KR19990044599A - Tin catalyst, preparation method thereof, use thereof and crosslinkable mixture containing the same - Google Patents
Tin catalyst, preparation method thereof, use thereof and crosslinkable mixture containing the same Download PDFInfo
- Publication number
- KR19990044599A KR19990044599A KR1019980701849A KR19980701849A KR19990044599A KR 19990044599 A KR19990044599 A KR 19990044599A KR 1019980701849 A KR1019980701849 A KR 1019980701849A KR 19980701849 A KR19980701849 A KR 19980701849A KR 19990044599 A KR19990044599 A KR 19990044599A
- Authority
- KR
- South Korea
- Prior art keywords
- tin catalyst
- phosphate
- crosslinkable
- rtv
- optionally
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000012974 tin catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 39
- -1 silicic acid ester Chemical class 0.000 claims description 39
- 150000002148 esters Chemical class 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 235000011007 phosphoric acid Nutrition 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 9
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000004971 Cross linker Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 8
- 150000003606 tin compounds Chemical class 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- OZFLRNPZLCUVFP-UHFFFAOYSA-N 8-methylnonyl dihydrogen phosphate Chemical compound CC(C)CCCCCCCOP(O)(O)=O OZFLRNPZLCUVFP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- SCIGVHCNNXTQDB-UHFFFAOYSA-N decyl dihydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(O)=O SCIGVHCNNXTQDB-UHFFFAOYSA-N 0.000 claims description 4
- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 claims description 4
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- GAJQCIFYLSXSEZ-UHFFFAOYSA-N tridecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(O)=O GAJQCIFYLSXSEZ-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 150000005691 triesters Chemical class 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000047 product Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CELFQJLWIWWAPB-UHFFFAOYSA-N bis(7-methyloctyl) hydrogen phosphate Chemical compound CC(C)CCCCCCOP(O)(=O)OCCCCCCC(C)C CELFQJLWIWWAPB-UHFFFAOYSA-N 0.000 description 1
- HVGFMUJLKBGRSF-UHFFFAOYSA-N bis(trimethylsilyl) hydrogen phosphate Chemical compound C[Si](C)(C)OP(O)(=O)O[Si](C)(C)C HVGFMUJLKBGRSF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- WFLLPKDDXLHZLQ-UHFFFAOYSA-N dibutoxy(dioctyl)stannane Chemical class CCCCCCCC[Sn](OCCCC)(OCCCC)CCCCCCCC WFLLPKDDXLHZLQ-UHFFFAOYSA-N 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- RNPXCFINMKSQPQ-UHFFFAOYSA-N dicetyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCC RNPXCFINMKSQPQ-UHFFFAOYSA-N 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 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
- 238000009472 formulation Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GJQSLHYMHWQOQY-UHFFFAOYSA-N n-[bis(butylamino)-methylsilyl]butan-1-amine Chemical compound CCCCN[Si](C)(NCCCC)NCCCC GJQSLHYMHWQOQY-UHFFFAOYSA-N 0.000 description 1
- WOFLNHIWMZYCJH-UHFFFAOYSA-N n-[bis(diethylaminooxy)-methylsilyl]oxy-n-ethylethanamine Chemical compound CCN(CC)O[Si](C)(ON(CC)CC)ON(CC)CC WOFLNHIWMZYCJH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000008028 secondary esters Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000008027 tertiary esters Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical compound CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- KENFVQBKAYNBKN-UHFFFAOYSA-N trihexadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCC KENFVQBKAYNBKN-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/58—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with silicon, germanium, tin, lead, antimony, bismuth or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
본 발명은 신규 주석 촉매, 그의 제조 방법 및 그의 용도 및 그러한 신규 주석 촉매를 함유하는 가교성 혼합물을 제공한다.The present invention provides novel tin catalysts, methods for their preparation and their use, and crosslinkable mixtures containing such new tin catalysts.
Description
본 발명은 신규 주석 촉매, 그의 제조 방법 및 그의 용도 및 그 신규 주석 촉매를 함유하는 가교성 혼합물에 관한 것이다.The present invention relates to novel tin catalysts, methods for their preparation and their use and crosslinkable mixtures containing the new tin catalysts.
축합-가교성 1 및 2 성분 폴리실록산 조성물, 이후 본 명세서에서는 RTV-1 또는 RTV-2 (실온 경화성 성분 1 또는 2;roomtemperaturevulcanising component1또는2)이라 칭해지는 조성물 중의 촉매로서 유기 주석 화합물을 사용하는 것이 일반적으로 공지되어 있으며, 이 조성물은 물의 작용 또는 대기 습기의 흡수 시에 경화하여 엘라스토머를 생성한다.Organic tin as a catalyst in a condensation-crosslinkable one and two component polysiloxane composition, hereafter referred to herein as RTV-1 or RTV-2 (room temperature curable component 1 or 2; r oom t emperature v ulcanising component 1 or 2 ). It is generally known to use compounds, which compositions cure upon action of water or absorption of atmospheric moisture to produce elastomers.
이유기 주석 화합물, 예를 들면 디알킬주석 디카르복실레이트 또는 알콕시실란과 그의 반응 생성물을 폴리실록산 조성물 중의 촉매로서 통상적으로 사용한다. 그러한 화합물에는, 특히 디부틸주석 디아세테이트, 디부틸주석 디옥토에이트, 디부틸주석 디라우레이트, 디옥틸주석 디옥토에이트, 디옥틸주석 디라우레이트 또는 산화 디부틸주석과 규산 에스테르와의 반응 생성물, 예를 들면 폴리메틸 실리케이트, 테트라에톡시 실리케이트 및 폴리에틸 실리케이트가 있다.Weanonic tin compounds such as dialkyltin dicarboxylates or alkoxysilanes and their reaction products are commonly used as catalysts in polysiloxane compositions. Such compounds include, in particular, the reaction products of dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dioctoate, dioctyltin dilaurate or dibutyltin oxide and silicic acid esters. Such as polymethyl silicate, tetraethoxy silicate and polyethyl silicate.
또한, 미국 특허 제3 525 778호에는 하기 화학식의 유기인산 주석 및 경화성 폴리실록산 조성물 중의 촉매로서 그의 용도가 기재되어 있다.U. S. Patent No. 3 525 778 also describes its use as a catalyst in organotin phosphate and curable polysiloxane compositions of the formula:
R4-m-nSn(Ym)[OP(O)(OR')2]n R 4-mn Sn (Y m ) [OP (O) (OR ') 2 ] n
상기 식 중에서,In the above formula,
Y는 할로겐, 알콕시 또는 아릴옥시기를 의미하고,Y means halogen, alkoxy or aryloxy group,
R 및 R'는 임의로 치환된 탄화 수소 잔기를 의미하고,R and R 'mean optionally substituted hydrocarbon residues,
m은 0, 1 또는 2를 의미하고, n은 1, 2 또는 3을 의미하고, m + n의 총합은 1, 2 또는 3이다. 이러한 생성물의 특징은 뚜렷한 활성 증가를 나타내어, 폴리실록산 조성물을 빠르게 경화시킨다는 것이다.m means 0, 1 or 2, n means 1, 2 or 3, and the sum of m + n is 1, 2 or 3. The characteristic of this product is that it shows a marked increase in activity, thereby rapidly curing the polysiloxane composition.
그러나, 폴리실록산 조성물에 사용될 때 문헌에 공지된 주석 촉매는 축합 반응 시에 목적하는 촉매 작용을 하는 것 뿐만 아니라 원치않는 중합체 분해 반응도 초래한다는 단점을 가지고 있다. 예를 들면, 이것은 RTV-1 생성물 가교 특성의 손실 또는 저하를 초래한다. 또한, 중합체 분해 반응이 RTV-2 생성물에서도 나타날 수 있는데, 이때 촉매는 대개 각각의 성분 중에 저장되고, 생성물에 사용하기 직전에만 다른 성분과 혼합된다. 이러한 결과로서, 특히 촉매 성분, 구체적으로는 페이스트 배합물이 저장 기간 동안 분해되고, 점도는 바람직하지 않게 떨어지거나, 또는 반응성이 변하게 된다.However, tin catalysts known in the literature, when used in polysiloxane compositions, have the disadvantage of not only performing the desired catalysis in the condensation reaction but also causing unwanted polymer degradation reactions. For example, this results in loss or degradation of the RTV-1 product crosslinking properties. In addition, polymer degradation reactions can also occur in RTV-2 products, where the catalyst is usually stored in each component and mixed with other components only immediately before use in the product. As a result of this, in particular the catalyst component, in particular the paste formulation, decomposes during the storage period and the viscosity undesirably drops or the reactivity changes.
본 발명의 목적은 공지된 생성물의 단점을 갖지 않으며, RTV-1 또는 RTV-2 조성물용의 촉매로서 적당한 주석 촉매를 제공하는 것이다.It is an object of the present invention to provide tin catalysts which do not have the disadvantages of known products and which are suitable as catalysts for RTV-1 or RTV-2 compositions.
놀랍게도, 유기 주석 화합물과 오르토인산 및(또는) 그의 에스테르와의 반응 생성물이 문헌에 공지된 화합물에 비해 상당한 이점을 가지고 있음이 밝혀졌다. 본 발명에 따른 신규 주석 촉매는 탁월하게 향상된 저장 안정성을 갖는 RTV 생성물 생성에 있어서 축합-가교성 폴리실록산 조성물용의 촉매로서 특히 적당하다. 또한, 신규 촉매는 반응성이 향상되었다는 점도 주목할 만 하다.Surprisingly, it has been found that the reaction product of organic tin compounds with orthophosphoric acid and / or esters thereof has significant advantages over compounds known in the literature. The novel tin catalysts according to the invention are particularly suitable as catalysts for condensation-crosslinkable polysiloxane compositions in the production of RTV products with excellently improved storage stability. It is also noteworthy that the novel catalysts have improved reactivity.
따라서, 본 발명은Therefore, the present invention
a) 적어도 1종의 유기 주석 화합물과,a) at least one organotin compound,
b) 적어도 1종의 모노오르토인산 에스테르 및(또는) 오르토인산 및b) at least one monoorthophosphoric acid ester and / or orthophosphoric acid and
c) 임의로 추가의 인산 에스테르 및c) optionally further phosphoric acid esters and
d) 임의로 알콕시실란 또는 2종 이상의 알콕시실란d) optionally alkoxysilane or two or more alkoxysilanes
을 반응시킴으로써 얻을 수 있는 주석 촉매를 제공한다.Provided is a tin catalyst obtainable by reacting.
용어 유기 주석 화합물 a)는 모든 선행 기술에서 공지된 화합물을 포함한다.The term organotin compound a) includes compounds known in all prior art.
바람직한 유기 주석 화합물 a)는 하기 화학식 I의 일-, 이- 및 삼유기 주석 화합물이다.Preferred organotin compounds a) are mono-, di- and triorganic tin compounds of the formula (I)
상기 식 중에서,In the above formula,
n은 1, 2 또는 3, 바람직하게는 n은 2이고,n is 1, 2 or 3, preferably n is 2,
R1은 직쇄 또는 분지쇄 C1-C30알킬, C5-C14시클로알킬 또는 C6-C14아릴 잔기이고, X는 할로겐, -OR1, -OC(O)R1-OH, -SR1, -NR1 2, -NHR1, -OSiR1 3, -OSi(OR)1 3및(또는) 화학식 R1 2SnX', R1 3SnX'1/2, 및(또는) R1SnX'3/2(여기에서, X'는 O, S임)의 화합물이다.R 1 is a straight or branched C 1 -C 30 alkyl, C 5 -C 14 cycloalkyl or C 6 -C 14 aryl moiety, X is halogen, -OR 1 , -OC (O) R 1 -OH,- SR 1 , -NR 1 2 , -NHR 1 , -OSiR 1 3 , -OSi (OR) 1 3 and / or Formula R 1 2 SnX ', R 1 3 SnX' 1/2 , and / or R 1 SnX ' 3/2 , where X' is O, S.
또한, 직쇄 또는 분지쇄 C1-C30알킬, C5-C14시클로알킬 또는 C6-C14아릴 잔기의 수소 원자는 할로겐 원자, OH, NH2, NO2또는 C1-C6알킬 잔기로 치환될 수도 있다.In addition, the hydrogen atom of a straight or branched C 1 -C 30 alkyl, C 5 -C 14 cycloalkyl or C 6 -C 14 aryl moiety is a halogen atom, OH, NH 2 , NO 2 or a C 1 -C 6 alkyl moiety. It may be substituted with.
분자 중의 X, X' 및 R1잔기가 1개 이상인 경우에는, 서로 같거나 다를 수 있다.When there are one or more X, X 'and R 1 residues in a molecule, they may be the same or different.
특히 바람직한 화합물에는 산화 디옥틸주석, 산화 디부틸주석, 이염화 디메틸주석, 이염화 디부틸주석, 염화 트리부틸주석, 디부틸주석 디라우레이트, 디부틸주석 디아세테이트, 디부틸주석 말레에이트, 디부틸주석 디헥소에이트, 디부틸주석 디옥토에이트, 디옥틸주석 디옥토에이트, 디옥틸주석 디라우레이트, 수소화 디옥틸디부톡시주석 및(또는) 수소화 트리부틸에톡시주석이 있다.Particularly preferred compounds include dioctyl tin oxide, dibutyltin oxide, dimethyltin dichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, di Butyltin dihexate, dibutyltin dioctoate, dioctyltin dioctoate, dioctyltin dilaurate, hydrogenated dioctyldibutoxytin and / or hydrogenated tributylethoxytin.
본 발명의 목적에 있어서, 모노오르토인산 에스테르 및(또는) 오르토인산 b)는 하기 화학식 II의 화합물의 오르토인산 및(또는) 그의 에스테르 및(또는) 하기 화학식 III의 화합물을 포함하는 것이 바람직하다.For the purposes of the present invention, the monoorthophosphoric acid esters and / or orthophosphoric acid b) preferably comprise orthophosphoric acid and / or esters thereof and / or compounds of the general formula III below.
상기 식 중에서,In the above formula,
m은 2 또는 3, 바람직하게는 2이고,m is 2 or 3, preferably 2,
R2는 직쇄 또는 분지쇄 C1-C30알킬, 아실, C2-C30알케닐 또는 알콕시알킬, C5-C14시클로알킬 또는 C6-C14아릴 잔기, 또는 삼유기 실릴 또는 이유기 알콕시실릴 잔기이고,R 2 is a straight or branched C 1 -C 30 alkyl, acyl, C 2 -C 30 alkenyl or alkoxyalkyl, C 5 -C 14 cycloalkyl or C 6 -C 14 aryl moiety, or triorganic silyl or wean group Alkoxysilyl residues,
R3은 수소 및(또는) 금속, 바람직하게는 알칼리 또는 알칼리 토금속이다.R 3 is hydrogen and / or a metal, preferably an alkali or alkaline earth metal.
상기 식 중에서,In the above formula,
X는 1 내지 3의 값으로 가정할 수 있고,X can be assumed to be a value of 1 to 3,
R5는 C1-C30알킬 및 (CH2)ZSi(OR6)3 R 5 is C 1 -C 30 alkyl and (CH 2 ) Z Si (OR 6 ) 3
(여기서, z는 1 내지 10, 바람직하게는 3이고, R6은 C1-C5알킬, C2-C6알킬알콕시 및(또는) 폴리인산의 에스테르임),Where z is 1 to 10, preferably 3 and R 6 is an ester of C 1 -C 5 alkyl, C 2 -C 6 alkylalkoxy and / or polyphosphoric acid,
이 때, a+b+c = 3이며,At this time, a + b + c = 3,
여기서, a를 1 내지 3의 값으로 가정하고, b를 0 내지 2의 값으로 가정하고, c를 0 내지 2의 값으로 가정할 수 있다.Here, a may be assumed to be a value of 1 to 3, b may be assumed to be a value of 0 to 2, and c may be assumed to be a value of 0 to 2.
본 발명의 바람직한 실시양태에는, 화학식 III의 화합물이 하기 화합물이다.In a preferred embodiment of the invention, the compound of formula III is the following compound.
또한, 직쇄 또는 분지쇄 C1-C30알킬, 아실, C2-C30알케닐 또는 알콕시알킬, C5-C14시클로알킬 또는 C6-C14아릴 잔기의 수소 원자는 예를 들면 할로겐 원자, OH, NH2, NO2또는 추가의 C1-C6알킬기로 치환될 수 있다.In addition, the hydrogen atom of a straight or branched C 1 -C 30 alkyl, acyl, C 2 -C 30 alkenyl or alkoxyalkyl, C 5 -C 14 cycloalkyl or C 6 -C 14 aryl moiety is for example a halogen atom , OH, NH 2 , NO 2 or additional C 1 -C 6 alkyl groups.
본 발명의 바람직한 실시양태에는, 모노오르토인산 에스테르는 R2로서 적어도 1종의 직쇄 또는 분지쇄 C4-C30알킬 잔기를 함유한다. 바람직한 에스테르에는 모노부틸 포스페이트, 모노이소데실 포스페이트, 모노-(2-에틸헥실)포스페이트, 모노데실 포스페이트, 모노헥실 포스페이트, 모노트리데실 포스페이트 및(또는) 모노옥타데실 포스페이트가 있다. 이 제조 방법의 결과로, 모노오르토인산 에스테르 b)는 오염 물질로서 폴리인산 및(또는) 오르토인산의 디에스테르, 에스테르를 함유할 수 있다. 오르토인산 단독은 다소 바람직하지 못하며, 그의 에스테르와의 혼합물로서 사용하는 것이 바람직하다.In a preferred embodiment of the invention, the monoorthophosphoric acid ester contains at least one straight or branched chain C 4 -C 30 alkyl moiety as R 2 . Preferred esters include monobutyl phosphate, monoisodecyl phosphate, mono- (2-ethylhexyl) phosphate, monodecyl phosphate, monohexyl phosphate, monotridecyl phosphate and / or monooctadecyl phosphate. As a result of this production process, the monoorthophosphoric acid ester b) may contain diesters, esters of polyphosphoric acid and / or orthophosphoric acid as contaminants. Orthophosphoric acid alone is somewhat undesirable and preferably used as a mixture with its esters.
n이 2인 바람직한 경우에는, 본 발명에 따른 주석 촉매가 바람직하게는 하기의 구조 단위 또는 화합물을 포함한다.In the preferred case where n is 2, the tin catalyst according to the invention preferably comprises the following structural units or compounds.
본 발명의 목적에 있어서, 인산 에스테르 c)는 바람직하게는 오르토인산 및(또는) 폴리인산의 디- 및 트리에스테르이다.For the purposes of the present invention, phosphoric acid esters c) are preferably di- and triesters of orthophosphoric acid and / or polyphosphoric acid.
바람직한 인산 에스테르 c) 예에는 오르토인산의 2급 및 3급 에스테르, 예를 들면 디부틸 포스페이트, 디-(2-에틸헥실) 포스페이트, 디헥사데실 포스페이트, 디이소노닐 포스페이트, 디-(트리메틸실릴) 포스페이트, 트리부틸 포스페이트, 트리-(2-에틸헥실) 포스페이트, 트리헥사데실 포스페이트, 트리이소노닐 포스페이트 및(또는) 트리-(트리메틸실릴) 포스페이트가 있다.Preferred phosphoric acid esters c) examples include secondary and tertiary esters of orthophosphoric acid, for example dibutyl phosphate, di- (2-ethylhexyl) phosphate, dihexadecyl phosphate, diisononyl phosphate, di- (trimethylsilyl) Phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, trihexadecyl phosphate, triisononyl phosphate and / or tri- (trimethylsilyl) phosphate.
또한, 성분 c)는 폴리인산의 에스테르 또는 2종 이상의 폴리인산 에스테르 및(또는) 오르토인산 에스테르의 혼합물을 포함한다. 오르토- 및 폴리인산 에스테르의 산성 또는 중성염, 예를 들면 알칼리 금속염 또한 적당하다.Component c) also comprises esters of polyphosphoric acid or mixtures of two or more polyphosphoric acid esters and / or orthophosphoric acid esters. Also suitable are acidic or neutral salts of ortho- and polyphosphoric acid esters, for example alkali metal salts.
본 발명의 목적에 있어서, 알콕시실란 d)는 규산 에스테르 (예를 들면 폴리메틸 실리케이트, 테트라메틸 실리케이트, 폴리에틸 실리케이트, 테트라에틸 실리케이트, 테트라프로필 실리케이트), 유기트리알콕시실란 (예를 들면, 비닐트리메톡시실란, 비닐트리에톡시실란, 메틸트리에톡시실란, 메틸트리메톡시실란, 비닐트리프로폭시실란 및 비닐트리에톡시실란) 또는 그의 부분 가수분해물이 바람직하다.For the purposes of the present invention, the alkoxysilane d) is a silicic acid ester (e.g. polymethyl silicate, tetramethyl silicate, polyethyl silicate, tetraethyl silicate, tetrapropyl silicate), organotrialkoxysilane (e.g. vinyltri Methoxysilane, vinyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, vinyltripropoxysilane and vinyltriethoxysilane) or partial hydrolysates thereof are preferred.
메틸트리메톡시-, 메틸트리에톡시, 비닐트리메톡시 및(또는) 비닐트리에톡시실란이 상기 경우에 특히 바람직하다.Methyltrimethoxy-, methyltriethoxy, vinyltrimethoxy and / or vinyltriethoxysilane are particularly preferred in this case.
또한, 본 발명에 따르는 혼합물은 추가의 보조 물질을 함유할 수 있다.In addition, the mixtures according to the invention may contain further auxiliary substances.
그러한 보조 물질에는 유기 용매 (예를 들면, 톨루엔, 헥산, 이소파라핀), 착색 안료 및(또는) 유기산 (예를 들면, 2-에틸헥산산, 벤조산, 도데실벤젠술폰산)이 바람직하다.Preferred such auxiliary materials are organic solvents (eg toluene, hexane, isoparaffin), colored pigments and / or organic acids (eg 2-ethylhexanoic acid, benzoic acid, dodecylbenzenesulfonic acid).
본 발명의 목적에 있어서, 바람직한 주석 촉매는For the purposes of the present invention, preferred tin catalysts are
a) 적어도 1종의 유기 주석 화합물, 특히 바람직하게는 이유기 주석 화합물 1 mol과a) at least one organotin compound, particularly preferably 1 mol of weaning tin compound
b) 적어도 1종의 모노오르토인산 에스테르 및(또는) 오르토인산, 바람직하게는 모노오르토인산 0.5 내지 4 mol, 바람직하게는 1 내지 3 mol, 특히 바람직하게는 1.5 내지 2.5 mol,b) at least one monoorthophosphoric acid ester and / or orthophosphoric acid, preferably 0.5 to 4 mol, preferably 1 to 3 mol, particularly preferably 1.5 to 2.5 mol,
c) 디- 및(또는) 트리오르토인산 에스테르 0 내지 2 mol, 바람직하게는 0 mol 및c) 0 to 2 mol, preferably 0 mol and di- and / or triorthophosphoric acid esters
d) 적어도 1종의 알콕시실란 0 내지 5 mold) 0 to 5 mol of at least one alkoxysilane
을 반응시킴으로써 얻을 수 있다.It can be obtained by reacting.
특히, 바람직한 주석 촉매는In particular, preferred tin catalysts are
a) 적어도 1종의 이유기 주석 화합물 1 mol과,a) 1 mol of at least one weaning tin compound,
b) 적어도 1종의 모노오르토인산 에스테르 1 내지 3 mol 및b) 1-3 mol of at least one monoorthophosphoric acid ester and
c) 적어도 1종의 알콕시실란 0 내지 5 molc) 0 to 5 mol of at least one alkoxysilane
을 반응시킴으로써 얻을 수 있다.It can be obtained by reacting.
본 발명에 따른 주석 촉매는 적당한 주석 화합물과 인 화합물을 20 내지 200 ℃ 사이, 바람직하게는 20 내지 140 ℃ 사이의 온도에서 반응시킴으로써 바람직하게 얻을 수 있다. 본 발명의 다른 실행에서는, 반응을 적당한 유기 용매 중에서 수행하는 것이 바람직하다. 모든 불활성 용매가 본 목적에 적당하며, 그 예로는 방향족 탄화수소 (예를 들면, 벤젠, 톨루엔, 크실렌) 뿐만 아니라, 임의로 할로겐화된 지방족 탄화수소 (예를 들면, 헥산, 헵탄 및 테트라클로로메탄)이 있다. 통상적으로는, 반응을 20 내지 200 ℃ 사이의 온도에서 수행하나, 용매를 사용하는 경우의 반응 온도는 용매의 비점에 의해서 결정하기도 한다.The tin catalyst according to the present invention can be preferably obtained by reacting a suitable tin compound and a phosphorus compound at a temperature between 20 and 200 ° C, preferably between 20 and 140 ° C. In other implementations of the invention, it is preferred to carry out the reaction in a suitable organic solvent. All inert solvents are suitable for this purpose, examples being aromatic hydrocarbons (eg benzene, toluene, xylene), as well as optionally halogenated aliphatic hydrocarbons (eg hexane, heptane and tetrachloromethane). Usually, the reaction is carried out at a temperature between 20 and 200 ° C, but the reaction temperature when using a solvent may be determined by the boiling point of the solvent.
다른 바람직한 실시양태에는, 주석 촉매를 a) 적어도 1종의 유기 주석 화합물과, b) 적어도 1종의 모노오르토인산 에스테르 및(또는) 오르토인산, c) 임의로 추가의 인산 에스테르 및 d) 임의로 1종 이상의 알콕시실란을 20 내지 140 ℃의 온도에서 반응시킴으로써 얻을 수 있다.In another preferred embodiment, the tin catalyst comprises a) at least one organic tin compound and b) at least one monoorthophosphoric acid ester and / or orthophosphoric acid, c) optionally further phosphoric acid esters and d) optionally one The alkoxysilane mentioned above can be obtained by making it react at the temperature of 20-140 degreeC.
또한, 본 발명은In addition, the present invention
a) 적어도 1종의 유기 주석 화합물과,a) at least one organotin compound,
b) 적어도 1종의 모노오르토인산 에스테르 및(또는) 오르토인산 및b) at least one monoorthophosphoric acid ester and / or orthophosphoric acid and
c) 임의로 추가의 인산 에스테르,c) optionally further phosphoric acid esters,
d) 임의로 1종 이상의 알콕시실란d) optionally at least one alkoxysilane
을 반응시키는 것을 특징으로 하는, 본 발명에 따른 주석 촉매의 제조 방법을 제공한다.It provides a method for producing a tin catalyst according to the invention, characterized in that the reaction.
또한, 추가의 보조 물질, 예를 들면 유기 용매 (예를 들면, 톨루엔, 헥산, 이소파라핀), 착색 안료 및(또는) 유기산 (예를 들면, 2-에틸헥산산, 벤조산, 도데실벤젠술폰산)을 본 발명에 따른 반응 동안에 넣을 수 있다.Further auxiliary substances such as organic solvents (eg toluene, hexane, isoparaffin), colored pigments and / or organic acids (eg 2-ethylhexanoic acid, benzoic acid, dodecylbenzenesulfonic acid) Can be put during the reaction according to the invention.
이 반응은 20 내지 200 ℃, 바람직하게는 20 내지 140 ℃사이의 온도에서 수행하는 것이 바람직하다.This reaction is preferably carried out at a temperature between 20 and 200 ° C, preferably between 20 and 140 ° C.
또한, 본 발명은 폴리올레핀, 폴리에스테르, 오일, 지방산, 폴리우레탄 및 폴리실록산 중의 촉매 및 안정화제로서 본 발명에 따른 주석 촉매의 용도를 제공한다. 가교성 RTV-1 및 RTV-2 조성물 중의 촉매로서 본 발명에 따른 주석 촉매를 사용하는 것이 특히 바람직하다.The invention also provides the use of the tin catalyst according to the invention as a catalyst and stabilizer in polyolefins, polyesters, oils, fatty acids, polyurethanes and polysiloxanes. Particular preference is given to using the tin catalyst according to the invention as catalyst in the crosslinkable RTV-1 and RTV-2 compositions.
RTV-2 생성물 중에 본 발명에 따른 촉매를 사용하는 경우에는, 페이스트 상을 얻기 위해 충전제, 예를 들면 고분산 실리카, 파라핀, 바세린 또는 왁스를 사용하는 것이 이롭다. 보조 물질의 양은 모든 성분 a) 내지 d)의 총량에 비례하여 사용되는 성분들의 특성 및 그의 농도에 따라 가변적이고, 페이스트 상의 목적하는 점조도에 따라 가변적이다.When using the catalyst according to the invention in the RTV-2 product, it is advantageous to use fillers such as highly disperse silica, paraffin, petrolatum or wax to obtain the paste phase. The amount of auxiliary material varies depending on the properties and concentrations of the components used in proportion to the total amount of all components a) to d), and depending on the desired consistency on the paste.
또한, 본 발명은In addition, the present invention
적어도 1종의 본 발명에 따른 주석 촉매,At least one tin catalyst according to the invention,
적어도 1종의 가교성 폴리실록산,At least one crosslinkable polysiloxane,
임의로 1종 이상의 실란 가교제,Optionally at least one silane crosslinker,
임의로 충전제 및Optionally fillers and
임의로 추가의 첨가제 및 보조 물질Optionally further additives and auxiliary substances
을 함유하는 가교성 RTV 조성물을 제공한다.It provides a crosslinkable RTV composition containing.
상기 경우에서는, 본 발명에 따른 RTV 조성물이 1- 또는 2- 성분계일 수 있다. 1-성분계에서는, 모든 구성분이 함께 혼합된다. 2-성분계는 2개의 별도의 성분 형태로 제조하여, 사용하기 직전에 바로 혼합된다. 여기에서, 가교성 폴리실록산은 통상적으로 1가지 성분 중에 따로 저장되고, 다른 성분 중에 실란 가교제 및 촉매가 저장된다.In this case, the RTV composition according to the invention may be a one- or two-component system. In one-component systems, all components are mixed together. The two-component system is prepared in the form of two separate components and mixed immediately before use. Here, the crosslinkable polysiloxane is usually stored separately in one component, and the silane crosslinker and catalyst are stored in the other component.
본 발명에 따른 주석 촉매의 양은 모든 성분의 총량에 대해 0.005 내지 5 중량%, 바람직하게는 0.01 내지 2.0 중량%, 특히 바람직하게는 0.1 내지 1 중량%가 바람직하다.The amount of tin catalyst according to the invention is preferably 0.005 to 5% by weight, preferably 0.01 to 2.0% by weight, particularly preferably 0.1 to 1% by weight, based on the total amount of all components.
본 발명의 목적에 있어서, 가교성 폴리실록산은 메틸기가 임의로 비닐, 페닐, C2내지 C8알킬 또는 할로알킬기로 부분적으로 치환된 폴리 이유기 실록산, 바람직하게는 폴리디메틸실록산이다. 폴리디메틸실록산이 실제적으로 직쇄인 것이 바람직하나, 가교 작용을 갖는 유기 실록시 단위가 적은 비율로 있을 수도 있다. 중합체의 점도는 바람직하게는 0.1 내지 1000 Pa.s, 특히 바람직하게는 5 내지 1000 Pa.s 사이이다. 가교성 폴리 이유기 실록산은 추가로 비반응성 잔기, 예를 들면 트리메틸실록시 잔기로 부분적으로 치환될 수 있다.For the purposes of the present invention, the crosslinkable polysiloxane is a poly wean siloxane, preferably polydimethylsiloxane, in which the methyl group is partially substituted with a vinyl, phenyl, C 2 to C 8 alkyl or haloalkyl group. It is preferable that the polydimethylsiloxane is substantially straight chain, but there may be a small proportion of organic siloxy units having a crosslinking action. The viscosity of the polymer is preferably between 0.1 and 1000 Pa · s, particularly preferably between 5 and 1000 Pa · s. The crosslinkable poly-base group siloxane may further be partially substituted with non-reactive moieties such as trimethylsiloxy moieties.
RTV-1 조성물 중의 폴리실록산의 바람직한 반응 잔기는 OH기 또는 트리알콕시실릴 또는 디알콕시실릴 잔기가 있다. 바람직한 트리알콕시실릴 또는 디알콕시실릴 잔기에는 트리에톡시실릴 및 트리메톡시실릴, 디에톡시메틸실릴, 디에톡시비닐실릴, 디메톡시메틸실릴 또는 디메톡시비닐실릴 잔기가 있다.Preferred reaction residues of the polysiloxanes in the RTV-1 composition are OH groups or trialkoxysilyl or dialkoxysilyl residues. Preferred trialkoxysilyl or dialkoxysilyl moieties include triethoxysilyl and trimethoxysilyl, diethoxymethylsilyl, diethoxyvinylsilyl, dimethoxymethylsilyl or dimethoxyvinylsilyl moieties.
본 발명의 바람직한 실시양태에는, 반응 잔기로서 트리알콕시실릴 또는 디알콕시실릴기를 갖는 가교성 폴리실록산이 RTV 생성물의 생성 과정 중에 적당한 방법으로 제조된다 (예를 들면, 독일 특허 공개 공보 제4 207 212호를 참조).In a preferred embodiment of the present invention, crosslinkable polysiloxanes having a trialkoxysilyl or dialkoxysilyl group as the reaction moiety are prepared in a suitable manner during the production of the RTV product (see, eg, German Patent Publication No. 4 207 212). Reference).
RTV-2 조성물 중의 폴리실록산의 반응성 잔기는 OH기가 바람직하다.The reactive moiety of the polysiloxane in the RTV-2 composition is preferably an OH group.
본 발명의 목적에 있어서는, 실란 가교제는 아세톡시, 알콕시, 알콕시알콕시, 아미녹시, 아미노, 아미도, 아세트아미노 및 옥시모기를 갖는 당 업계에 공지된 실란이다. 그 예로는 메틸트리아세톡시실란, 에틸트리아세톡시실란, 메틸트리메톡시실란, 메틸트리에톡시실란, 테트라에틸 실리케이트, 비닐트리에톡시실란, 비닐트리메톡시실란, 테트라프로필 실리케이트, 메틸트리스-(메틸에틸케톡시모)실란, 메틸에톡시디-N-메틸벤즈아미도실란, 메틸트리스-(부틸아미노)실란 및 메틸트리스-(디에틸아미녹시)실란이 있다.For the purposes of the present invention, silane crosslinkers are silanes known in the art having acetoxy, alkoxy, alkoxyalkoxy, aminoxy, amino, amido, acetamino and oxymo groups. Examples include methyltriacetoxysilane, ethyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraethyl silicate, vinyltriethoxysilane, vinyltrimethoxysilane, tetrapropyl silicate, methyltris- (Methylethylketoxymo) silane, methylethoxydi-N-methylbenzamidosilane, methyltris- (butylamino) silane and methyltris- (diethylaminooxy) silane.
RTV-2 조성물 중의 실란 가교제는 적어도 1종의 알콕시실란, 예를 들면 메틸트리메톡시실란, 테트라에틸 실리케이트, 비닐트리에톡시실란, 비닐트리메톡시실란, 테트라프로필 실리케이트 및(또는) 그의 부분 가수분해물이 바람직하다.The silane crosslinking agent in the RTV-2 composition is at least one alkoxysilane, for example methyltrimethoxysilane, tetraethyl silicate, vinyltriethoxysilane, vinyltrimethoxysilane, tetrapropyl silicate and / or partial valences thereof. Decomposition products are preferred.
충전제는 보강제 및 비보강제가 바람직하며, 그 예로는 열분해법 또는 침강 실리카, 카본 블랙 또는 실리카 가루가 있다. 충전제는 임의로 표면을 개질시킬 수 있다. 또한, 원하는 조성의 충전제 혼합물도 사용할 수 있다. 본 발명의 바람직한 실시양태에서의 충전제는 실리카이다.Fillers are preferably reinforcing and non-reinforcing agents, examples being pyrolysis or precipitated silica, carbon black or silica powder. The filler may optionally modify the surface. In addition, filler mixtures of the desired composition can also be used. In a preferred embodiment of the invention the filler is silica.
본 발명의 목적에 있어서의 첨가제는 가소제, 커플링제 (coupling agent), 안료, 안정화제, 추가의 조촉매 및 살진균제가 바람직하다.Additives for the purposes of the present invention are preferably plasticizers, coupling agents, pigments, stabilizers, additional promoters and fungicides.
본 발명의 바람직한 실시양태에는, 보조 물질은 실리콘 가소제, 예를 들면 트리메틸실록시기를 말단기로 하고, 0.1 내지 5 Pa.s의 점도를 갖는 폴리디메틸실록산, 안정화제, 예를 들면 헥사메틸디실라잔 및(또는) 미국 특허 제4 417 042호에 기재된 화합물, 커플링제, 예를 들면 하기 화학식 IV 및 하기 화학식 V의 유기 관능성 실란 또는 요소 유도체가 있다.In a preferred embodiment of the invention, the auxiliary material is a polydimethylsiloxane, stabilizer, for example hexamethyldisila, having a silicone plasticizer such as trimethylsiloxy group as the end group and having a viscosity of 0.1 to 5 Pa · s. Glass and / or the compounds described in US Pat. No. 4,417,042, coupling agents, for example organofunctional silanes or urea derivatives of formula IV and formula V.
상기 식 중에서,In the above formula,
d는 0 또는 1이고,d is 0 or 1,
Z는 -NH2, -NH-CH2-CH2-NH2, Z is -NH 2 , -NH-CH 2 -CH 2 -NH 2 ,
-O-C(O)-C(CH3)=CH2, -SH, -OH, -Cl, -CN이고,-OC (O) -C (CH 3 ) = CH 2 , -SH, -OH, -Cl, -CN,
R4는 직쇄 또는 분지쇄 C1-C30알킬잔기이다.R 4 is a straight or branched C 1 -C 30 alkyl residue.
식 중에서, R4중의 수소 원자는 할로겐 원자, OH, NH2, NO2또는 추가의 C1-C6알킬 잔기로 부분적으로 치환될 수 있다.In the formula, the hydrogen atom in R 4 may be partially substituted with halogen atom, OH, NH 2 , NO 2 or additional C 1 -C 6 alkyl residues.
본 발명의 바람직한 실시양태에는, 본 발명에 따른 주석 촉매가 가교성 RTV 조성물 중에서 반응계 내에서 생성된다.In a preferred embodiment of the invention, the tin catalyst according to the invention is produced in the reaction system in the crosslinkable RTV composition.
따라서, 본 발명은 적어도 1종의 주석 촉매, 적어도 1종의 가교성 폴리실록산, 임의로 1종 이상의 실란 가교제 및 임의로 추가의 첨가제 및 보조 물질을 함유하는 가교된 RTV 조성물을 제공하며, 주석 촉매가 a) 적어도 1종의 유기 주석 화합물과, b) 적어도 1종의 모노오르토인산 에스테르 및(또는) 오르토인산, 및 c) 임의로 추가의 인산 에스테르, d) 1종 이상의 알콕시실란 및(또는) e) 추가의 보조 물질의 반응에 의한 가교성 RTV 조성물의 제조 중에 반응계 내에서 생성되는 것을 특징으로 한다.Accordingly, the present invention provides a crosslinked RTV composition containing at least one tin catalyst, at least one crosslinkable polysiloxane, optionally at least one silane crosslinker and optionally further additives and auxiliary materials, wherein the tin catalyst is a) At least one organotin compound and b) at least one monoorthophosphoric acid ester and / or orthophosphoric acid, and c) optionally further phosphoric acid ester, d) at least one alkoxysilane and / or e) additional Characterized in that it is produced in the reaction system during the preparation of the crosslinkable RTV composition by reaction of the auxiliary material.
유기 주석 화합물은 이유기 주석 산화물과 규산 에스테르 및(또는) 이유기 주석 카르복실레이트 (예를 들면, 산화 디부틸주석 및 산화 디옥틸주석, 디부틸주석 디아세테이트 및 디옥틸주석 디옥토에이트)의 반응생성물이며, 성분 b)는 오르토인산의 적어도 1종의 모노에스테르 (예를 들면, 모노부틸 포스페이트, 모노이소데실 포스페이트, 모노-(2-에틸헥실) 포스페이트, 모노데실 포스페이트, 모노헥실 포스페이트, 모노트리데실 포스페이트 및 모노옥타데실 포스페이트)가 바람직하다. 모노이소데실 포스페이트, 모노-(2-에틸헥실) 포스페이트, 모노데실 포스페이트, 모노헥실 포스페이트, 모노트리데실 포스페이트 및(또는) 모노옥타데실 포스페이트가 특히 바람직하다.The organotin compound may be selected from weaning tin oxides and silicic acid esters and / or weaning tin carboxylates (eg, dibutyltin oxide and dioctyltin oxide, dibutyltin diacetate and dioctyltin dioctoate). Reaction product, component b) is at least one monoester of orthophosphoric acid (e.g., monobutyl phosphate, monoisodecyl phosphate, mono- (2-ethylhexyl) phosphate, monodecyl phosphate, monohexyl phosphate, mono Tridecyl phosphate and monooctadecyl phosphate) are preferred. Particular preference is given to monoisodecyl phosphate, mono- (2-ethylhexyl) phosphate, monodecyl phosphate, monohexyl phosphate, monotridecyl phosphate and / or monooctadecyl phosphate.
본 발명의 바람직한 실시양태에는, 가교성 RTV 조성물은 하기의 조성을 갖는다.In a preferred embodiment of the present invention, the crosslinkable RTV composition has the following composition.
적어도 1종의 가교성 폴리실록산 100 중량부,100 parts by weight of at least one crosslinkable polysiloxane,
적어도 1종의 실란 가교제 0.5 내지 20 중량부,0.5 to 20 parts by weight of at least one silane crosslinker,
적어도 1종의 본 발명에 따른 주석 촉매 0.005 내지 5 중량부,0.005 to 5 parts by weight of at least one tin catalyst according to the invention,
적어도 1종의 충전제 0 내지 500 중량부 및0 to 500 parts by weight of at least one filler and
추가의 첨가제 및 보조 물질 0 내지 200 중량부.0 to 200 parts by weight of additional additives and auxiliary substances.
바람직하게는, 첨가제 및 보조 물질은 하기와 같은 조성이다.Preferably, the additives and auxiliary substances are of the following composition.
가소제 0 내지 100 중량부,0 to 100 parts by weight of a plasticizer,
커플링제 0 내지 20 중량부,0 to 20 parts by weight of a coupling agent,
안료 0 내지 100 중량부,Pigment 0 to 100 parts by weight,
살진균제 0 내지 20 중량부 및0-20 parts by weight of fungicide and
조촉매 및 안정화제 0 내지 20 중량부 및0 to 20 parts by weight of the promoter and stabilizer and
스캐빈저 0 내지 5 중량부,Scavenger 0-5 parts by weight,
여기에서, 혼합물 중의 모든 첨가제 및 보조 물질의 총량은 0 보다 크며, 200 중량부 이하이다.Here, the total amount of all additives and auxiliary substances in the mixture is greater than zero and is 200 parts by weight or less.
가교성 RTV 조성물의 각각 성분을 소정의 목적하는 순서로 함께 혼합할 수 있다. 성분들을 실온에서 혼합하는 것이 바람직하다. 본 발명에 따른 주석 촉매가 반응계 내에서 생성되는 경우에는, 각각의 성분을 실온에서 함께 교반하는 것이 바람직하다.Each component of the crosslinkable RTV composition can be mixed together in any desired order. Preference is given to mixing the components at room temperature. When the tin catalyst according to the invention is produced in the reaction system, it is preferable to stir each component together at room temperature.
RTV 조성물은 통상의 선행 기술의 혼합 장치, 예를 들면 유성형 혼합기, 고속 혼합기, 접형 혼합기 또는 연속 작동 혼합 스크류로 제조할 수 있다.RTV compositions can be prepared with conventional prior art mixing devices such as planetary mixers, high speed mixers, tangent mixers or continuous operation mixing screws.
하기에 실시예는 본 발명을 설명하는 것으로, 본 발명을 한정하는 것은 아니다.The following Examples illustrate the invention and do not limit the invention.
〈실시예 1〉<Example 1>
산화 디옥틸주석 150 g, 모노-2-에틸헥실 포스페이트 87.2 g을 교반기, 온도계, 환류 응축기 및 물 분리기가 장착된 삼구 플라스크의 톨루엔 400 g 중으로 질소 대기하에서 도입시켰다. 혼합물을 교반하면서 125 ℃로 천천히 가열하고, 반응 중에 형성되는 물은 톨루엔과 공비성 혼합물로서 물 분리기로 증류, 분리하였다. 약 3시간 후에, 반응이 완료되었고, 더 이상 물을 증류할 수 없었다. 그 뒤, 반응 혼합물을 50 mbar의 감압하에서 80 내지 100 ℃로 증발시켜 톨루엔 잔류 함량을 17 중량%로 낮추었다. 투명한 연황색 액체를 수득하였다. 원소 분석에 따르면, 생성물의 주석 함량은 17.8 %이었다.150 g of dioctyltin oxide and 87.2 g of mono-2-ethylhexyl phosphate were introduced under nitrogen atmosphere into 400 g of toluene in a three-necked flask equipped with a stirrer, thermometer, reflux condenser and water separator. The mixture was slowly heated to 125 ° C. with stirring, and the water formed during the reaction was distilled off and separated by a water separator as an azeotropic mixture with toluene. After about 3 hours, the reaction was complete and no more water could distill. The reaction mixture was then evaporated to 80-100 ° C. under reduced pressure of 50 mbar to lower the toluene residual content to 17% by weight. A clear pale yellow liquid was obtained. According to the elemental analysis, the tin content of the product was 17.8%.
〈실시예 2〉<Example 2>
산화 디옥틸주석 150 g, 모노-2-에틸헥실 포스페이트 174.4 g 및 테트라프로필 실리케이트 178.7 g을 교반기, 온도계 및 환류 응축기가 장착된 삼구 플라스크에 질소 대기 하에서 도입하였다. 혼합물을 교반하면서 160 ℃로 천천히 가열한 뒤, 그 온도에서 추가로 3 시간 동안 교반하였다. 그 뒤, 혼합물을 냉각하고, 환류 응축기를 응축기가 장착된 증류 장치로 대체하고, 모든 휘발성 성분을 정상 압력하의 최고온 160 ℃에서 1시간 동안 증발시켰다. 증류물 73.3 g을 분리하여, 크로마토그래피로 검증한 결과 프로판올이었다. 반응 생성물은 주석 함량이 11.2 % (원소 분석에 의함)인 투명한 연황색 액체였다.150 g of dioctyltin oxide, 174.4 g of mono-2-ethylhexyl phosphate and 178.7 g of tetrapropyl silicate were introduced into a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser under nitrogen atmosphere. The mixture was slowly heated to 160 ° C. with stirring and then stirred for an additional 3 hours at that temperature. Thereafter, the mixture was cooled down, the reflux condenser was replaced with a distillation unit equipped with a condenser, and all volatile components were evaporated at a maximum temperature of 160 ° C. under normal pressure for 1 hour. 73.3 g of distillate was separated and verified by chromatography to give propanol. The reaction product was a clear pale yellow liquid with a tin content of 11.2% (by elemental analysis).
〈실시예 3〉<Example 3>
산화 디옥틸주석 200 g, 디-2-에틸헥실 포스페이트 178.3 g 및 85 %의 인산 64 g을 교반기, 온도계, 환류 응축기 및 물 분리기가 장착된 삼구 플라스크의 톨루엔 400 g 중으로 질소 대기하에서 도입시켰다. 혼합물을 교반하면서 120 ℃로 천천히 가열하고, 반응 중에 생성되는 물은 톨루엔과 공비성 혼합물로서 물 분리기로 증류, 분리하였다. 약 2시간 후에, 반응이 완료되었고, 더 이상 물을 증류할 수 없었다. 그 뒤, 반응 혼합물을 초기에는 표준압력으로, 그 뒤에는 5 mbar의 감압하에서 최고 110 ℃로 증발시켜, 톨루엔 잔류 함량을 10 중량%로 낮추었다. 투명한 연황색 액체를 수득하였다. 원소 분석에 따르면, 생성물의 주석 함량은 14.4 %이었다.200 g of dioctyltin oxide, 178.3 g of di-2-ethylhexyl phosphate and 64 g of 85% phosphoric acid were introduced under nitrogen atmosphere into 400 g of toluene in a three-necked flask equipped with a stirrer, thermometer, reflux condenser and water separator. The mixture was slowly heated to 120 ° C. while stirring, and the water produced during the reaction was distilled off and separated by a water separator as an azeotropic mixture with toluene. After about 2 hours, the reaction was complete and no more water could distill. The reaction mixture was then initially evaporated to standard pressure and then up to 110 ° C. under reduced pressure of 5 mbar to lower the toluene residual content to 10% by weight. A clear pale yellow liquid was obtained. According to the elemental analysis, the tin content of the product was 14.4%.
〈비교 실시예 4〉<Comparative Example 4>
산화 디옥틸주석 1368 g 및 테트라프로필 실리케이트 1632 g을 교반기, 온도계 및 환류 응축기가 장착된 삼구 플라스크에 질소 대기하에서 도입하였다. 혼합물을 교반하면서 160 ℃로 천천히 가열하고, 그 온도에서 추가로 5시간 동안 교반하였다. 반응 생성물은 투명한 황색 액체였다. 원소 분석에 따르면, 생성물의 주석 함량은 14.5 %이었다.1368 g of dioctyltin oxide and 1632 g of tetrapropyl silicate were introduced under a nitrogen atmosphere into a three-necked flask equipped with a stirrer, thermometer and reflux condenser. The mixture was slowly heated to 160 ° C. with stirring and stirred for an additional 5 hours at that temperature. The reaction product was a clear yellow liquid. According to the elemental analysis, the tin content of the product was 14.5%.
〈실시예 5〉<Example 5>
실시예 4에서 제조한 생성물 70 g을 모노-2-에틸헥실 포스페이트 37 g과 실온에서 반응시켰다. 혼합물은 투명한 무색 액체이었고, 이후 시험용 RTV-1 조성물에 사용하였다.70 g of the product prepared in Example 4 were reacted with 37 g of mono-2-ethylhexyl phosphate at room temperature. The mixture was a clear colorless liquid which was then used in the test RTV-1 composition.
〈실시예 6〉<Example 6>
산화 디부틸주석 100 g, 디-2-에틸헥실 포스페이트 168.7 g을 교반기, 온도계, 환류 응축기 및 물 분리기가 장착된 삼구 플라스크의 톨루엔 300 g 중으로 질소대기 하에서 도입하였다. 혼합물을 교반하면서 125 ℃로 천천히 가열하고, 반응 중에 생성되는 물은 톨루엔과 공비성 혼합물로서 물 분리기로 약 3시간 동안 증류, 분리하였다. 그 뒤, 반응 혼합물을 10 mbar 감압하에서 110 ℃로 증발시켜, 톨루엔 잔류 함량을 약 11 중량%로 낮추었다. 투명한 연황색 액체를 수득하였다. 원소 분석에 따르면, 생성물의 주석 함량은 15.4 %이었다.100 g of dibutyltin oxide and 168.7 g of di-2-ethylhexyl phosphate were introduced under nitrogen atmosphere into 300 g of toluene in a three-necked flask equipped with a stirrer, thermometer, reflux condenser and water separator. The mixture was slowly heated to 125 ° C. with stirring, and the water produced during the reaction was distilled and separated for about 3 hours using a water separator as an azeotropic mixture with toluene. The reaction mixture was then evaporated to 110 ° C. under 10 mbar reduced pressure to lower the toluene residual content to about 11 wt%. A clear pale yellow liquid was obtained. According to the elemental analysis, the tin content of the product was 15.4%.
〈비교 실시예 7〉<Comparative Example 7>
50 % 톨루엔 중의 디부틸주석 디옥토에이트 용액을 제조하였다. 이 주석 촉매를 비교 목적으로 사용하였고, 촉매로서 선행 기술에서 공지되어 사용되는 생성물이었다.A solution of dibutyltin dioctoate in 50% toluene was prepared. This tin catalyst was used for comparison purposes and was the product known and used in the prior art as a catalyst.
RTV-1 조성물의 제조 및 평가를 위한 일반적 절차General Procedures for the Preparation and Evaluation of RTV-1 Compositions
조성물을 하기 실시예에 따라 1 L의 유성형 혼합기에서 생성하였다. 생성이 완료된 후에, 조성물을 플라스틱 카트리지로 옮겼다. 추가 시험을 위해 재료를 봉합된 카트리지에서 꺼냈다.The composition was produced in a 1 L planetary mixer according to the examples below. After production was complete, the composition was transferred to a plastic cartridge. The material was removed from the sealed cartridge for further testing.
폴리실록산 조성물의 가교성 거동은 유리 시트 상에서 시험하는데, 유리 단부의 40 × 60 mm의 면 위에 2 mm 두께로 페이스트를 도포하였다. 24 시간 후에, 재료가 유리 표면에 완전히 경화되었는지를 측정하는 시험을 하였다.The crosslinkable behavior of the polysiloxane composition was tested on a glass sheet, with the paste applied 2 mm thick on the 40 × 60 mm face of the glass end. After 24 hours, a test was conducted to determine whether the material had completely cured to the glass surface.
경화물의 기계적 특성을 2 mm 두께로 페이스트를 시트로 만들고, 23 ℃의 온도 및 50 %의 상대 대기 습도에서 14일 간의 경화 후에 DIN 53 504로 시험함으로써 측정하였다. 경도를 21일 후에 DIN 53 505로 측정하였다.The mechanical properties of the cured product were measured by sheeting the paste to a thickness of 2 mm and testing to DIN 53 504 after 14 days of curing at a temperature of 23 ° C. and a relative atmospheric humidity of 50%. The hardness was measured to DIN 53 505 after 21 days.
밀봉 튜브 중의 페이스트를 50 ℃ 또는 100 ℃로 저장함으로써 생성물의 저장 안정성을 평가하였다. 50 ℃에서 저장한 표본을 1주일 간격으로 튜브에서 재료를 꺼내어 가교성 시험을 하였다. 만일, 표본이 1주일 후에 완벽하게 가교되었다면, 시험에 통과된 것으로 간주하였다. 재료 표본을 100 ℃에서 저장한 표본으로부터 매일 취해 시험하였다. 만일, 표본이 1일 후에 완벽하게 가교되었다면, 시험에 통과된 것으로 간주하였다. 50 ℃ 또는 100 ℃에서의 저장 안정성 시험은 상대적으로 짧은 시간 내에 실제적으로 생성물의 저장 안정성을 평가할 수 있는 통상의 실란트 시험 방법이었다.The storage stability of the product was evaluated by storing the paste in a sealed tube at 50 ° C. or 100 ° C. Samples stored at 50 ° C. were removed from the tubes at weekly intervals for crosslinkability testing. If the specimen was fully crosslinked after one week, it was considered to pass the test. Material samples were taken daily from samples stored at 100 ° C. and tested. If the specimen was fully crosslinked after 1 day, it was considered to pass the test. The storage stability test at 50 ° C. or 100 ° C. was a conventional sealant test method that could evaluate the storage stability of the product in a relatively short time.
〈실시예 8 내지 13〉<Examples 8 to 13>
Si(CH=CH2)(OCH3)2를 말단기로 하는 폴리디메틸실록산 55.0 중량부 (이것의 점도는 25 ℃에서 80 Pa.s임)과 -OSi(CH3)3를 말단기로 하는 폴리디메틸실록산 29.0 중량부 (이것의 점도는 25 ℃에서 100 mPa.s임) 및 비닐트리메톡시실란 2.5 중량부을 유성형 혼합기에서 혼합하였다. 데구사 (Degussa)에서 에어로질 (Aerosil; 상품명) R 972로 시판하는 소수성 실리카 9.5 중량부를 상기 혼합물에 혼입시키고, 혼합물을 섞어 균질한 페이스트를 얻었다. 그 뒤, 3-아미노프로필트리에톡시실란 0.8 중량부를 상기 혼합물에 가하고, 표 1에 기재된 양의 주석 촉매를 가함으로써 시험을 종결하였다.55.0 parts by weight of polydimethylsiloxane having Si (CH = CH 2 ) (OCH 3 ) 2 as its end group, the viscosity of which is 80 Pa · s at 25 ° C. and -OSi (CH 3 ) 3 as the end group 29.0 parts by weight of polydimethylsiloxane (its viscosity is 100 mPa · s at 25 ° C.) and 2.5 parts by weight of vinyltrimethoxysilane were mixed in a planetary mixer. 9.5 parts by weight of hydrophobic silica sold by Degussa as Aerosil (R) R 972 were incorporated into the mixture, and the mixture was mixed to obtain a homogeneous paste. The test was then terminated by adding 0.8 parts by weight of 3-aminopropyltriethoxysilane to the mixture and adding a tin catalyst in the amounts shown in Table 1.
실시예 8 내지 13의 RTV-1 조성물 모두는 제조후에 완벽하게 경화되었다. 시험 결과는 표 1에 나타내었다. 실시예 13은 본 발명의 주석 촉매가 실란트 제조 동안의 반응계 내에서 생성될 수 있음을 나타내었다.All of the RTV-1 compositions of Examples 8-13 were fully cured after preparation. The test results are shown in Table 1. Example 13 showed that the tin catalyst of the present invention can be produced in the reaction system during sealant preparation.
〈실시예 14 내지 19〉<Examples 14 to 19>
Si(CH=CH2)(OCH3)2를 말단기로 하는 폴리디메틸실록산 55.0 중량부 (이것의 점도는 25 ℃에서 80 Pa.s임)과 -OSi(CH3)3를 말단기로 하는 폴리디메틸실록산 29.0 중량부 (이것의 점도는 25 ℃에서 100 mPa.s임) 및 비닐트리메톡시실란 2.5 중량부을 유성형 혼합기에서 혼합하였다. 데구사에서 에어로질 (Aerosil; 상품명) R 972로 시판하는 소수성 실리카 9.5 중량부를 상기 혼합물에 혼입시키고, 혼합물을 섞어 균질한 페이스트를 얻었다. 그 뒤, 3-아미노프로필트리에톡시실란 0.8 중량부를 상기 혼합물에 가하고, 표 2에 언급된 양의 헥사메틸디실라잔 및 주석 촉매를 가함으로써 시험을 종결시켰다.55.0 parts by weight of polydimethylsiloxane having Si (CH = CH 2 ) (OCH 3 ) 2 as its end group, the viscosity of which is 80 Pa · s at 25 ° C. and -OSi (CH 3 ) 3 as the end group 29.0 parts by weight of polydimethylsiloxane (its viscosity is 100 mPa · s at 25 ° C.) and 2.5 parts by weight of vinyltrimethoxysilane were mixed in a planetary mixer. 9.5 parts by weight of hydrophobic silica, commercially available from Degussa as Aerosil R 972, was incorporated into the mixture, and the mixture was mixed to obtain a homogeneous paste. The test was then terminated by adding 0.8 parts by weight of 3-aminopropyltriethoxysilane to the mixture and adding hexamethyldisilazane and tin catalyst in the amounts mentioned in Table 2.
RTV-1 생성물 모두는 제조후에 완벽하게 경화하였다. 시험 결과는 표 2에 나타내었다. 실시예 17 내지 19는 안정화제인 헥사메틸디실라잔의 양이 증가함에 따라 (0.4 중량부, 실시예 18, 표 2 참조) 저장 안정성이 확연히 향상됨을 보여준다. 통상의 주석 촉매와 비교해볼 때 (비교 시험 15, 16), 본 발명의 촉매 및 헥사메틸디실라잔의 조합물의 저장 안정성이 뚜렷히 향상되었다.All RTV-1 products were fully cured after preparation. The test results are shown in Table 2. Examples 17-19 show that storage stability is significantly improved as the amount of the stabilizer hexamethyldisilazane increases (0.4 parts by weight, see Example 18, Table 2). Compared with conventional tin catalysts (comparative tests 15, 16), the storage stability of the combination of the catalyst of the invention and hexamethyldisilazane was markedly improved.
Claims (14)
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DE19549425A DE19549425A1 (en) | 1995-09-13 | 1995-09-13 | Crosslinkable RTV silicone materials |
DE1995133963 DE19533963C1 (en) | 1995-09-13 | 1995-09-13 | Phosphorus-contg. organo-tin catalysts for silicone materials |
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