferably fumed silica.
Falls die erfindungsgemäßen Massen Füllstoffe (F) enthalten, handelt es sich um Mengen von vorzugsweise 10 bis 150 Gewichts teilen, besonders bevorzugt 10 bis 130 Gewichtsteilen, insbe sondere 10 bis 100 Gewichtsteilen, jeweils bezogen auf 100 Ge wichtsteile Organopolysiloxane (A). Die erfindungsgemäßen Mas sen enthalten bevorzugt Füllstoff (F).
Beispiele für Additive (G) sind Pigmente, Farbstoffe, Riech stoffe, Oxidationsinhibitoren, Mittel zur Beeinflussung der elektrischen Eigenschaften, wie leitfähiger Ruß, flammabweisend machende Mittel, Lichtschutzmittel, Biozide wie Fungizide, Bac- tericide und Acarizide, zellenerzeugende Mittel, z.B. Azodicar- bonamid, Hitzestabilisatoren, Scavenger, wie Si-N enthaltende Silazane oder Silylamide, z.B. N,N'-Bis-trimethylsilyl-harn- stoff oder Hexamethyldisilazan, Cokatalysatoren, Thixotropier- mittel, wie beispielsweise einseitig oder beidseitig OH-endter- miniertes Polyethylenglykol oder gehärtetes Rizinusöl, Mittel zur weiteren Regulierung des Moduls wie Polydimethylsiloxane mit einer OH-Endgruppe, sowie beliebige Siloxane, die unter schiedlich zu Komponenten (A), (B) und (C) sind. If the compositions according to the invention contain fillers (F), the amounts involved are preferably 10 to 150 parts by weight, particularly preferably 10 to 130 parts by weight, in particular 10 to 100 parts by weight, based in each case on 100 parts by weight of organopolysiloxanes (A). The compositions according to the invention preferably contain filler (F). Examples of additives (G) are pigments, dyes, fragrances, oxidation inhibitors, agents for influencing the electrical properties, such as conductive carbon black, flame retardants, light stabilizers, biocides such as fungicides, bactericides and acaricides, cell-generating agents, for example azodicarbonamide , Heat stabilizers, scavengers, such as Si-N-containing silazanes or silylamides, for example N,N'-bis-trimethylsilylurea or hexamethyldisilazane, cocatalysts, thixotropic agents, such as polyethylene glycol end-terminated on one or both sides or hydrogenated castor oil , Agents to further regulate the modulus such as polydimethylsiloxanes with an OH end group, as well as any siloxanes that are different from components (A), (B) and (C).
Abhängend von Art und Menge der als Komponente (B) erfindungs gemäß eingesetzten Mischung (M) kann auf den Zusatz von Thixo- tropiermitteln (G) verzichtet werden. Depending on the type and amount of the mixture (M) used according to the invention as component (B), the addition of thixotropic agents (G) can be dispensed with.
Bei den einzelnen Bestandteilen der erfindungsgemäßen Massen kann es sich jeweils um eine Art eines solchen Bestandteils wie auch um ein Gemisch aus mindestens zwei verschiedenen Arten derartiger Bestandteile handeln. The individual components of the compositions according to the invention can each be one type of such a component or a mixture of at least two different types of such components.
Bevorzugt handelt es sich bei den erfindungsgemäßen Zusammen setzungen um solche, die The compositions according to the invention are preferably those which
(A) Organopolysiloxane der Formel (V), (A) organopolysiloxanes of formula (V),
(B) Mischungen (M), gegebenenfalls (C) Silane der Formel (VI) und/oder deren Teil- hydrolysate, gegebenenfalls (D) Härtungsbeschleuniger, gegebenenfalls (E) Weichmacher, gegebenenfalls (F) Füllstoffe und
gegebenenfalls (G) Additive enthalten. (B) Mixtures (M), optionally (C) silanes of the formula (VI) and/or their partial hydrolyzates, optionally (D) curing accelerators, optionally (E) plasticizers, optionally (F) fillers and optionally (G) contain additives.
Besonders bevorzugt handelt es sich bei den erfindungsgemäßen Zusammensetzungen um solche, die The compositions according to the invention are particularly preferably those which
(A) Organopolysiloxane der Formel (V), (A) organopolysiloxanes of formula (V),
(B) Mischungen (M), (B) mixtures (M),
(C) Silane der Formel (VI) und/oder deren Teilhydrolysate, gegebenenfalls (D) Härtungsbeschleuniger, gegebenenfalls (E) Weichmacher, gegebenenfalls (F) Füllstoffe und gegebenenfalls (G) Additive enthalten. (C) silanes of the formula (VI) and/or their partial hydrolyzates, optionally (D) curing accelerators, optionally (E) plasticizers, optionally (F) fillers and optionally (G) additives.
Insbesondere handelt es sich bei den erfindungsgemäßen Zusam mensetzungen um solche, die In particular, the compositions according to the invention are those that
(A) Organopolysiloxane der Formel (V), (A) organopolysiloxanes of formula (V),
(B) Mischungen (M), (B) mixtures (M),
(C) Silane der Formel (VI) und/oder deren Teilhydrolysate,(C) silanes of the formula (VI) and/or their partial hydrolyzates,
(D) Härtungsbeschleuniger, (D) curing accelerator,
(F) Füllstoffe, gegebenenfalls (E) Weichmacher und gegebenenfalls (G) Additive enthalten. (F) fillers, optionally (E) plasticizers and optionally (G) additives.
Die erfindungsgemäßen Massen enthalten außer den Komponenten (A) bis (G) bevorzugt keine weiteren Bestandteile. Apart from components (A) to (G), the compositions according to the invention preferably contain no further constituents.
Bei den erfindungsgemäßen Zusammensetzungen handelt es sich be vorzugt um zähflüssig bis pastöse Massen. The compositions according to the invention are preferably viscous to pasty masses.
Zur Bereitung der erfindungsgemäßen Massen können alle Bestand teile in beliebiger Reihenfolge miteinander vermischt werden.
Dieses Vermischen kann bei Raumtemperatur und dem Druck der um gebenden Atmosphäre, also etwa 900 bis 1100 hPa, erfolgen. To prepare the compositions according to the invention, all of the components can be mixed together in any order. This mixing can take place at room temperature and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa.
Falls erwünscht, kann dieses Vermischen aber auch bei höheren Temperaturen erfolgen, z.B. bei Temperaturen im Bereich von 35 bis 135°C. Weiterhin ist es möglich, zeitweilig oder ständig unter vermindertem Druck zu mischen, wie z.B. bei 30 bis 500 hPa Absolutdruck, um unerwünschte flüchtige Verbindungen oder Luft zu entfernen). However, if desired, this mixing can also be carried out at higher temperatures, e.g., at temperatures in the range of from 35 to 135°C. Furthermore, it is possible to mix intermittently or continuously under reduced pressure (e.g. at 30 to 500 hPa absolute pressure to remove unwanted volatile compounds or air).
Das erfindungsgemäße Vermischen findet bevorzugt unter weitest gehendem Ausschluss von Wasser aus der Atmosphäre statt. Alle Rohstoffe mit Ausnahme von (M) haben einen Wassergehalt von vorzugsweise weniger als 10000 mg/kg, bevorzugt von weniger als 5000 mg/kg, insbesondere von weniger als 1000 mg/kg. Während des Mischprozesses wird bevorzugt mit trockener Luft oder Schutzgas wie Stickstoff beschleiert, wobei das jeweilige Gas einen Feuchtegehalt von vorzugsweise weniger als 10000 pg/kg, bevorzugt von weniger als 1000 pg/kg, insbesondere von weniger als 500 pg/kg, aufweist. Die Pasten werden nach dem Herstellen in handelsübliche feuchtigkeitsdichte Gebinde gefüllt, wie Kar tuschen, Schlauchbeutel, Eimer und Fässer. The mixing according to the invention preferably takes place with the greatest possible exclusion of water from the atmosphere. All raw materials with the exception of (M) have a water content of preferably less than 10000 mg/kg, preferably less than 5000 mg/kg, in particular less than 1000 mg/kg. Dry air or protective gas such as nitrogen is preferably used as a blanket during the mixing process, with the respective gas having a moisture content of preferably less than 10,000 pg/kg, preferably less than 1000 pg/kg, in particular less than 500 pg/kg. After production, the pastes are filled into commercially available moisture-proof containers, such as cartridges, tubular bags, buckets and barrels.
In einer bevorzugten Verfahrensweise werden zunächst die Kompo nenten (A), gegebenenfalls (C) und (E) miteinander vermischt, danach gegebenenfalls Füllstoffe (F) zugegeben und schließlich (B) und gegebenenfalls weitere Bestandteile (D) und (G) zugege ben, wobei bevorzugt die Temperatur beim Mischen 60°C nicht übersteigt . In a preferred procedure, the components (A), optionally (C) and (E) are first mixed together, then optionally fillers (F) are added and finally (B) and optionally further components (D) and (G) are added, the temperature during mixing preferably not exceeding 60°C.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Zusammensetzungen durch Ver mischen der einzelnen Bestandteile.
Das erfindungsgemäße Verfahren kann kontinuierlich, diskontinu ierlich oder semikontinuierlich nach bekannten Verfahren und unter Verwendung von bekannten Apparaturen erfolgen. Another object of the invention is a process for preparing the compositions according to the invention by mixing the individual components. The process according to the invention can be carried out continuously, batchwise or semicontinuously according to known processes and using known apparatus.
Die erfindungsgemäßen bzw. erfindungsgemäß hergestellten Zusam mensetzungen sind unter Ausschluss von Feuchtigkeit lagerfähig und bei Zutritt von Feuchtigkeit vernetzbar. The compositions according to the invention or those produced according to the invention can be stored in the absence of moisture and can be crosslinked if moisture is present.
Für die Vernetzung der erfindungsgemäßen Zusammensetzungen reicht der übliche Wassergehalt der Luft aus. Die Vernetzung der erfindungsgemäßen Massen erfolgt vorzugsweise bei Raumtem peratur. Sie kann, falls erwünscht, auch bei höheren oder nied rigeren Temperaturen als Raumtemperatur, z.B. bei -5° bis 15°C oder bei 30°C bis 50°C und/oder mittels den normalen Wassergeh alt der Luft übersteigenden Konzentrationen von Wasser durchge führt werden. The usual water content of the air is sufficient for the crosslinking of the compositions according to the invention. The compositions according to the invention are preferably crosslinked at room temperature. If desired, it can also be carried out at temperatures higher or lower than room temperature, e.g. at -5° to 15°C or at 30°C to 50°C and/or using concentrations of water that exceed the normal water content of air will.
Vorzugsweise wird die Vernetzung bei einem Druck von 100 bis 1100 hPa, insbesondere beim Druck der umgebenden Atmosphäre, also etwa 900 bis 1100 hPa, durchgeführt. The crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Form körper, hergestellt durch Vernetzung der erfindungsgemäßen Zu sammensetzungen . A further subject of the present invention are moldings produced by crosslinking the compositions according to the invention.
Die erfindungsgemäßen Massen können für alle Verwendungszwecke eingesetzt werden, für die unter Ausschluss von Wasser lagerfä hige, bei Zutritt von Wasser bei Raumtemperatur zu Elastomeren vernetzende Massen eingesetzt werden können. The compositions according to the invention can be used for all purposes for which compositions which can be stored in the absence of water and which crosslink to form elastomers at room temperature when exposed to water can be used.
Die erfindungsgemäßen Massen eignen sich somit ausgezeichnet beispielsweise als Abdichtmassen für Fugen, einschließlich senkrecht verlaufender Fugen, und ähnlichen Leerräumen von z.B.
10 bis 40 mm lichter Weite, z.B. von Gebäuden, Land-, Wasser- und Luftfahrzeugen, oder als Klebstoffe oder Verkittungsmassen, z.B. im Fensterbau oder bei der Herstellung von Vitrinen, sowie beispielsweise zur Herstellung von Schutzüberzügen, einschließ lich solcher für der ständigen Einwirkung von Süß- oder Meer wasser ausgesetzte Oberflächen oder das Gleiten verhindernde Überzüge oder von gummielastischen Formkörpern. The compositions of the invention are therefore excellent, for example, as a sealing compound for joints, including vertical joints, and similar voids of z 10 to 40 mm clear width, e.g. of buildings, land vehicles, watercraft and aircraft, or as adhesives or cementing compounds, e.g. in window construction or in the manufacture of showcases, and for example for the production of protective coatings, including those for the constant exposure to Surfaces exposed to freshwater or seawater or coatings that prevent sliding or rubber-elastic molded bodies.
Die erfindungsgemäßen Massen haben den Vorteil, dass sie leicht herzustellen sind und sich durch eine sehr hohe Lagerstabilität auszeichnen . The masses according to the invention have the advantage that they are easy to produce and are characterized by a very high storage stability.
Des Weiteren bevorzugt können die erfindungsgemäßen Mischungen (M) als Neutralisationsmittel in Verfahren zur Herstellung von Polymeren mit hydrolysierbaren Endgruppen verwendet werden. The mixtures (M) according to the invention can furthermore preferably be used as neutralizing agents in processes for preparing polymers with hydrolyzable end groups.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Organyloxygruppen aufweisenden Organosilicium- verbindungen, dadurch gekennzeichnet, dass in einem 1. Schritt mindestens eine Silanolgruppe aufweisende Organosiliciumverbin- dung (a) mit mindestens zwei Organyloxygruppen enthaltender Verbindung (b) in Anwesenheit von stark basischen Katalysatoren (c) umgesetzt werden und in einem 2. Schritt nach erfolgter Re aktion der Hydroxylgruppen von Komponente (a) mit den Organy loxygruppen enthaltenden Verbindungen (b) die erfindungsgemäße Mischung (M) zugegeben wird. Another subject of the invention is a process for preparing organyloxy-containing organosilicon compounds, characterized in that in a 1st step at least one silanol group-containing organosilicon compound (a) with at least two organyloxy-containing compound (b) in the presence of strongly basic Catalysts (c) are reacted and, in a 2nd step, after reaction of the hydroxyl groups of component (a) with the compounds (b) containing organyloxy groups, the mixture (M) according to the invention is added.
Bei dem erfindungsgemäßen Verfahren kann es sich bei den stark basischen Katalysatoren (c) um Lithiumverbindungen, wie Lithi- umalkoxylate oder Lithiumhydroxyid, sowie Amidine oder Guani- dine handeln, wobei als Komponente (c) cyclische Guanidine be vorzugt sind, besonders bevorzugt 1,5,7-Triazabicyclo[4.4.0]- dec-5-en .
In einer bevorzugten Ausführungsform des erfindungsgemäßen Ver fahrens werden in einem 1. Schritt mindestens eine Silanolgrup- pe aufweisende Organosiliciumverbindung (a) mit mindestens zwei Organyloxygruppen enthaltender Verbindung (b) in Anwesenheit von 1,5,7-Triazabicyclo [4.4.0]dec-5-en (c) umgesetzt und in ei nem 2. Schritt erfindungsgemäße Mischung (M) zugegeben. In the process according to the invention, the strongly basic catalysts (c) can be lithium compounds, such as lithium alkoxylates or lithium hydroxide, and also amidines or guanidines, cyclic guanidines being preferred as component (c), particularly preferably 1,5 ,7-Triazabicyclo[4.4.0]dec-5-ene. In a preferred embodiment of the process according to the invention, in a 1st step, organosilicon compound (a) containing at least one silanol group is reacted with compound (b) containing at least two organyloxy groups in the presence of 1,5,7-triazabicyclo[4.4.0]dec- 5-ene (c) and, in a 2nd step, mixture (M) according to the invention was added.
Bei der erfindungsgemäß eingesetzten Komponente (a) kann es sich um beliebige, bisher bekannte Organosiliciumverbindungen mit mindestens einer Silanolgruppen handeln. Component (a) used according to the invention can be any previously known organosilicon compound having at least one silanol group.
Bevorzugt handelt es sich bei Organosiliciumverbindung (a) um mindestens zwei Silanolgruppen aufweisende Organosiliciumver bindungen. The organosilicon compound (a) is preferably an organosilicon compound having at least two silanol groups.
Bevorzugt handelt es sich bei Organosiliciumverbindung (a) um im Wesentlichen lineare Organopolysiloxane. The organosilicon compound (a) is preferably an essentially linear organopolysiloxane.
Die erfindungsgemäß eingesetzten Organosiliciumverbindungen (a) haben eine Viskosität von bevorzugt 102 bis 108 mPas, besonders bevorzugt von 1 000 bis 350 000 mPas, jeweils bei 25°C. The organosilicon compounds (a) used according to the invention have a viscosity of preferably 10 2 to 10 8 mPas, particularly preferably 1,000 to 350,000 mPas, in each case at 25.degree.
Beispiele für erfindungsgemäß eingesetzte Organosiliciumverbin dung (a) sind Examples of organosilicon compound (a) used according to the invention are
HO (Si (CH3) 20) 29-ioooSi (CH3) 2 (CH2) 3NH2, HO (Si (CH 3 ) 2 0) 29-i oooSi (CH 3 ) 2 (CH 2 ) 3 NH 2 ,
HO (Si (CH3) 20) 29-ioooSi (CH3) 2 (OH), HO(Si(CH3)20) 29-i oooSi(CH3) 2 ( OH),
HO (Si (CH3) 20) 29-ioooSi (CH3) 3, HO (Si (CH 3 ) 2 0) 29-i oooSi (CH 3 ) 3 ,
HO (Si (CH3) 20) o-iooSi (CH3) 2 (CH2) 30 (CH2CH (CH3) O) io-iooo (CH2) 3 (Si (CH3) 20) 0_ looSi (CH3)2 (OH) , HO (Si (CH 3 ) 2 0) o-iooSi (CH 3 ) 2 (CH 2 ) 3 0 (CH 2 CH (CH 3 ) O) io-iooo (CH 2 ) 3 (Si (CH 3 ) 2 0 ) 0 _ l ooSi (CH 3 ) 2 (OH) ,
HO (Si (CH3) 20) 3-5ooSi (O) 3 [ (Si (CH3) 20) 3-5ooH] 3 und HO ( Si (CH3) 20) 3-5ooSi (CH3) (0)2[ (Si (CH3) 20) 3-5ooH] 2, wobei HO (Si (CH3) 20) 30-ioooSi (CH3) 2 (CH2) 3NH2,
HO (Si(CH3) 20)30-ioooSi(CH3) 2(OH), HO(Si(CH3 )20)3-5ooSi(O)3 [ ( Si( CH3 )20 )3-5ooH]3 and HO (Si(CH3 ) 20 ) 3-5ooSi ( CH3 ) (0) 2 [ (Si (CH 3 ) 2 0) 3-5 ooH] 2 , where HO (Si (CH 3 ) 2 0) 30-i oooSi (CH 3 ) 2 (CH 2 ) 3 NH 2 , HO (Si(CH 3) 2 0) 30-i oooSi(CH 3) 2(OH),
HO (Si(CH3) 20)3o-ioooSi(CH3) 3 und HO (Si(CH 3) 2 0) 3 o-ioooSi(CH 3) 3 and
HO (Si(CH3)20)3-5ooSi(CH3)(0)2 [(Si(CH3)20)3-5ooH]2 bevorzugt und HO (Si(CH3)20)30-ioooSi(CH3)2 (OH) besonders bevorzugt sind. HO (Si(CH 3 ) 2 0) 3- 5ooSi(CH 3 )(0) 2 [(Si(CH 3 ) 2 0) 3-5 ooH] 2 preferred and HO (Si(CH 3 ) 2 0) 30 -i oooSi(CH 3 ) 2 (OH) are particularly preferred.
Komponente (a) sind handelsübliche Produkte bzw. nach in der Chemie gängigen Verfahren herstellbar. Component (a) are commercially available products or can be produced by methods customary in chemistry.
Bei der erfindungsgemäß eingesetzten Komponente (b) kann es sich um beliebige, bisher bekannte Verbindungen mit mindestens zwei Organyloxygruppen handeln, bevorzugt um Siloxane oder Silane. Component (b) used according to the invention can be any previously known compound having at least two organyloxy groups, preferably siloxanes or silanes.
Besonders bevorzugt handelt es sich bei Komponente (b) um Silane der Formel (VI) und/oder dessen Teilhydrolysate. Component (b) is particularly preferably a silane of the formula (VI) and/or its partial hydrolyzates.
Beispiele für erfindungsgemäß eingesetzte Verbindung (b) sind Methyltrimethoxysilan, Dimethyldimethoxysilan, Tetramethoxy- silan, Vinyltrimethoxysilan, Methylvinyldimethoxysilan, Methyl- triethoxysilan, Tetraethoxysilan, Phenyltrimethoxysilan, n-Bu- tyltrimethoxysilan, iso-Butyltrimethoxysilan und tert-Butyltri- methoxysilan, sowie deren Teilhydrolysate, wobei Methyltrime thoxysilan, Tetramethoxysilan, Vinyltrimethoxysilan, Methylvi nyldimethoxysilan, Methyltriethoxysilan, Tetraethoxysilan und n-Butyltrimethoxysilan bevorzugt sowie Methyltrimethoxysilan, Tetramethoxysilan, Vinyltrimethoxysilan, Tetraethoxysilan und n-Butyltrimethoxysilan besonders bevorzugt sind. Examples of compound (b) used according to the invention are methyltrimethoxysilane, dimethyldimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, methylvinyldimethoxysilane, methyltriethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane and tert-butyltrimethoxysilane, and their partial hydrolyzates, where Methyltrimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, methylvinyldimethoxysilane, methyltriethoxysilane, tetraethoxysilane and n-butyltrimethoxysilane are preferred, and methyltrimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, tetraethoxysilane and n-butyltrimethoxysilane are particularly preferred.
Komponente (b) sind handelsübliche Produkte bzw. nach in der Chemie gängigen Verfahren herstellbar.
Bei dem erfindungsgemäßen Verfahren wird Komponente (b) bevor zugt in 1 bis 100-fachem Überschuss, besonders bevorzugt in 2 bis 50-fachem molaren Überschuss, jeweils bezogen auf die mo lare Menge an Si-OH Gruppen in der Verbindung (a), eingesetzt. Component (b) are commercially available products or can be produced by methods customary in chemistry. In the process according to the invention, component (b) is preferably used in a 1-fold to 100-fold excess, particularly preferably in a 2-fold to 50-fold molar excess, based in each case on the molar amount of Si—OH groups in the compound (a). .
Bei dem erfindungsgemäßen Verfahren wird Katalysator (c) in Mengen von bevorzugt 5 bis 10000 Gew.-ppm, besonders bevorzugt 100 bis 3000 Gew.-ppm, jeweils bezogen auf die Gesamtmenge an Komponente (a) und (b), eingesetzt. In the process according to the invention, catalyst (c) is used in amounts of preferably 5 to 10,000 ppm by weight, particularly preferably 100 to 3000 ppm by weight, based in each case on the total amount of component (a) and (b).
Bei dem erfindungsgemäßen Verfahren können die einzelnen Kompo nenten in beliebiger Reihenfolge und auf bisher bekannte Art und Weise miteinander vermischt werden. Es können aus einigen Komponenten auch Vormischungen hergestellt werden, wie z.B. eine Mischung aus den Komponenten (b) und (c), die dann mit den anderen Komponenten vermischt werden. Einzelne Bestandteile können auch gleich zu Beginn oder während des Mischprozesses anwesend sein bzw. zugeführt werden. So können z.B. ein Teil der Komponente (b) oder die Zubereitung (c) auch erst 1 bis 60 Minuten nach dem Vermischen der jeweils anderen Bestandteile zugegeben werden. In the process according to the invention, the individual compo nents can be mixed with one another in any order and in a previously known manner. Premixes can also be made from some components, such as a mixture of components (b) and (c), which are then mixed with the other components. Individual components can also be present or added right at the beginning or during the mixing process. For example, part of component (b) or preparation (c) can also be added 1 to 60 minutes after the other components have been mixed.
Bei den im erfindungsgemäßen Verfahren eingesetzten Komponenten kann es sich jeweils um eine Art einer solchen Komponente wie auch um ein Gemisch aus mindestens zwei Arten einer jeweiligen Komponente handeln. The components used in the process according to the invention can each be one type of such a component or a mixture of at least two types of a respective component.
Das erfindungsgemäße Verfahren wird bevorzugt ohne zusätzliches Heizen bei Umgebungstemperaturen bzw. den Temperaturen, die sich beim Mischen der einzelnen Komponenten ergeben, durchge führt. Es handelt sich dabei bevorzugt um Temperaturen von 10 bis 60°C, besonders bevorzugt 15 bis 40°C.
Das erfindungsgemäße Verfahren wird bevorzugt beim Druck der umgebenden Atmosphäre, also 900 bis 1100 hPa, durchgeführt; es kann aber auch bei Überdruck gearbeitet werden, wie bei Drücken zwischen 1100 und 3000 hPa Absolutdruck, insbesondere bei kon tinuierlicher Arbeitsweise, wenn z.B. diese Drücke sich bei ge schlossenen Systemen durch den Druck beim Pumpen und durch den Dampfdruck der eingesetzten Materialien bei erhöhten Temperatu ren ergeben. The process according to the invention is preferably carried out without additional heating at ambient temperatures or at the temperatures which result when the individual components are mixed. The temperatures involved are preferably from 10 to 60.degree. C., particularly preferably from 15 to 40.degree. The process according to the invention is preferably carried out at the pressure of the surrounding atmosphere, ie from 900 to 1100 hPa; However, it is also possible to work at overpressure, such as at pressures between 1100 and 3000 hPa absolute pressure, in particular with continuous operation, if, for example, these pressures in closed systems are due to the pressure during pumping and the vapor pressure of the materials used at elevated temperatures result.
Das erfindungsgemäße Verfahren wird bevorzugt unter Ausschluss von Feuchtigkeit durchgeführt, wie in getrockneter Luft oder Stickstoff. The process according to the invention is preferably carried out in the absence of moisture, such as in dried air or nitrogen.
Das erfindungsgemäße Verfahren kann - falls erwünscht - unter Schutzgas, wie Stickstoff, durchgeführt werden. If desired, the process according to the invention can be carried out under an inert gas such as nitrogen.
Bei dem erfindungsgemäßen Verfahren kann nach Beendigung der Reaktion die Reaktionsmischung entflüchtigt werden, wobei die Entflüchtigung mittels Vakuum im selben Apparat oder in einem nachgeschalteten Apparat, mit oder ohne Inertgaseinspeisung, bei Raumtemperaturen oder erhöhten Temperaturen durchgeführt wird. Bei den leichtflüchtigen Bestandteilen handelt es sich bevorzugt um Alkohole, wie Methanol oder Ethanol. In the process according to the invention, after the reaction has ended, the reaction mixture can be devolatilized, the devolatilization being carried out by means of a vacuum in the same apparatus or in a downstream apparatus, with or without inert gas being fed in, at room temperatures or elevated temperatures. The volatile components are preferably alcohols, such as methanol or ethanol.
Das erfindungsgemäße Verfahren kann kontinuierlich oder diskon tinuierlich durchgeführt werden. The process according to the invention can be carried out continuously or batchwise.
Nach dem erfindungsgemäßen Verfahren kann vorteilhafterweise eine Vielzahl von Organyloxygruppen aufweisende Organosilicium- verbindungen hergestellt werden.
Das erfindungsgemäße Verfahren hat den Vorteil, dass auf einfa che Art und Weise Organyloxygruppen aufweisende Organosilicium- verbindungen hergestellt werden können. A large number of organosilicon compounds containing organyloxy groups can advantageously be prepared by the process according to the invention. The process according to the invention has the advantage that organosilicon compounds containing organyloxy groups can be prepared in a simple manner.
In den nachstehend beschriebenen Beispielen beziehen sich alle Viskositätsangaben auf eine Temperatur von 25°C. Sofern nicht anders angegeben, werden die nachstehenden Beispiele bei einem Druck der umgebenden Atmosphäre, also etwa bei 1000 hPa, und bei Raumtemperatur, also bei etwa 23°C, bzw. bei einer Tempera tur, die sich beim Zusammengeben der Reaktanden bei Raumtempe ratur ohne zusätzliche Heizung oder Kühlung einstellt, sowie bei einer relativen Luftfeuchtigkeit von etwa 50 % durchge führt. Des Weiteren beziehen sich alle Angaben von Teilen und Prozentsätzen, soweit nichts anderes angegeben ist, auf das Ge wicht. In the examples described below, all viscosity data relate to a temperature of 25°C. Unless otherwise stated, the examples below are carried out at a pressure of the surrounding atmosphere, i.e. around 1000 hPa, and at room temperature, i.e. around 23° C., or at a temperature which arises when the reactants are combined at room temperature without additional heating or cooling is set and the relative humidity is about 50%. Furthermore, unless otherwise stated, all parts and percentages are by weight.
Im Rahmen der vorliegenden Erfindung wird die dynamische Vis kosität der Organosiliciumverbindungen nach DIN 53019 gemessen. Dabei wurde bevorzugt wie folgt vorgegangen: Die Viskosität wird, sofern nicht anders angegeben, bei 25°C mittels eines Rotationsrheometers "Physica MCR 300" von der Firma Anton Paar gemessen. Dabei wird für Viskositäten von 1 bis 200 mPa -s ein koaxiales Zylinder-Messsystem (CC 27) mit einem Ring-Messspalt von 1,13 mm genutzt und für Viskositäten von größer als 200 mPa -s ein Kegel-Platte-Messsystem (Searle-System mit Messkegel CP 50-1) verwendet. Die Schergeschwindigkeit wird der Polymer viskosität angepasst (1 bis 99 mPa -s bei 100 s1; 100 bis 999 mPa -s bei 200 s1; 1000 bis 2999 mPa -s bei 120 s1; 3000 bisIn the context of the present invention, the dynamic viscosity of the organosilicon compounds is measured according to DIN 53019. The procedure was preferably as follows: unless otherwise stated, the viscosity is measured at 25° C. using a “Physica MCR 300” rotational rheometer from Anton Paar. A coaxial cylinder measuring system (CC 27) with an annular measuring gap of 1.13 mm is used for viscosities from 1 to 200 mPa -s and a cone-plate measuring system (Searle System with measuring cone CP 50-1) used. The shear rate is adjusted to the polymer viscosity (1 to 99 mPa -s at 100 s 1 ; 100 to 999 mPa -s at 200 s 1 ; 1000 to 2999 mPa -s at 120 s 1 ; 3000 to
4999 mPa -s bei 80 s1; 5000 bis 9999 mPa -s bei 62 s1; 10000 bis4999 mPa -s at 80 s 1 ; 5000 to 9999 mPa -s at 62 s 1 ; 10000 to
12499 mPa -s bei 50 s1; 12500 bis 15999 mPa -s bei 38,5 s1; 16000 bis 19999 mPa -s bei 33 s1; 20000 bis 24999 mPa -s bei 25 s1; 12499 mPa -s at 50 s 1 ; 12500 to 15999 mPa -s at 38.5 s -1 ; 16000 to 19999 mPa -s at 33 s 1 ; 20000 to 24999 mPa -s at 25 s 1 ;
25000 bis 29999 mPa -s bei 20 s1; 30000 bis 39999 mPa -s bei 17 s1; 40000 bis 59999 mPa -s bei 10 s1; 60000 bis 149999 bei 5 s1;
150000 bis 199999 mPa -s bei 3,3 s1; 200000 bis 299999 mPa -s bei 2,5 s1; 300000 bis 1000000 mPa -s bei 1,5 s1. 25000 to 29999 mPa -s at 20 s 1 ; 30000 to 39999 mPa -s at 17 s 1 ; 40000 to 59999 mPa -s at 10 s 1 ; 60000 to 149999 at 5 s 1 ; 150000 to 199999 mPa -s at 3.3 s 1 ; 200000 to 299999 mPa -s at 2.5 s 1 ; 300000 to 1000000 mPa -s at 1.5 s 1 .
Die zahlenmittlere Molmasse Mn wird dabei im Rahmen der vorlie genden Erfindung mittels Size Exclusion Chromatography (SEC) gegen Polystyrol-Standard, in THF, bei 60°C, Flow Rate 1,2 ml/min und Detektion mit RI (Brechungsindex-Detektor) auf einem Säulenset Styragel HR3-HR4-HR5-HR5 von Waters Corp. USA mit ei nem Injektionsvolumen von 100 mΐ bestimmt. In the context of the present invention, the number-average molar mass M n is determined by means of size exclusion chromatography (SEC) against a polystyrene standard, in THF, at 60° C., flow rate 1.2 ml/min and detection with RI (refractive index detector) on a Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA determined with an injection volume of 100 mΐ.
PPG 425: Polypropylenglycol mit einem mittleren Molgewicht Mn von 425 g/mol; PPG 425: Polypropylene glycol with an average molecular weight M n of 425 g/mol;
PPG 1000: Polypropylenglycol mit einem mittleren Molgewicht Mn von 1000 g/mol; PPG 1000: polypropylene glycol with an average molecular weight M n of 1000 g/mol;
PPG 400: Polypropylenglycol mit einem mittleren Molgewicht Mn von 400 g/mol; PPG 400: polypropylene glycol with an average molecular weight M n of 400 g/mol;
OPS 75: n-Octylphosphonsäure, 75 Gew.-%ig in Wasser und Ethanol (käuflich erhältlich z.B. unter der Bezeichnung „Hostaphat OPS 75" bei Clariant). OPS 75: n-octylphosphonic acid, 75% by weight in water and ethanol (commercially available, for example, under the name "Hostaphat OPS 75" from Clariant).
Beispiel 1 example 1
100g OPS 75 wurden mit 75g PPG 425 vermischt und unter vermin dertem Druck von 20 mbar bis auf 105°C erwärmt und eine Stunde bei dieser Temperatur gehalten. Dabei destilliert das Ethanol und das Wasser ab. 100 g OPS 75 were mixed with 75 g PPG 425 and heated to 105° C. under a reduced pressure of 20 mbar and kept at this temperature for one hour. In the process, the ethanol and the water are distilled off.
Es wurde eine klare Lösung erhalten, die bei 28°C beginnt zu kristallisieren und bei Raumtemperatur fest ist. A clear solution was obtained which begins to crystallize at 28°C and is solid at room temperature.
Die Ergebnisse finden sich in Tabelle 1. The results can be found in Table 1.
Beispiel 2 example 2
100g OPS 75 wurden mit 75g PPG 1000 vermischt und unter vermin dertem Druck von 20 mbar bis auf 105°C erwärmt und eine Stunde
bei dieser Temperatur gehalten. Dabei destilliert das Ethanol und das Wasser ab. 100 g OPS 75 were mixed with 75 g PPG 1000 and heated to 105° C. for one hour under a reduced pressure of 20 mbar kept at this temperature. In the process, the ethanol and the water are distilled off.
Es wurde eine klare Lösung erhalten, die bei 25°C beginnt zu kristallisieren und bei Raumtemperatur fest ist. Es konnte des- wegen keine Viskosität bei 25°C gemessen werden. A clear solution was obtained which begins to crystallize at 25°C and is solid at room temperature. Therefore, no viscosity could be measured at 25°C.
Die Ergebnisse finden sich in Tabelle 1. The results can be found in Table 1.
Beispiele 4 bis 7 Examples 4 to 7
Die in Beispiel 1 beschriebene Arbeitsweise wurde wiederholt mit den in Tabelle 1 angegeben Mengen an Einsatzstoffen. The procedure described in Example 1 was repeated using the amounts of starting materials given in Table 1.
In den Beispielen 4 und 7 wurde nach Beendigung der Destillati onsphase das Gemisch auf 80°C abgekühlt und die in der Tabelle 1 angegebenen Mengen an deionisiertem Wasser zugesetzt. Um ho- mogene Lösungen zu erhalten, wurde in diesen Fällen eine wei tere Stunde gerührt. Es wurden klare Lösungen erhalten mit den in der Tabelle 1 angegebenen Viskositäten und Temperaturen des Kristallisationsbeginns . Tabelle 1:
In Examples 4 and 7, after the end of the distillation phase, the mixture was cooled to 80° C. and the amounts of deionized water given in Table 1 were added. In these cases, stirring was continued for a further hour in order to obtain homogeneous solutions. Clear solutions were obtained with the viscosities and temperatures at the start of crystallization given in Table 1. Table 1:
* nicht messbar wegen Kristallisation
Beispiel 8 * not measurable due to crystallization example 8
Die in Beispiel 7 beschriebene Arbeitsweise wurde wiederholt mit der Abänderung, dass anstelle von PPG 425 PPG 400 verwendet wurde. Dabei wurden keinerlei Unterschiede festgestellt. Insbe sondere war der Schmelzpunkt ebenfalls kleiner -30°C. The procedure described in Example 7 was repeated with the modification that PPG 425 was used instead of PPG 400. No differences were found. In particular, the melting point was also less than -30°C.
Beispiel 9 example 9
309 g eines a,w-Bis[(tetrahydro-1,4-oxazin-4-yl)methyldiethoxy- silyl]polydimethylsiloxans mit einer Viskosität von 80000 mPa -s, 130 g eines ,w-Bis(trimethylsiloxy)polydimethylsilox ans mit einer Viskosität von 1000 mPa -s (käuflich erhältlich unter der Bezeichnung "Weichmacher 1000" bei der Wacker Chemie AG, D-München), 1 g eines Produkts welches aus 16,0 Mol-% Ein heiten der Formel MeSi(OEt)2O1/2, 46,4 Mol-% Einheiten der For mel MeSi(OEt)Q212, 36,5 Mol-% Einheiten der Formel MeSiC>3/2, 0,2 Mol-% Einheiten der Formel Me2Si(OEt)O1/2 und 0,9 Mol-% Einhei ten der Formel Me2SiC>2/2 bestand, 8 g 3-Aminopropyltriethoxy- silan (käuflich erhältlich unter der Bezeichnung GENIOSIL® GF 93 bei der Wacker Chemie AG, D-München), 2 g Vinyltriethoxy- silan (käuflich erhältlich unter der Bezeichnung GENIOSIL® GF 56 bei der Wacker Chemie AG, D-München) und 5 g Tetraethylsili- kat (käuflich erhältlich unter der Bezeichnung "Silikat TES 28" bei der Wacker Chemie AG, D-München) wurden in einem Planeten mischer vorgelegt und für eine Dauer von 30 Minuten vermischt. Anschließend wurden 45 g einer pyrogenen Kieselsäure mit einer spezifischen Oberfläche nach BET von 150 m2/g (käuflich erhält lich unter der Bezeichnung HDK® V15 bei der Wacker Chemie AG, D-München) eingemischt und bei einem Druck von 50 hPa vollstän dig homogenisiert. Zuletzt wurden 1 g der in Beispiel 1 herge stellten Mischung und 2 g eines Reaktionsproduktes aus Di- butylzinndiacetat und Tetraethoxysilan (käuflich erhältlich un ter der Bezeichnung "Katalysator 41" bei der Wacker Chemie AG,
D-München) zugegeben und nochmals 5 Minuten bei einem Druck von ca. 50 hPa (absolut) homogenisiert. 309 g of a,w-bis[(tetrahydro-1,4-oxazin-4-yl)methyldiethoxysilyl]polydimethylsiloxane with a viscosity of 80,000 mPa -s, 130 g of a,w-bis(trimethylsiloxy)polydimethylsiloxane with a Viscosity of 1000 mPa -s (commercially available under the name "Softener 1000" from Wacker Chemie AG, D-Munich), 1 g of a product which consists of 16.0 mol% units of the formula MeSi(OEt)2O1 / 2 , 46.4 mol% units of the formula MeSi(OEt)Q212, 36.5 mol% units of the formula MeSiC>3 / 2, 0.2 mol% units of the formula Me2Si(OEt)O1/2 and 0 .9 mol % units of the formula Me2SiC>2/2, 8 g 3-aminopropyltriethoxysilane (commercially available under the name GENIOSIL® GF 93 from Wacker Chemie AG, D-Munich), 2 g vinyltriethoxysilane ( commercially available under the name GENIOSIL® GF 56 from Wacker Chemie AG, D-Munich) and 5 g of tetraethyl silicate (commercially available under the name "Silikat TES 28" from Wacker Chemie AG, D-Munich) were placed in a plane ten mixer and mixed for a period of 30 minutes. Then 45 g of a pyrogenic silica with a BET specific surface area of 150 m 2 /g (commercially available under the name HDK® V15 from Wacker Chemie AG, D-Munich) were mixed in and completely homogenized at a pressure of 50 hPa . Finally, 1 g of the mixture produced in Example 1 and 2 g of a reaction product of dibutyltin diacetate and tetraethoxysilane (commercially available under the name "Katalysator 41" from Wacker Chemie AG, D-Munich) was added and the mixture was homogenized again for 5 minutes at a pressure of about 50 hPa (absolute).
Die so erhaltene RTVl-Masse wurde in feuchtigkeitsdichte han delsübliche Polyethylen-Kartuschen abgefüllt und bei Raumtempe ratur für 24h sowie eine weitere Probe bei 70°C für 7 Tage ge lagert. Danach wurden von diesen so gelagerten Proben jeweils 2mm dicke Platten ausgestrichen und 7 Tage bei 23°C und 50% re lativer Luftfeuchte gelagert. Aus den dabei ausgehärteten Mate rialien wurden Prüfkörper gemäß DIN 53504 der Form S2 ausge stanzt und die mechanischen Kennwerte gemessen. Die Ergebnisse finden sich in Tabelle 2. The RTVI mass obtained in this way was filled into moisture-proof commercially available polyethylene cartridges and stored at room temperature for 24 h and another sample at 70° C. for 7 days. Thereafter, 2 mm thick plates were spread out from each of the samples stored in this way and stored for 7 days at 23° C. and 50% relative atmospheric humidity. Test specimens in accordance with DIN 53504 of form S2 were punched out of the materials cured in the process and the mechanical parameters were measured. The results can be found in Table 2.
Beispiel 10 Example 10
Beispiel 9 wurde wiederholt mit der Abänderung, dass anstelle von lg der Mischung gemäß Beispiel 11,57g einer Mischung gemäß Beispiel 7 zugegeben wurden. Example 9 was repeated with the modification that instead of 1 g of the mixture according to example 11.57 g of a mixture according to example 7 were added.
Die Ergebnisse finden sich in Tabelle 2. The results can be found in Table 2.
Beispiel 11 Example 11
880 kg eines a,w-Dihydroxypolydimethylsiloxans mit einer Visko sität von 80000 mPa -s (käuflich erhältlich unter der Bezeich nung POLYMER FD 80 bei der Wacker Chemie AG, D-München) wurden mit einer Lösung von 91 g Triazabicyclo[4.4.0]dec-5-en in 27 kg Vinyltrimethoxysilan (käuflich erhältlich unter der Bezeichnung GENIOSIL® XL 10 bei der Wacker Chemie AG, D-München) vermischt. Nach einer Reaktionszeit von 45 min bei Raumtemperatur wurden 255 g der Mischung gemäß Beispiel 1 zugegeben und homogen ver mischt. 880 kg of an a,w-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPa -s (commercially available under the designation POLYMER FD 80 from Wacker Chemie AG, D-Munich) were mixed with a solution of 91 g of triazabicyclo[4.4.0] dec-5-ene in 27 kg of vinyltrimethoxysilane (commercially available under the name GENIOSIL® XL 10 from Wacker Chemie AG, D-Munich). After a reaction time of 45 minutes at room temperature, 255 g of the mixture according to Example 1 were added and mixed homogeneously.
Es wurde ohne weitere Aufarbeitung als ein klares farbloses Produkt ein a,w-Bis-(Vinyldimethoxysilyl)polydimethylsiloxan mit einer Viskosität von 100 Pas erhalten.
Beispiel 12 Without further processing, an a,w-bis(vinyldimethoxysilyl)polydimethylsiloxane having a viscosity of 100 Pas was obtained as a clear, colorless product. Example 12
300g des gemäß Beispiel 11 hergestellten Produktes wurden mit 130 g eines a,w-Bis(trimethylsiloxy)polydimethylsiloxans mit einer Viskosität von 1000 mPa -s (käuflich erhältlich unter der Bezeichnung "Weichmacher 1000" bei der Wacker Chemie AG, D-Mün- chen), 5 g N-(2-Aminoethyl)-3-aminopropyltrimethoxysilan (käuf lich erhältlich unter der Bezeichnung GENIOSIL® GF 91 bei der Wacker Chemie AG, D-München), 2 g Vinyltrimethoxysilan (käuf lich erhältlich unter der Bezeichnung GENIOSIL® XL 10 bei der Wacker Chemie AG, D-München) in einem Planetenmischer vorgelegt und für eine Dauer von 30 Minuten vermischt. Anschließend wur den 45 g einer pyrogenen Kieselsäure mit einer spezifischen Oberfläche nach BET von 150 m2/g (käuflich erhältlich unter der Bezeichnung HDK® V15 bei der Wacker Chemie AG, D (München) ein gemischt und bei einem Druck von 50 hPa vollständig homogeni siert. Zuletzt wurden 1 g einer Lösung gemäß Beispiel 1 und 2 g eines Reaktionsproduktes aus Dibutylzinndiacetat und Tetra- ethoxysilan (käuflich erhältlich unter der Bezeichnung "Kataly sator 41" bei der Wacker Chemie AG, D-München) zugegeben und nochmals 5 Minuten bei einem Druck von ca. 50 hPa (absolut) ho mogenisiert . 300 g of the product produced according to Example 11 were mixed with 130 g of an a,w-bis(trimethylsiloxy)polydimethylsiloxane with a viscosity of 1000 mPa -s (commercially available under the name "Softener 1000" from Wacker Chemie AG, D-Munich ), 5 g N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (commercially available under the name GENIOSIL® GF 91 from Wacker Chemie AG, D-Munich), 2 g vinyltrimethoxysilane (commercially available under the name GENIOSIL® XL 10 at Wacker Chemie AG, D-Munich) in a planetary mixer and mixed for a period of 30 minutes. Then 45 g of a pyrogenic silica with a BET specific surface area of 150 m 2 /g (commercially available under the name HDK® V15 from Wacker Chemie AG, D (Munich)) were mixed in and completely homogenized at a pressure of 50 hPa Finally, 1 g of a solution according to Example 1 and 2 g of a reaction product of dibutyltin diacetate and tetraethoxysilane (commercially available under the designation "Katalysator 41" from Wacker Chemie AG, D-Munich) were added and another 5 minutes at a Pressure of approx. 50 hPa (absolute) homogenized.
Die so erhaltene RTVl-Masse wurde in feuchtigkeitsdichte han delsübliche Polyethylen-Kartuschen abgefüllt und bei Raumtempe ratur für 24h sowie eine weitere Probe bei 70°C für 7 Tage ge lagert. Danach wurden von diesen so gelagerten Proben jeweils 2mm dicke Platten ausgestrichen und 7 Tage bei 23°C und 50% re lativer Luftfeuchte gelagert. Aus den dabei ausgehärteten Mate rialien wurden Prüfkörper gemäß DIN 53504 der Form S2 ausge stanzt und die mechanischen Kennwerte gemessen. The RTVI mass obtained in this way was filled into moisture-proof commercially available polyethylene cartridges and stored at room temperature for 24 h and another sample at 70° C. for 7 days. Thereafter, 2 mm thick plates were spread out from each of the samples stored in this way and stored for 7 days at 23° C. and 50% relative atmospheric humidity. Test specimens in accordance with DIN 53504 of form S2 were punched out of the materials cured in the process and the mechanical parameters were measured.
Die Ergebnisse finden sich in Tabelle 2.
Beispiel 13 The results can be found in Table 2. Example 13
Herstellung eines Oligomerengemischs 13a: Preparation of an oligomer mixture 13a:
240 g (3,25 mol) eines a,w-Bis(trimethylsiloxy)polydimethylsilo- xans mit einer Viskosität von 1000 mPas, 234 g (1,0 mol) Trime- thoxy (2,4,4-trimethylpentyl)silan (= iOctSi(OMe)3), erhältlich bei der Wacker Chemie AG unter der Bezeichnung SILRES® BS 1316, und 0,80 g einer Lösung von Natriumethylat (21%ig) in Ethanol werden vermischt und 4 Stunden auf 110°C erhitzt. Nach dem Ab¬ kühlen der Lösung wird die Mischung durch Zugabe von 1,60 g ei ner Lösung von Dimethyldichlorsilan (10%ig) in n-Heptan neutra lisiert. Diese Mischung wurde bei reduziertem Druck von 50 mbar bei 120°C an einem Rotationsverdampfer entflüchtigt. Die Zusam mensetzung des Gemisches wurde mittels 29-Si-NMR Spektroskopie ermittelt. Das Gemisch enthielt 1,4 Gew.-% iOctSi(OMe)3, 0,4 Gew.-% Me2Si(OMe)2 und 98,2 Gew.-% eines Oligomerengemisches der mittleren Zusammensetzung von [iOctSi(OMe)2O1/2]o,os[iO¬ ctSi (OMe)O2/2]0,15[iOctSiO3/2]0,05 [Me2S1O2/2]0,43[Me2Si(OMe)O1/2]0,29·240 g (3.25 mol) of an a,w-bis(trimethylsiloxy)polydimethylsiloxane with a viscosity of 1000 mPas, 234 g (1.0 mol) of trimethoxy(2,4,4-trimethylpentyl)silane (= iOctSi(OMe)3), available from Wacker Chemie AG under the name SILRES® BS 1316, and 0.80 g of a solution of sodium ethoxide (21%) in ethanol are mixed and heated to 110° C. for 4 hours. After the solution has been cooled, the mixture is neutralized by adding 1.60 g of a solution of dimethyldichlorosilane (10%) in n-heptane. This mixture was devolatilized at a reduced pressure of 50 mbar at 120° C. on a rotary evaporator. The composition of the mixture was determined by means of 29-Si NMR spectroscopy. The mixture contained 1.4% by weight of iOctSi(OMe)3, 0.4% by weight of Me2Si(OMe)2 and 98.2% by weight of an oligomer mixture with the average composition of [iOctSi(OMe)2O1 / 2 ]o,os[iO ¬ ctSi(OMe)O2 / 2]0.15[iOctSiO3 / 2]0.05 [Me2S1O2 / 2]0.43[Me2Si(OMe)O1 / 2]0.29
Die mittels Gelpermeationschromatographie bestimmten Molekular¬ gewichte betrugen 929 g/mol (Mw - Gewichtsmittel) und 635 (Mn - Zahlenmittel) . Die Polydispersität (Mw/Mn) war 1,46. The molecular weights determined by means of gel permeation chromatography were 929 g/mol (Mw—weight average) and 635 (Mn—number average). The polydispersity (Mw/Mn) was 1.46.
Eine Mischung aus 660 g eines a,w-Dihydroxypolydimethylsiloxans mit einer Viskosität von 80 000 mPas und 220 g eines a,w-Dihyd- roxypolydimethylsiloxans mit einer Viskosität von 20000 mPas wurden mit 30,44 g einer Lösung von 0,04 g 1,5,7-Triazabicyc- lo [4.4.0]dec-5-en in 30,4 g (2,3,5,6-Tetrahydro-l,4-oxazin-4- yl)methyltriethoxysilan für 5 Minuten bei 200 Umdrehungen/min gerührt. Nach 5 Minuten Reaktionszeit erhält man ein Gemisch aus 98,0 Gew.-% a,w-Bis((2,3,5,6-Tetrahydro-l,4-oxazin-4-yl)me- thyldiethoxysilyl)polydimethylsiloxan, 1,9 Gew.-% (2,3,5,6-Tet- rahydro-1,4-oxazin-4-yl )methyltriethoxysilan und 0,1 Gew.-% Ethanol mit einer Viskosität von 52000 mPas.
RTVl-Dichtmasse unter Verwendung des Oligomerengemisches 13a: A mixture of 660 g of a,w-dihydroxypolydimethylsiloxane with a viscosity of 80,000 mPas and 220 g of a,w-dihydroxypolydimethylsiloxane with a viscosity of 20,000 mPas were mixed with 30.44 g of a solution of 0.04 g 1, 5,7-Triazabicyclo[4.4.0]dec-5-ene in 30.4 g (2,3,5,6-Tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane for 5 minutes at 200 rpm /min stirred. After a reaction time of 5 minutes, a mixture of 98.0% by weight of a,w-bis((2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyldiethoxysilyl)polydimethylsiloxane, 1 9% by weight of (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane and 0.1% by weight of ethanol with a viscosity of 52,000 mPas. RTVL sealant using the oligomer mixture 13a:
455 g des so erhaltenen Reaktionsgemischs wurden mit 10,6 g Tetraethoxysilanhydrolysat-Oligomer mit einem Gehalt an S1O2 von 40% bei Totalhydrolyse und Kondensation, erhältlich bei der Wacker Chemie AG, D-München unter der Bezeichnung „SILIKAT TES 40", 12,6 g eines Äquilibrierungsproduktes aus 6,3 g Methyl- triethoxysilan-Hydrolysat-Oligomeren mit durchschnittlich 10 Si-Atomen pro Molekül und 6,3 g 3-Aminopropyltriethoxysilan zu gegeben und für weitere 5 Minuten bei 200 Umdrehungen/min ge rührt. Danach wurden 44 g einer hydrophilen pyrogenen Kiesel säure mit einer Oberfläche von 150 m2/g, erhältlich bei der Wa cker Chemie AG unter der Bezeichnung HDK® V15A, zugegeben und zunächst bei 200 Umdrehungen/min für weitere 5 Minuten gerührt, bis die gesamte pyrogene Kieselsäure benetzt war. Danach wurden 10 Minuten bei 600 Umdrehungen/min gerührt bei vermindertem Druck von 200 mbar. Zum Schluss wurden 1,58 g einer Lösung von 0,27 g Dioctyl-zinnoxid in 1,31 g eines Äquilibrierungsproduk tes aus 0,655 g Methyltriethoxysilan-Hydrolysat-Oligomeren mit durchschnittlich 10 Si-Atomen pro Molekül und 0,655 g 3-Aminop ropyltriethoxysilan und 2,6 des erfindungsgemäßen Zusatzes ge mäß Beispiel 7 und 25,6 g des Oligomerengemisches 13a zugegeben und weitere 5 min unter vermindertem Druck (200 mbar) gerührt. 455 g of the reaction mixture obtained in this way were treated with 10.6 g of tetraethoxysilane hydrolyzate oligomer containing 40% S1O2 in the case of total hydrolysis and condensation, available from Wacker Chemie AG, D-Munich under the name "SILIKAT TES 40", 12.6 g of an equilibration product consisting of 6.3 g of methyltriethoxysilane hydrolyzate oligomers having an average of 10 Si atoms per molecule and 6.3 g of 3-aminopropyltriethoxysilane and stirring at 200 rpm for a further 5 minutes a hydrophilic pyrogenic silica with a surface area of 150 m 2 / g, available from Wa cker Chemie AG under the designation HDK® V15A, and initially stirred at 200 revolutions / min for a further 5 minutes until the entire pyrogenic silica was wetted Thereafter, stirring was carried out for 10 minutes at 600 revolutions/min under a reduced pressure of 200 mbar Finally, 1.58 g of a solution of 0.27 g of dioctyltin oxide in 1.31 g of an equilibration product a 0.655 g of methyltriethoxysilane hydrolyzate oligomers having an average of 10 Si atoms per molecule and 0.655 g of 3-aminopropyltriethoxysilane and 2.6 of the additive according to the invention according to Example 7 and 25.6 g of the oligomer mixture 13a were added and a further 5 minutes under reduced pressure (200 mbar) stirred.
Anschließend wird die Mischung in handelsübliche Kartuschen ab gefüllt und unter Ausschluss von Feuchtigkeit gelagert. 24h nach der Herstellung der Mischungen wurden aus diesen Mischun gen 2 mm dicke Platten ausgezogen und daraus nach 7 Tagen Aus härtung bei 23°C und 50% relativer Luftfeuchte hantelförmige Prüfkörper des Typs 2 gemäß ISO 37, 6. Ausgabe 2017-11, herge stellt. The mixture is then filled into commercially available cartridges and stored away from moisture. 24 hours after the preparation of the mixtures, 2 mm thick plates were drawn out of these mixtures and, after curing for 7 days at 23°C and 50% relative humidity, dumbbell-shaped test specimens of type 2 according to ISO 37, 6th edition 2017-11, were produced .
Die Ergebnisse finden sich in Tabelle 2.
Ohne den erfindungsgemäßen Zusatz gemäß Beispiel 7 härtete eine Mischung analog Beispiel 13 nach Vorlagerung von 7 Tagen bei 70 °C nicht mehr zu einem klebfreien Material aus. Tabelle 2: Mechanische Kennwerte
The results can be found in Table 2. Without the additive according to Example 7, a mixture analogous to Example 13 no longer cured to a tack-free material after storage for 7 days at 70.degree. Table 2: Mechanical characteristics
Die Hautbildungszeiten lagen jeweils im üblichen Bereich zwi schen 15 und 25 Minuten. The skin formation times were in the usual range between 15 and 25 minutes.
Ohne die erfindungsgemäßen Zusätze härteten die Mischungen ge- mäß den Beispielen 9, 10, 12 und 13 nach Vorlagerung von 7 Ta gen bei 70 °C nicht mehr zu klebfreien Materialen aus. Without the additives according to the invention, the mixtures according to Examples 9, 10, 12 and 13 no longer cured to tack-free materials after storage for 7 days at 70.degree.
Beispiel 14 Example 14
In einem Labordissolver wurden 400 g des a,w-Dihydroxypolydime- thylsiloxans mit 8,5 g Phenyltrimethoxysilan und 0,25 g einer Lösung von 20 Ma-% 1,5,7-Triazabicyclo[4.4.0]dec-5-en in iso- Octyltriethoxysilan bei einer Ausgangstemperatur von 25°C 5 Mi nuten intensiv miteinander vermischt. Die Mischwelle mit Dis- solverzahnkranz, dessen Durchmesser ca. 5 cm betrug, wurde auf 1000 Umdrehungen je Minute eingestellt.
Dass die Mischung nach 30 Minuten frei von Silanolgruppen war, wurde mittels des in EP 2 170 995 Bl auf Seite 7 beschriebenen Titanat-Schnelltestes festgestellt. Die Endcappingreaktion war somit zu diesem Zeitpunkt bereits beendet. In a laboratory dissolver, 400 g of the a,w-dihydroxypolydimethylsiloxane were mixed with 8.5 g of phenyltrimethoxysilane and 0.25 g of a solution of 20% by mass of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in iso-octyltriethoxysilane at an initial temperature of 25° C. for 5 minutes and intensively mixed with one another. The mixing shaft with dissolver toothed ring, whose diameter was about 5 cm, was set to 1000 revolutions per minute. The rapid titanate test described on page 7 of EP 2 170 995 B1 was used to determine that the mixture was free of silanol groups after 30 minutes. The endcapping reaction was thus already over at this point in time.
Anschließend wurde 0,5 g des erfindungsgemäßen Zusatzes aus Beispiel 7 über 10 min eingemischt Then 0.5 g of the additive according to the invention from Example 7 was mixed in over 10 minutes
Viskosität nach 2 Stunden: 90,0 Pa.s Viskosität nach 22 Stunden: 85,5 Pa.s Viscosity after 2 hours: 90.0 Pa.s Viscosity after 22 hours: 85.5 Pa.s
Beispiel 15 (nicht erfindungsgemäß) Example 15 (not according to the invention)
Der Versuch 13 wurde wiederholt mit der Abänderung, dass nach träglich kein erfindungsgemäßer Zusatz eingemischt wurde. Experiment 13 was repeated with the modification that no additive according to the invention was subsequently mixed in.
Viskosität nach 2 Stunden: 89,0 Pa.s Viskosität nach 22 Stunden: 48,5 Pa.s Viscosity after 2 hours: 89.0 Pa.s Viscosity after 22 hours: 48.5 Pa.s
Es ist erkennbar, dass ohne den erfindungsgemäßen Stabilisator ein starker Viskositätsabbau stattfindet. It can be seen that without the stabilizer according to the invention, there is a strong reduction in viscosity.
Beispiel 16 Example 16
In einem Labordissolver wurden 400 g des a,w-Dihydroxypolydime- thylsiloxans mit 7 g 4-(Triethoxysilylmethyl)tetrahydro-1,4-o- xazin und 0,25 g einer Lösung von 20 Ma-% 1,5,7- Triazabicyc- lo [4.4.0]dec-5-en in iso-Octyltriethoxysilan bei einer Aus gangstemperatur von 25°C 5 Minuten intensiv miteinander ver mischt. Die Mischwelle mit Dissolverzahnkranz, dessen Durchmes ser ca. 5 cm betrug, wurde auf 1000 Umdrehungen je Minute ein gestellt. In a laboratory dissolver, 400 g of a,w-dihydroxypolydimethylsiloxane were mixed with 7 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-o-xazine and 0.25 g of a solution of 20% by mass of 1,5,7-triazabicyc - lo [4.4.0]dec-5-ene in iso-octyltriethoxysilane at an initial temperature of 25° C. for 5 minutes are intensively mixed with one another. The mixing shaft with the dissolver ring gear, the diameter of which was about 5 cm, was set to 1000 revolutions per minute.
Dass die Mischung nach 30 Minuten frei von Silanolgruppen war, wurde mittels des in EP 2 170 995 Bl auf Seite 7 beschriebenen
Titanat-Schnelltestes festgestellt. Die Endcappingreaktion war somit zu diesem Zeitpunkt bereits beendet. The fact that the mixture was free of silanol groups after 30 minutes was demonstrated by means of the procedure described on page 7 of EP 2 170 995 B1 titanate rapid test. The endcapping reaction was thus already over at this point in time.
Anschließend wurde 0,5 g des erfindungsgemäßen Zusatzes aus Beispiel 7 über 10 min eingemischt. Then 0.5 g of the additive according to the invention from Example 7 was mixed in over 10 minutes.
Viskosität nach 2 Stunden: 190,0 Pa.s Viskosität nach 22 Stunden: 162,5 Pa.s Beispiel 17 (nicht erfindungsgemäß) Viscosity after 2 hours: 190.0 Pa.s Viscosity after 22 hours: 162.5 Pa.s Example 17 (not according to the invention)
Der Versuch 15 wurde wiederholt mit der Abänderung, dass nach träglich kein erfindungsgemäßer Zusatz eingemischt wurde. Experiment 15 was repeated with the modification that no additive according to the invention was subsequently mixed in.
Viskosität nach 2 Stunden: 184,5 Pa.s Viskosität nach 22 Stunden: 113,0 Pa.s Viscosity after 2 hours: 184.5 Pa.s Viscosity after 22 hours: 113.0 Pa.s
Es ist wieder erkennbar, dass ohne den erfindungsgemäßen Zusatz ein extremer Viskositätsabbau stattfindet.
It can again be seen that without the additive according to the invention an extreme reduction in viscosity takes place.
Claims
1. Mischungen (M) enthaltend 1. Mixtures (M) containing
(X) Polyether der allgemeinen Formel (X) Polyethers of the general formula
R1- (O-R2)p-O-R1 (I), wobei R 1 - (OR 2 ) p -OR 1 (I), where
R1 gleich oder verschieden sein kann und Wasserstoffatom oder Kohlenwasserstoffreste darstellt, R 1 can be the same or different and represents hydrogen atom or hydrocarbon radicals,
R2 gleich oder verschieden sein kann und zweiwertige, gegebe nenfalls substituierte Kohlenwasserstoffreste bedeutet und p eine ganze Zahl von 4 bis 110 ist, R 2 can be the same or different and is divalent, optionally substituted hydrocarbon radicals and p is an integer from 4 to 110,
(Y) Phosphorverbindungen der Formel (Y) phosphorus compounds of the formula
0=PR5 m(0R6)n(0H)3-(m+n) (II) wobei 0=PR 5 m (0R 6 ) n (0H) 3-(m+n) (II) where
R5 gleich oder verschieden sein kann und gegebenenfalls substi tuierte Kohlenwasserstoffreste bedeutet, R 5 can be the same or different and is optionally substituted hydrocarbon radicals,
R6 gleich oder verschieden sein kann und gegebenenfalls substi tuierte Kohlenwasserstoffreste bedeutet, m gleich 0 oder 1, bevorzugt 1, ist und n gleich 0, 1 oder 2 ist, mit der Maßgabe, dass m+n gleich 1 oder 2, bevorzugt 1, ist, und gegebenenfalls R 6 can be the same or different and is optionally substituted hydrocarbon radicals, m is 0 or 1, preferably 1, and n is 0, 1 or 2, with the proviso that m+n is 1 or 2, preferably 1, is, and if necessary
(Z) Wasser. (Z) water.
2. Mischungen (M) gemäß Anspruch 1, dadurch gekennzeichnet, dass es sich bei den Polyethern (X) um solche der Formel
R1 (OCH2CH2)q (OCHCH3CH2)r (OCH2CH2)sOR1 (III) handelt, wobei 2. Mixtures (M) according to Claim 1, characterized in that the polyethers (X) are those of the formula R 1 is (OCH 2 CH 2 ) q (OCHCH 3 CH 2 ) r (OCH 2 CH 2 ) s OR 1 (III) wherein
R1 eine der obengenannten Bedeutungen hat, q 0 oder eine ganze Zahl von 1 bis 30, bevorzugt 0 oder eine ganze Zahl von 1 bis 15, ist, s 0 oder eine ganze Zahl von 1 bis 30, bevorzugt 0 oder eine ganze Zahl von 1 bis 15, ist sowie r eine ganze Zahl von 4 bis 50, bevorzugt eine ganze Zahl von 4 bis 35, ist. R 1 has one of the meanings given above, q is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15, s is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15, and r is an integer from 4 to 50, preferably an integer from 4 to 35.
3. Mischungen (M) gemäß Anspruch 1 oder 2, dadurch gekennzeich net, dass es sich bei den Phosphorverbindungen (Y) um Alkylph- osphonsäuren mit 4 bis 18 Kohlenstoffatomen handelt. 3. Mixtures (M) according to Claim 1 or 2, characterized in that the phosphorus compounds (Y) are alkylphosphonic acids having 4 to 18 carbon atoms.
4. Mischungen (M) gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie Phosphorverbindungen (Y) in Mengen von 10 bis 50 Gewichtsteile enthalten. 4. Mixtures (M) as claimed in one or more of claims 1 to 3, characterized in that they contain phosphorus compounds (Y) in amounts of 10 to 50 parts by weight.
5. Mischungen (M) gemäß einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie Wasser (Z) in Mengen von 0,5 bis 3,0 mol, bezogen auf 1 mol Phosphorverbindung (Y), ent halten. 5. Mixtures (M) as claimed in one or more of claims 1 to 4, characterized in that they contain water (Z) in amounts of 0.5 to 3.0 mol, based on 1 mol of phosphorus compound (Y).
6. Verfahren zur Herstellung der Mischungen (M) gemäß einem o- der mehreren der Ansprüche 1 bis 5 durch Vermischen der einzel nen Bestandteile. 6. A process for preparing the mixtures (M) as claimed in one or more of claims 1 to 5 by mixing the individual components.
7. Vernetzbare Zusammensetzungen auf der Basis von Organosili- ciumverbindungen erhältlich durch Vermischen von 7. Crosslinkable compositions based on organosilicon compounds obtainable by mixing
(A) Organopolysiloxane der Formel
(R70)3-aSiR3 aO (SiR4 20)nSiR3 x (OR7)3-a (V), wobei (A) Organopolysiloxanes of the formula (R 7 0) 3-a SiR 3 a O (SiR 4 2 0) n SiR 3 x (OR 7 )3-a (V), where
R4 gleich oder verschieden sein kann und einwertige, gegebenen falls substituierte Kohlenwasserstoffreste bedeutet, R 4 may be the same or different and are monovalent, optionally substituted hydrocarbon radicals,
R7 gleich oder verschieden sein kann und einwertige, gegebenen falls substituierte Kohlenwasserstoffreste bedeutet, R 7 can be the same or different and means monovalent, optionally substituted hydrocarbon radicals,
R3 gleich oder verschieden sein kann und einwertige, gegebenen falls substituierte Kohlenwasserstoffreste bedeutet, a gleich oder verschieden sein kann und 0 oder 1, bevorzugt 1, ist und x eine ganze Zahl von 30 bis 2000 ist, und R 3 may be the same or different and are monovalent, optionally substituted hydrocarbon radicals, a may be the same or different and is 0 or 1, preferably 1, and x is an integer from 30 to 2000, and
(B) Mischungen (M) enthaltend (B) containing mixtures (M).
(X) Polyether der allgemeinen Formel (I), (X) polyethers of general formula (I),
(Y) Phosphorverbindungen der Formel (II) und gegebenenfalls (Y) phosphorus compounds of formula (II) and optionally
(Z) Wasser. (Z) water.
8 Zusammensetzungen gemäß Anspruch 7, dadurch gekennzeichnet, dass es sich um solche handelt, die 8 compositions according to claim 7, characterized in that it is such that
(A) Organopolysiloxane der Formel (V), (A) organopolysiloxanes of formula (V),
(B) Mischungen (M), gegebenenfalls (C) Silane der Formel (VI) und/oder deren Teil- hydrolysate, gegebenenfalls (D) Härtungsbeschleuniger, gegebenenfalls (E) Weichmacher, gegebenenfalls (F) Füllstoffe und gegebenenfalls (G) Additive enthalten.
(B) mixtures (M), optionally (C) silanes of the formula (VI) and/or their partial hydrolyzates, optionally (D) curing accelerators, optionally (E) plasticizers, optionally (F) fillers and optionally (G) additives .
9. Verfahren zur Herstellung der Zusammensetzungen gemäß An spruch 7 oder 8 durch Vermischen der einzelnen Bestandteile. 9. A process for preparing the compositions according to claim 7 or 8 by mixing the individual components.
10. Formkörper, hergestellt durch Vernetzung der Zusammenset- zungen gemäß Anspruch 7 oder 8 oder hergestellt gemäß Anspruch10. Moldings produced by crosslinking the compositions according to claim 7 or 8 or produced according to claim
9. 9.
11. Verfahren zur Herstellung von Organyloxygruppen aufweisen den Organosiliciumverbindungen, dadurch gekennzeichnet, dass in einem 1. Schritt mindestens eine Silanolgruppe aufweisende Or- ganosiliciumverbindung (a) mit mindestens zwei Organyloxygrup pen enthaltender Verbindung (b) in Anwesenheit von stark basi schen Katalysatoren (c) umgesetzt werden und in einem 2. 11. Process for preparing organyloxy groups containing organosilicon compounds, characterized in that in a 1st step, at least one silanol group-containing organosilicon compound (a) is combined with at least two organyloxy group-containing compound (b) in the presence of strongly basic catalysts (c) be implemented and in a 2.
Schritt nach erfolgter Reaktion der Hydroxylgruppen von Kompo- nente (a) mit den Organyloxygruppen enthaltenden Verbindungen (b) die erfindungsgemäße Mischung (M) zugegeben wird.
Step after the reaction of the hydroxyl groups of component (a) with the compounds (b) containing organyloxy groups has taken place, the mixture (M) according to the invention is added.
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| PCT/EP2021/054778 WO2022179691A1 (en) | 2021-02-26 | 2021-02-26 | Mixtures containing phosphorus compounds and use thereof |
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| US (1) | US20230399513A1 (en) |
| EP (1) | EP4251691A1 (en) |
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| DE102007034711A1 (en) | 2007-07-25 | 2009-01-29 | Wacker Chemie Ag | Process for the preparation of organosilicon-containing organosilicon compounds |
| DE102007041857A1 (en) | 2007-09-03 | 2009-03-05 | Wacker Chemie Ag | Process for the continuous preparation of crosslinkable compositions based on organosilicon compounds |
| DE102015216598A1 (en) | 2015-08-31 | 2017-03-02 | Wacker Chemie Ag | Process for the preparation of organosilicon-containing organosilicon compounds |
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