EP2195387A2 - Flame-resistant sealing material - Google Patents
Flame-resistant sealing materialInfo
- Publication number
- EP2195387A2 EP2195387A2 EP08836532A EP08836532A EP2195387A2 EP 2195387 A2 EP2195387 A2 EP 2195387A2 EP 08836532 A EP08836532 A EP 08836532A EP 08836532 A EP08836532 A EP 08836532A EP 2195387 A2 EP2195387 A2 EP 2195387A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- composition
- composition according
- carbon atoms
- polymer
- 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.)
- Withdrawn
Links
- 239000003566 sealing material Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 71
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 platinum metals Chemical class 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 238000009833 condensation Methods 0.000 claims abstract description 16
- 230000005494 condensation Effects 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000565 sealant Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 239000004014 plasticizer Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002318 adhesion promoter Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 150000002894 organic compounds Chemical group 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- UCVPKAZCQPRWAY-UHFFFAOYSA-N dibenzyl benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC=2C=CC=CC=2)C=1C(=O)OCC1=CC=CC=C1 UCVPKAZCQPRWAY-UHFFFAOYSA-N 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 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
- 239000001273 butane Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- XIKIUQUXDNHBFR-UHFFFAOYSA-N monobenzyl phthalate Chemical class OC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 XIKIUQUXDNHBFR-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UADWUILHKRXHMM-UHFFFAOYSA-N 2-ethylhexyl benzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-UHFFFAOYSA-N 0.000 description 1
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- GYZFQLGZYUPQIN-UHFFFAOYSA-L Cl[Pt]Cl.CC1=CC=NC=C1 Chemical compound Cl[Pt]Cl.CC1=CC=NC=C1 GYZFQLGZYUPQIN-UHFFFAOYSA-L 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 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 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 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
- 239000004568 cement Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- YAJIVAPCZRKADM-UHFFFAOYSA-L cycloocta-1,3-diene;platinum(2+);dichloride Chemical compound Cl[Pt]Cl.C1CCC=CC=CC1 YAJIVAPCZRKADM-UHFFFAOYSA-L 0.000 description 1
- UBDOHRFXPUJBOY-UHFFFAOYSA-L cyclopenta-1,3-diene;dichloroplatinum Chemical compound Cl[Pt]Cl.C1C=CC=C1 UBDOHRFXPUJBOY-UHFFFAOYSA-L 0.000 description 1
- QSELGNNRTDVSCR-UHFFFAOYSA-L dichloroplatinum;4-methylpyridine Chemical compound Cl[Pt]Cl.CC1=CC=NC=C1.CC1=CC=NC=C1 QSELGNNRTDVSCR-UHFFFAOYSA-L 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical class [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal 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
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 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
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOAJIYVOSJHEQB-UHFFFAOYSA-N trimethyl trimethoxysilyl silicate Chemical compound CO[Si](OC)(OC)O[Si](OC)(OC)OC XOAJIYVOSJHEQB-UHFFFAOYSA-N 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
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
Definitions
- the present invention relates to flame retardant compositions which can be used as sealants and to a process for their preparation.
- the sealants of the present invention contain silane-modified copolymers having one or more silicon-bonded and hydrolyzable groups (silyl groups) at the chain ends. These react when moisture enters and form elastomers with crosslinkers under the influence of catalysts. Two (or more) of such end groups result in crosslinking of the sealant. Crosslinking produces elastomers that are widely used, for example as adhesives, sealants or sealants.
- organopolysiloxane compositions which contain substantially organopolysiloxanes terminated with organoxy, catalysts and optionally additives.
- DE 197 57 308 A1 discloses elastomers which crosslink with elimination of alcohols to give organopolysiloxane compositions.
- an HO-terminated organopolysiloxane reacts in the presence of a suitable catalyst with an alkoxysilane which has at least three alkoxy groups and / or its partial hydrolyzate.
- the cross-linking process is odorless, since neutral, environmentally compatible alcohols release as cleavage products.
- DE 43 41 136 C2 discloses crosslinkable organopolysiloxane compositions which are difficult to burn elastomers.
- the starting material used is an organopolysiloxane having per molecule at least 2 SiC-bonded, aliphatically reacted hydrocarbon radicals, as well as further inorganic fillers and organopolysiloxane.
- organopolysiloxane having per molecule at least 2 SiC-bonded, aliphatically reacted hydrocarbon radicals, as well as further inorganic fillers and organopolysiloxane.
- DE 43 41 136 C2 only the use of an organopolysiloxane is disclosed as a prepolymer.
- Sealants made from such hybrids have very good properties, however, the use of these sealants in areas where flame retardant sealants are prescribed is not possible. There is therefore a need in the art to modify the known sealants to be flame retardant.
- a technical object of the present invention is thus to modify sealants containing silyl end group-modified polyethers so that elastomers prepared therefrom are flame retardant, and to provide a process for producing the same.
- the technical object of the present invention is achieved by a composition obtained by mixing
- n is a number from 0 to 3
- R 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of hydrogen and alkyl group having 1 to 8 carbon atoms, m is a number from 0 to 10 and
- o is a number from 1 to 1000
- polymer of general formula 1 has preferably been modified with acrylic acid
- composition (i) is obtained with admixing further constituents or (ii) without admixing further constituents.
- each variable with the same name can have its meaning independently of the other variables with the same name.
- variables with the same name also have the same meaning.
- composition according to the invention which is obtained by the mixing described above, with homogenization taking place after mixing component a and b.
- the homogenization is preferably carried out over a period of at least one hour, more preferably over a period of at least six hours to 48 hours.
- the homogenization takes place at room temperature by simply leaving it to stand.
- the homogenization is carried out for twelve hours or more, more preferred is homogenization for twenty hours or more, more preferably homogenization for twenty-four hours or more.
- Preferred upper limits for the homogenization time in this case are 48 hours, more preferably 40 hours, and particularly preferably 30 hours.
- up to 99.99% by weight and more preferably from 50 to 99.9% by weight of the polymer of formula 1 are added to the composition, based on the total weight of the composition. Alternatively, it is preferred to have 15 to 49% by weight.
- the polymer of formula 1 more preferably 20 to 40 wt .-%, each based on the total weight of the composition.
- the metal, compound or complex of the group of platinum metals is preferably in a proportion of 0.001 to 1.0% by weight, preferably 0.001 to 0.5% by weight, and more preferably, based on the total weight of the composition from 0.01 to 0.25% by weight in the composition.
- the condensation catalyst is preferably contained in a proportion of from 0.001 to 1% by weight, and more preferably from 0.01 to 0.5% by weight, in the composition, based on the total weight of the composition.
- the curing agent is preferably contained in a proportion of 0.1 to 10% by weight, and more preferably 1 to 5% by weight, in the composition, based on the total weight of the composition.
- the proportions of components from which the composition is obtained should be such that the sum of the selected ranges is 100% by weight.
- R 1 and R 2 of the polymer of general formula 1 are independently selected from the group consisting of methyl group, ethyl group, methoxy group and ethoxy group.
- R 1 is a methyl group
- R 2 is a methoxy group
- n is 1.
- R 3 , R 4 , R 5 and R 6 may be independently selected from the group consisting of hydrogen, methyl group and ethyl group.
- each m is 1, 2, 3 and / or 4 and / or o is a number from 1 to 100.
- o is a number from 1 to 50, more preferably 1 to 20 and especially 1, 2, 3 , 4, 5, 6, 7, 8, 9, or 10.
- R3, R4 and R5 are hydrogen and R6 is a methyl group.
- the metal, compound or complex of the group of platinum metals is platinum or palladium or comprises platinum or palladium.
- metallic or finely divided platinum supported on a support such as silica, alumina or activated carbon is added to the composition.
- Compounds or complexes of platinum such as platinum, for example, PtCl 6, H 2 PtCl 6 ⁇ 6H 2 O, Na 2 PtCl 4 ⁇ 4H 2 O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum Ether complexes, platinum-aldehyde
- platinum-ketone complexes including reaction products of H 2 PtCl 6 ⁇ 6H 2 O and cyclohexanone, platinum-vinylsiloxane complexes such as platinum-1, 3-divinyl-1, 1, 3,3-tetramethyldisiloxane complexes with or without of detectable inorganic halogen, bis ( ⁇ -picoline) platinum dichloride, trimethylenedipyridineplatinum dichloride, dicyclopentadiene platinum dichloride, dimethylsulfoxydethylenoplatinum (II) dichloride, cyclooctadiene platinum dichloride, norbonadiene platinum dichloride, ⁇ -picoline platinum dichloride and / or cyclopentadiene platinum dichloride are preferably used.
- the condensation catalyst to be added to the composition is preferably an organic compound of tin, zirconium, titanium and / or aluminum.
- Preferred among these condensation catalysts are butyl titanates and organic tin compounds, such as di-n-butyltin diacetate, di-n-butyltin dilaurate and reaction products of at least two oxygen-bonded to silicon, optionally substituted by an alkoxy group, monovalent hydrocarbon radicals as hydrolyzable groups silane or its oligomer with Diorga- nozinndiacetat, wherein in these reaction products all valences of the tin atoms are saturated by oxygen atoms of the group -SiOSn- or by SnC-bonded, monovalent organic radicals.
- the curing agent preferably leads to crosslinking of the composition.
- the curing agent is preferably an alkoxysilane, which preferably has at least three alkoxy groups and / or its partial hydrolyzate.
- a preferred alkoxysilane is vinyltrimethoxysilane or vinyltriethoxysilane.
- a partial hydrolyzate is preferably obtained by hydrolysis and condensation of preferably 2 to 4 alkoxysilanes. Partial hydrolysates are, for example, hexamethoxydisiloxane and hexahydoxydisiloxane.
- a filler is additionally added to the composition.
- the fillers may be selected from oxides or mixed oxides of metals and / or semimetals. Preference is given to fillers, 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, non-reinforcing fillers such as pyrogenic silica, precipitated silica, carbon black such as furnace or acetylene black and silicon-aluminum mixed oxides with high BET surface area and fibrous Fillers, such as asbestos, as well as plastic fibers.
- fillers such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powder
- the fillers mentioned may be rendered hydrophobic, for example by treatment with organosilane or siloxane, with stearic acid or by etherification of hydroxyl groups with alkoxy groups.
- One type of filler or else a mixture of at least two fillers may be added to the composition.
- the filler is preferably contained in a proportion of 1 to 80% by weight, preferably 5 to 70% by weight, and more preferably 10 to 60% by weight, based on the total weight of the composition.
- a plasticizer is added to the composition.
- plasticizers it is possible to use all plasticizers which are familiar to the person skilled in the art.
- trimethylsiloxy-endblocked dimethylpolysiloxanes or phosphoric acid esters which are liquid at room temperature may be added.
- alkylaryl phosphates which are added as plasticizers.
- the plasticizer is selected from the group of benzyl phthalate esters,
- Dibenzoate esters phosphate esters, polymeric adipic acid esters and mixtures thereof.
- the plasticizer is preferably contained in a proportion of 0.1 to 30% by weight, preferably 5 to 25% by weight, and more preferably 1 to 15% by weight, based on the total weight of the composition. Depending on the mixing method, it is preferred to add the plasticizer before a possible homogenization and / or after a possible homogenization of the composition.
- adhesion promoters are added to the composition.
- the adhesion promoters are preferably alkoxysilanes, aminosilanes and / or alkoxyaminosilanes which, in addition to alkoxy groups and / or amino groups, radicals selected from the group consisting of hydrogen atom, SiC-bonded hydrocarbon radicals, and SiC-bonded, substituted hydrocarbon radicals, and mixtures thereof and partial or mixed hydrolysates.
- the alkoxy groups having 1 to 6 carbon atoms are preferred, in particular methoxy, ethoxy and propoxy groups.
- hydrocarbon radicals alkyl and alkenyl radicals, and in particular the vinyl and 2-propynyl radicals, are preferred.
- the hydrocarbyl group is a hydrocarbyl group having from 1 to 18 carbon atoms optionally substituted with epoxy, (poly) glycol or acid anhydride groups or groups of the formula --O (CO) - R 7 wherein R 7 is hydrogen or hydrocarbyl.
- the coupling agent is preferably contained in a proportion of 0.1 to 10% by weight, and more preferably 1 to 5% by weight, in the composition, based on the total weight of the composition.
- the adhesion promoter is added before possible homogenization and / or after possible homogenization.
- all ingredients of the composition are dried before mixing.
- essentially anhydrous or anhydrous ingredients are used to prepare the composition.
- the composition of the present invention exhibits very good flame retardancy.
- the low flammability can be determined according to DIN 4102 in the fire shaft.
- the improved flame retardancy is likely, but without being bound by theory, achieved by the combination of the metal selected from the group of platinum metals with the condensation catalyst.
- Compositions which do not contain the combination of both substances show a significantly higher flammability and are suitable for use in in which flame retardant sealing materials are prescribed are not suitable.
- a further aspect of the present invention is a process for the preparation of the aforementioned composition comprising the steps:
- R 1 and R 2 are independently selected from the group consisting of alkyl group having 1 to 8 carbon atoms and alkyloxy group having 1 to 8 carbon atoms, n is a number from 0 to 3,
- R 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of hydrogen and alkyl group having 1 to 8 carbon atoms, m is a number from 0 to 10 and o is a number from 1 to 1000, wherein the polymer of the is optionally modified with acrylic acid, b) a metal, a compound or a complex from the group of platinum metals
- homogenization takes place after step b), preferably in the manner indicated above.
- R 1 and R 2 of the polymer of general formula 1 are independently selected from the group consisting of methyl group, ethyl group, methoxy group and ethoxy group.
- R 1 is a methyl group and R 2 is a methoxy group, where n is 1.
- R 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of hydrogen, methyl group and ethyl group. It is further preferred that each m is 1, 2 3 and / or and / or o is a number from 1 to 100. Preferably, R 3, R 4 and R 5 are hydrogen and R 6 is a methyl group.
- the metal used is preferably platinum or palladium, wherein the aforementioned specific metal compounds can be preferably used.
- condensation catalyst is preferably an organic compound of tin, zirconium, titanium and / or aluminum.
- the aforementioned condensation catalysts may preferably be used.
- fillers, plasticizers and / or adhesion promoters can be used in the process.
- part of the invention is also a composition which can be prepared by a process according to the invention. Also part of the invention is a compound of a composition according to the invention as a sealant, adhesive and / or sealant.
- compositions according to the invention show a pronounced low flammability.
- the low flammability can be determined by a test of the fire behavior according to DIN 4102-1: 1998-05. By way of reference, this standard becomes part of this application. Accordingly, according to the invention, preferred mixtures according to the invention are hardly inflammable. It has been found that the homogenization described above after addition of a metal, a compound or a complex from the group of platinum metals has a positive effect on the degree of flame retardancy. The combination of a metal, a compound or a complex from the group of platinum metals with a condensation catalyst also seems to have a positive effect on the flame retardancy.
- compositions which do not contain a combination of the last two groups of substances show a significantly higher flammability and are not suitable for use in areas where flame-retardant sealing materials are prescribed. It proved to be preferable to let a homogenization take place as described above before the condensation catalyst and / or the curing agent was added to the composition.
- the resulting sealant composition exhibits a very good flame retardancy after curing. According to DIN 4102-1: 1998-05, the low flammability in the fire shaft is sufficient.
- the sealing properties of the sealant composition are comparable to the prior art sealant compositions.
- aminopropyltrimethoxysilane aminopropyltrimethoxysilane (silane A1 110, obtained from SWOP-Chemie, Berchtoldsdorf) and 3 kg of platinum catalyst (Pt-Kat512, Hansechemie, Hamburg) were added. To homogenize the mixture was allowed to stand for 24 hours at room temperature. Then, 10 kg of vinyltrimethoxysilane (VTMO, available from Momentive, Leverkusen) and 2 kg of dibutyltin diketanoate (TEGOKAT 226, Goldschmittt, Mannheim) were added.
- VTMO vinyltrimethoxysilane
- TEGOKAT 226, Goldschmittt, Mannheim dibutyltin diketanoate
- Example 2 Analogously to Example 2, a sealant was prepared, although dispensed with the metered addition of the platinum catalyst.
- the fire test was carried out according to DIN 4102-1 section 6.2.5. Five edge flames according to Section 6.2.5.2 (Samples Nos. 1 to 5) and five surface flames according to Section 6.2.5.3 (Samples Nos. 6 to 10) were performed. The test results are listed in the following table:
- a jointing compound was placed in a 15 mm wide joint between two fiber cement carriers and pulled flush with the carriers.
- the joint depth was 10 mm.
- Fig. 1 illustrates the course of the flue gas temperature.
- Fig. 2 illustrates the course of the light attenuation.
- Table 3 summarizes test results in tabular form:
- the sealant produced according to Example 2 meets the requirements of building material class B1 (flame retardant) according to DIN 4102-1: 1998-05.
- the sealant is according to DIN 4102-16: 1998-05 as non-burning falling / dripping.
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Abstract
Description
Bremen, 25. September 2008 Bremen, September 25, 2008
Unser Zeichen: RM 5143-01 EP GDO/vriOur sign: RM 5143-01 EP GDO / vri
Anmelder/Inhaber: Ramsauer DichtstoffeApplicant / owner: Ramsauer Dichtstoffe
Amtsaktenzeichen: NeuanmeldungOfficial file: new registration
KREIDEWERK JOSEF RAMSAUER KG, 5351 Aigen-Voglhub, ÖsterreichKREIDEWERK JOSEF RAMSAUER KG, 5351 Aigen-Voglhub, Austria
Schwerentflamm bares DichtungsmittelFlame-resistant sealant
Die vorliegende Erfindung betrifft schwerentflammbare Zusammensetzungen, die als Dichtungsmittel verwendet werden können, sowie ein Verfahren zu ihrer Herstellung.The present invention relates to flame retardant compositions which can be used as sealants and to a process for their preparation.
Die Dichtungsmittel der vorliegenden Erfindung enthalten silanmodifizierte Copolymere, die an den Kettenenden ein oder mehrere, an Silicium gebundene und hydrolysierbare Gruppen aufweisen (Silylgruppen). Diese reagieren bei Zutritt von Feuchtigkeit und bilden mit Vernetzern unter Einfluß von Katalysatoren Elastomere aus. Zwei (oder mehr) solcher Endgruppen führen zur Vernetzung des Dichtungsmittels. Bei der Vernetzung entstehen Elastomere, die breite Anwendung finden, beispielsweise als Kleber, Versiegelungs- oder Dichtungsmittel.The sealants of the present invention contain silane-modified copolymers having one or more silicon-bonded and hydrolyzable groups (silyl groups) at the chain ends. These react when moisture enters and form elastomers with crosslinkers under the influence of catalysts. Two (or more) of such end groups result in crosslinking of the sealant. Crosslinking produces elastomers that are widely used, for example as adhesives, sealants or sealants.
Im Stand der Technik sind Organopolysiloxan-Massen bekannt, die im Wesentlichen mit Organoxygruppen terminierte Organopolysiloxane, Katalysatoren und ggf. Additive enthalten.In the prior art organopolysiloxane compositions are known which contain substantially organopolysiloxanes terminated with organoxy, catalysts and optionally additives.
In der DE 197 57 308 A1 werden Elastomere offenbart, die unter Abspaltung von Alkoholen zu Organopolysiloxan-Massen vernetzen. Hierbei reagiert ein HO-terminiertes Orga- nopolysiloxan in Gegenwart eines geeigneten Katalysators mit einem Alkoxysilan, das mindestens drei Alkoxygruppen aufweist und/oder dessen Teilhydrolysat. Der Vernetzungsvorgang ist geruchlos, da sich neutrale, umweltverträgliche Alkohole als Spaltprodukte freisetzen. Die DE 43 41 136 C2 offenbart zu schwer brennbaren Elastomeren vernetzbare Organo- polysiloxan-Massen. Als Ausgangsmaterial wird ein Organopolysiloxan mit pro Molekül mindestens 2 SiC-gebundenen, aliphatisch umgesetzten Kohlenwasserstoffresten, sowie weiteren anorganischen Füllstoffen und Organopolysiloxan eingesetzt. In der DE 43 41 136 C2 wird nur die Verwendung eines Organopolysiloxans als Präpolymer offenbart.DE 197 57 308 A1 discloses elastomers which crosslink with elimination of alcohols to give organopolysiloxane compositions. In this case, an HO-terminated organopolysiloxane reacts in the presence of a suitable catalyst with an alkoxysilane which has at least three alkoxy groups and / or its partial hydrolyzate. The cross-linking process is odorless, since neutral, environmentally compatible alcohols release as cleavage products. DE 43 41 136 C2 discloses crosslinkable organopolysiloxane compositions which are difficult to burn elastomers. The starting material used is an organopolysiloxane having per molecule at least 2 SiC-bonded, aliphatically reacted hydrocarbon radicals, as well as further inorganic fillers and organopolysiloxane. In DE 43 41 136 C2, only the use of an organopolysiloxane is disclosed as a prepolymer.
Allerdings ergibt sich im Stand der Technik der Bedarf, die sonst als Dichtungsmittel verwendeten Polyetherelastomere, die mit terminalen Silylgruppen eine Funktionalität aufweisen, die es erlaubt, in Anwesenheit von Feuchtigkeit und Alkoxysilanen zu einem Elastomer zu vernetzen, schwerentflammbar aufzurüsten, da die im Stand der Technik bekannten Elastomere leicht entflammbar sind. Die vorgenannten Dichtungsmassen werden aufgrund ihrer chemischen Struktur üblicherweise auch als Hybride bezeichnet, da sie eine Polyetherkette in Kombination mit Silylendgruppen aufweisen.However, in the prior art, the need to upgrade the polyether elastomers otherwise used as sealants to silane functional groups which permit crosslinking to form an elastomer in the presence of moisture and alkoxysilanes results in the difficulty of flame retardant upgrading, as is known in the art known elastomers are highly flammable. Because of their chemical structure, the abovementioned sealants are usually also referred to as hybrids, since they have a polyether chain in combination with silyl end groups.
Dichtungsmittel, die aus solchen Hybriden hergestellt werden, weisen sehr gute Eigenschaften auf, allerdings ist die Verwendung dieser Dichtungsmittel in Bereichen, in denen schwerentflammbare Dichtungsmittel vorgeschrieben sind, nicht möglich. Es besteht deshalb im Stand der Technik der Bedarf, die bekannten Dichtungsmittel derart zu modifizieren, dass sie schwer entflammbar sind.Sealants made from such hybrids have very good properties, however, the use of these sealants in areas where flame retardant sealants are prescribed is not possible. There is therefore a need in the art to modify the known sealants to be flame retardant.
Eine technische Aufgabe der vorliegenden Erfindung ist somit Dichtungsmittel enthaltend Silylendgruppen-modifizierte Polyether zu modifizieren, so dass hieraus hergestellte Elastomere schwerentflammbar sind, sowie die Bereitstellung eines Verfahrens zur Herstellung derselben.A technical object of the present invention is thus to modify sealants containing silyl end group-modified polyethers so that elastomers prepared therefrom are flame retardant, and to provide a process for producing the same.
Die technische Aufgabe der vorliegenden Erfindung wird durch eine Zusammensetzung, die durch Vermischen vonThe technical object of the present invention is achieved by a composition obtained by mixing
a) einem Polymer der allgemeinen Formel 1a) a polymer of general formula 1
R1 nR23-nSi(CR3R4)m-(O-CR3R4-CR5R6)o-O-(CR3R4)mSiR1 nR23-n (1 ), wobei R1 und R2 unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Alkylgruppe mit 1 bis 8 Kohlenstoffatomen und Alkyloxygruppe mit 1 bis 8 Kohlenstoffatomen,R 1 n R 2 3-n Si (CR 3 R 4 ) m - (O-CR 3 R 4 -CR 5 R 6 ) o -O- (CR 3 R 4 ) m SiR 1 n R 2 3-n (1 wherein R 1 and R 2 are independently selected from the group consisting of alkyl group of 1 to 8 carbon atoms and alkyloxy group of 1 to 8 carbon atoms,
n eine Zahl von 0 bis 3 ist,n is a number from 0 to 3,
R3, R4, R5 und R6 unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und Alkylgruppe mit 1 bis 8 Kohlenstoffatomen, m eine Zahl von 0 bis 10 undR 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of hydrogen and alkyl group having 1 to 8 carbon atoms, m is a number from 0 to 10 and
o eine Zahl von 1 bis 1000 ist,o is a number from 1 to 1000,
wobei das Polymer der allgemeinen Formel 1 vorzugsweise mit Acrylsäure modifiziert worden ist,wherein the polymer of general formula 1 has preferably been modified with acrylic acid,
b) einem Metall, einer Verbindung oder einem Komplex aus der Gruppe der Platinmetalle,b) a metal, a compound or a complex of the group of platinum metals,
c) einem Kondensationskatalysator, undc) a condensation catalyst, and
d) einem Härtungsmitteld) a curing agent
erhalten wird, wobei die Zusammensetzung (i) unter Zumischen weiterer Bestandteile oder (ii) ohne Zumischen weiterer Bestandteile erhalten wird, gelöst.is obtained, wherein the composition (i) is obtained with admixing further constituents or (ii) without admixing further constituents.
Selbstverständlich ist dem Fachmann klar, dass sofern eine Variable in der Formel 1 mehrfach vergeben ist (R1, R2, R3, R4) jede Variable mit der gleichen Bezeichnung ihre Bedeutung unabhängig von den anderen Variablen mit der gleichen Bezeichnung haben kann. Bevorzugt besitzen aber Variablen mit der gleichen Bezeichnung auch die gleiche Bedeutung.Of course, it is clear to the person skilled in the art that if a variable in formula 1 is assigned several times (R 1 , R 2 , R 3 , R 4 ), each variable with the same name can have its meaning independently of the other variables with the same name. Preferably, however, variables with the same name also have the same meaning.
Erfindungsgemäß bevorzugt ist eine erfindungsgemäße Zusammensetzung, die durch das oben beschriebene Vermischen erhalten wird, wobei nach Vermischen der Komponente a und der b eine Homogenisierung erfolgt. Die Homogenisierung erfolgt vorzugsweise über einen Zeitraum von mindestens einer Stunde, weiter bevorzugt über einen Zeitraum von mindestens sechs Stunden bis 48 Stunden.According to the invention, preference is given to a composition according to the invention which is obtained by the mixing described above, with homogenization taking place after mixing component a and b. The homogenization is preferably carried out over a period of at least one hour, more preferably over a period of at least six hours to 48 hours.
Besonders bevorzugt ist, dass die Homogenisierung bei Raumtemperatur durch einfaches Stehenlassen erfolgt. In diesem Fall ist es bevorzugt, dass die Homogenisierung für zwölf Stunden oder mehr erfolgt, weiter bevorzugt ist eine Homogenisierung für zwanzig Stunden oder mehr, besonders bevorzugt eine Homogenisierung für 24 Stunden oder mehr. Bevorzugte Obergrenzen für die Homogenisierungsdauer in diesem Falle sind 48 Stunden, weiter bevorzugt 40 Stunden, und besonders bevorzugt 30 Stunden.It is particularly preferred that the homogenization takes place at room temperature by simply leaving it to stand. In this case, it is preferable that the homogenization is carried out for twelve hours or more, more preferred is homogenization for twenty hours or more, more preferably homogenization for twenty-four hours or more. Preferred upper limits for the homogenization time in this case are 48 hours, more preferably 40 hours, and particularly preferably 30 hours.
In der Zusammensetzung werden bezogen auf das Gesamtgewicht der Zusammensetzung vorzugsweise bis zu 99,99 Gew.-% und weiter bevorzugt 50 bis 99,9 Gew.- % des Polymers der Formel 1 zugegeben. Alternativ ist bevorzugt, 15 bis 49 Gew.-% - A -Preferably, up to 99.99% by weight and more preferably from 50 to 99.9% by weight of the polymer of formula 1 are added to the composition, based on the total weight of the composition. Alternatively, it is preferred to have 15 to 49% by weight. - A -
des Polymers der Formel 1 zuzugeben, besonders bevorzugt 20 bis 40 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung.of the polymer of formula 1, more preferably 20 to 40 wt .-%, each based on the total weight of the composition.
Das Metall, die Verbindung oder der Komplex aus der Gruppe der Platinmetalle ist bezogen auf das Gesamtgewicht der Zusammensetzung vorzugsweise in einem An- teil von 0,001 bis 1 ,0 Gew.-%, vorzugsweise 0,001 bis 0,5 Gew.-% und weiter bevorzugt von 0,01 bis 0,25 Gew.-% in der Zusammensetzung enthalten.The metal, compound or complex of the group of platinum metals is preferably in a proportion of 0.001 to 1.0% by weight, preferably 0.001 to 0.5% by weight, and more preferably, based on the total weight of the composition from 0.01 to 0.25% by weight in the composition.
Der Kondensationskatalysator ist bezogen auf das Gesamtgewicht der Zusammensetzung vorzugsweise in einem Anteil von 0,001 bis 1 Gew.-% und weiter bevorzugt von 0,01 bis 0,5 Gew.-% in der Zusammensetzung enthalten.The condensation catalyst is preferably contained in a proportion of from 0.001 to 1% by weight, and more preferably from 0.01 to 0.5% by weight, in the composition, based on the total weight of the composition.
Das Härtungsmittel ist bezogen auf das Gesamtgewicht der Zusammensetzung vorzugsweise in einem Anteil von 0,1 bis 10 Gew.-% und weiter bevorzugt von 1 bis 5 Gew.-% in der Zusammensetzung enthalten.The curing agent is preferably contained in a proportion of 0.1 to 10% by weight, and more preferably 1 to 5% by weight, in the composition, based on the total weight of the composition.
Die Anteile an Komponenten, aus denen die Zusammensetzung erhalten wird, sind so zu wählen, dass die Summe der gewählten Bereiche 100 Gew.-% ergibt.The proportions of components from which the composition is obtained should be such that the sum of the selected ranges is 100% by weight.
Vorzugsweise sind R1 und R2 des Polymers der allgemeinen Formel 1 unabhängig voneinander ausgewählt aus der Gruppe enthaltend Methylgruppe, Ethylgruppe, Me- thoxygruppe und Ethoxygruppe.Preferably, R 1 and R 2 of the polymer of general formula 1 are independently selected from the group consisting of methyl group, ethyl group, methoxy group and ethoxy group.
In einer weiter bevorzugten Ausführungsform ist in der allgemeinen Formel 1 R1 eine Methylgruppe, R2 eine Methoxygruppe und n 1.In a further preferred embodiment, in the general formula 1, R 1 is a methyl group, R 2 is a methoxy group and n is 1.
Bevorzugt können R3, R4, R5 und R6 unabhängig voneinander ausgewählt sein aus der Gruppe bestehend aus Wasserstoff, Methylgruppe und Ethylgruppe.Preferably, R 3 , R 4 , R 5 and R 6 may be independently selected from the group consisting of hydrogen, methyl group and ethyl group.
Vorzugsweise sind m jeweils 1 , 2, 3 und/oder 4 und/oder o ist eine Zahl von 1 bis 100. In einer bevorzugten Ausführungsform ist o eine Zahl von 1 bis 50, weiter bevorzugt 1 bis 20 und insbesondere 1 , 2, 3, 4, 5, 6, 7, 8, 9, oder 10.Preferably, each m is 1, 2, 3 and / or 4 and / or o is a number from 1 to 100. In a preferred embodiment, o is a number from 1 to 50, more preferably 1 to 20 and especially 1, 2, 3 , 4, 5, 6, 7, 8, 9, or 10.
Es ist weiter bevorzugt, dass R3, R4 und R5 Wasserstoff und R6 eine Methylgruppe ist.It is further preferred that R3, R4 and R5 are hydrogen and R6 is a methyl group.
In einer bevorzugten Ausführungsform ist das Metall, die Verbindung oder der Komplex aus der Gruppe der Platinmetalle Platin oder Palladium bzw. umfasst Platin oder Palladium. Vorzugsweise wird metallisches oder feinverteiltes Platin, das sich auf einem Träger, wie Siliciumdioxid, Aluminiumoxid oder Aktivkohle befindet, der Zusammensetzung zugegeben. Verbindungen oder Komplexe von Platin, wie Platinhalogenide, z.B. PtCI6, H2PtCI6 ■ 6H2O, Na2PtCI4 ■ 4H2O, Platin-Olefin-Komplexe, Platin-Alkohol- Komplexe, Platin-Alkoholat-Komplexe, Platin-Ether-Komplexe, Platin-Aldehyd-In a preferred embodiment, the metal, compound or complex of the group of platinum metals is platinum or palladium or comprises platinum or palladium. Preferably, metallic or finely divided platinum supported on a support such as silica, alumina or activated carbon is added to the composition. Compounds or complexes of platinum, such as platinum, for example, PtCl 6, H 2 PtCl 6 ■ 6H 2 O, Na 2 PtCl 4 ■ 4H 2 O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum Ether complexes, platinum-aldehyde
Komplexe, Platin-Keton-Komplexe, einschließlich Umsetzungsprodukten von H2PtCI6 ■ 6H2O und Cyclohexanon, Platin-Vinylsiloxan-Komplexe, wie Platin-1 ,3-Divinyl- 1 ,1 ,3,3-tetramethyldisiloxankomplexe mit oder ohne Gehalt an nachweisbaren anorganisch gebundenem Halogen, Bis-(γ-picolin)-platindichlorid, Trimethylendipyridinpla- tindichlorid, Dicyclopentadienplatindichlorid, Dimethylsulfoxydethylenplatin-(ll)- dichlorid, Cyclooctadien-Platindichlorid, Norbonadien-Platindichlorid, γ-picolin- Platindichlorid und/oder Cyclopentadien-Platindichlorid können bevorzugt eingesetzt werden.Complexes, platinum-ketone complexes, including reaction products of H 2 PtCl 6 ■ 6H 2 O and cyclohexanone, platinum-vinylsiloxane complexes such as platinum-1, 3-divinyl-1, 1, 3,3-tetramethyldisiloxane complexes with or without of detectable inorganic halogen, bis (γ-picoline) platinum dichloride, trimethylenedipyridineplatinum dichloride, dicyclopentadiene platinum dichloride, dimethylsulfoxydethylenoplatinum (II) dichloride, cyclooctadiene platinum dichloride, norbonadiene platinum dichloride, γ-picoline platinum dichloride and / or cyclopentadiene platinum dichloride are preferably used.
Der Kondensationskatalysator, der der Zusammensetzung zugegeben wird, ist vor- zugsweise eine organische Verbindung von Zinn, Zirkonium, Titan und/oder Aluminium. Bevorzugt unter diesen Kondensationskatalysatoren sind Butyltitanate und organische Zinnverbindungen, wie Di-n-butylzinndiacetat, Di-n-butylzinndilaurat und Umsetzprodukte von je Molekül mindestens zwei über Sauerstoff an Silicium gebundene, ggf. durch eine Alkoxygruppe substituierte, einwertige Kohlenwasserstoffreste als hydrolysierbare Gruppen aufweisendem Silan oder dessen Oligomer mit Diorga- nozinndiacetat, wobei in diesen Umsetzungsprodukten alle Valenzen der Zinnatome durch Sauerstoffatome der Gruppierung -SiOSn- bzw. durch SnC-gebundene, einwertige organische Reste abgesättigt sind.The condensation catalyst to be added to the composition is preferably an organic compound of tin, zirconium, titanium and / or aluminum. Preferred among these condensation catalysts are butyl titanates and organic tin compounds, such as di-n-butyltin diacetate, di-n-butyltin dilaurate and reaction products of at least two oxygen-bonded to silicon, optionally substituted by an alkoxy group, monovalent hydrocarbon radicals as hydrolyzable groups silane or its oligomer with Diorga- nozinndiacetat, wherein in these reaction products all valences of the tin atoms are saturated by oxygen atoms of the group -SiOSn- or by SnC-bonded, monovalent organic radicals.
Das Härtungsmittel führt vorzugsweise zu einer Vernetzung der Zusammensetzung. Das Härtungsmittel ist vorzugsweise ein Alkoxysilan, das vorzugsweise mindestens drei Alkoxygruppen aufweist und/oder dessen Teilhydrolysat. Ein bevorzugtes Alkoxysilan ist Vinyltrimethoxysilan oder Vinyltriethoxysilan. Ein Teilhydrolysat wird vorzugsweise durch Hydrolyse und Kondensation von vorzugsweise 2 bis 4 Alkoxysila- nen erhalten. Teilhydrolysate sind beispielsweise Hexamethoxydisiloxan und Hexae- thoxydisiloxan.The curing agent preferably leads to crosslinking of the composition. The curing agent is preferably an alkoxysilane, which preferably has at least three alkoxy groups and / or its partial hydrolyzate. A preferred alkoxysilane is vinyltrimethoxysilane or vinyltriethoxysilane. A partial hydrolyzate is preferably obtained by hydrolysis and condensation of preferably 2 to 4 alkoxysilanes. Partial hydrolysates are, for example, hexamethoxydisiloxane and hexahydoxydisiloxane.
Vorzugsweise wird der Zusammensetzung zusätzlich ein Füllstoff beigegeben. Die Füllstoffe können ausgewählt sein aus Oxiden oder Mischoxiden von Metallen und/oder Halbmetallen. Bevorzugt sind Füllstoffe, wie Quarz, Diatomeenerde, CaI- ciumsilikat, Zirkoniumsilikat, Zeolithe, Metalloxidpulver, wie Aluminium-, Titan-, Ei- sen-, oder Zinkoxide bzw. deren Mischoxide, Bariumsulfat, Calciumcarbonat, Gips, Siliciumnitrid, Siliciumcarbid, Bornitrid, Glas- und Kunststoffpulver, wie Polyacrylnitril- pulver, verstärkende Füllstoffe, nichtverstärkende Füllstoffe, wie pyrogen hergestellte Kieselsäure, gefällte Kieselsäure, Ruß, wie Furnace- oder Acetylenruß und Silicium- Aluminium-Mischoxide mit großer BET-Oberfläche und faserförmige Füllstoffe, wie Asbest, sowie Kunststofffasern.Preferably, a filler is additionally added to the composition. The fillers may be selected from oxides or mixed oxides of metals and / or semimetals. Preference is given to fillers, 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, non-reinforcing fillers such as pyrogenic silica, precipitated silica, carbon black such as furnace or acetylene black and silicon-aluminum mixed oxides with high BET surface area and fibrous Fillers, such as asbestos, as well as plastic fibers.
Die genannten Füllstoffe können hydrophobiert sein, beispielsweise durch die Behandlung mit Organosilan bzw. Siloxan, mit Stearinsäure oder durch Veretherung von Hydroxylgruppen mit Alkoxygruppen. Es kann eine Art von Füllstoff, oder aber ein Gemisch aus mindestens zwei Füllstoffen der Zusammensetzung beigegeben wer- den.The fillers mentioned may be rendered hydrophobic, for example by treatment with organosilane or siloxane, with stearic acid or by etherification of hydroxyl groups with alkoxy groups. One type of filler or else a mixture of at least two fillers may be added to the composition.
Der Füllstoff ist bezogen auf das Gesamtgewicht der Zusammensetzung vorzugsweise in einem Anteil von 1 bis 80 Gew.-%, vorzugsweise 5 bis 70 Gew.-% und weiter bevorzugt von 10 bis 60 Gew.-% in der Zusammensetzung enthalten.The filler is preferably contained in a proportion of 1 to 80% by weight, preferably 5 to 70% by weight, and more preferably 10 to 60% by weight, based on the total weight of the composition.
In einer weiter bevorzugten Ausführungsform wird der Zusammensetzung ein Weichmacher zugegeben. Als Weichmacher können alle Weichmacher verwendet werden, die dem Fachmann geläufig sind. Insbesondere können bei Raumtemperatur flüssige, durch Trimethylsiloxygruppen endblockierte Dimethylpolysiloxane oder Phosphorsäureester zugegeben werden. Besonders bevorzugt sind Alkylarylphos- phate, die als Weichmacher zugesetzt werden. In einer weiter bevorzugten Ausfüh- rungsform ist der Weichmacher ausgewählt aus der Gruppe der Benzylphthalatester,In a further preferred embodiment, a plasticizer is added to the composition. As plasticizers, it is possible to use all plasticizers which are familiar to the person skilled in the art. In particular, trimethylsiloxy-endblocked dimethylpolysiloxanes or phosphoric acid esters which are liquid at room temperature may be added. Particular preference is given to alkylaryl phosphates which are added as plasticizers. In a further preferred embodiment, the plasticizer is selected from the group of benzyl phthalate esters,
Dibenzoatester, Phosphatester, polymere Adipinsäureester und Mischungen derselben. Insbesondere sind Butylbenzylphthalat, Alkyl (C7-C9)benzylphthalat, Texanol- benzylphthalat, modifiziertes Benzylphthalat, Dipropylenglykoldibenzoat, modifiziertes Dibenzoat, Benzylphthalat, Dipropylenglykol/Diethylenglykol dibenzoat, 2- Ethylhexylmonobenzoat, Octyldiphenylphosphat, Isodecyldiphenylphosphat, Al- kyl(C12-C16)arylphosphat, PoIy(1 , 3-butan/1 ,2-propandiol)adipat, Poly(neo- pentan/1 ,2-propandiol)adipat, PoIy(1 , 3-butan)adipat, Poly(neo- pentan/butandiol)adipat, PoIy(1 , 2-propandiol)adipat/phthalat und Mischungen derselben als Weichmacher bevorzugt.Dibenzoate esters, phosphate esters, polymeric adipic acid esters and mixtures thereof. In particular, butylbenzyl phthalate, alkyl (C7-C9) benzyl phthalate, texanol benzyl phthalate, modified benzyl phthalate, dipropylene glycol dibenzoate, modified dibenzoate, benzyl phthalate, dipropylene glycol / diethylene glycol dibenzoate, 2-ethylhexyl monobenzoate, octyldiphenyl phosphate, isodecyldiphenyl phosphate, alkyl (C12-C16) aryl phosphate, poly (1,3-butane / 1,2-propanediol) adipate, poly (neopentane / 1,2-propanediol) adipate, poly (1,3-butane) adipate, poly (neopentane / butanediol) adipate, poly (1, 2-propanediol) adipate / phthalate and mixtures thereof as a plasticizer preferred.
Der Weichmacher ist bezogen auf das Gesamtgewicht der Zusammensetzung vorzugsweise in einem Anteil von 0,1 bis 30 Gew.-%, vorzugsweise 5 bis 25 Gew.-% und weiter bevorzugt von 1 bis 15 Gew.-% in der Zusammensetzung enthalten. Je nach Mischungsverfahren ist es bevorzugt, den Weichmacher vor einem eventuellen Homogenisieren und/oder nach einem eventuellen Homogensieren der Zusammensetzung zuzufügen.The plasticizer is preferably contained in a proportion of 0.1 to 30% by weight, preferably 5 to 25% by weight, and more preferably 1 to 15% by weight, based on the total weight of the composition. Depending on the mixing method, it is preferred to add the plasticizer before a possible homogenization and / or after a possible homogenization of the composition.
Weiter bevorzugt werden der Zusammensetzung Haftvermittler zugegeben. Die Haft- Vermittler sind vorzugsweise Alkoxysilane, Aminosilane und/oder Alkoxyaminosilane, die zusätzlich zu Alkoxygruppen und/oder Aminogruppen Reste, ausgewählt aus der Gruppe bestehend aus Wasserstoffatom, SiC-gebundenen Kohlenwasserstoffresten, sowie SiC-gebundenen, substituierten Kohlenwasserstoffresten, aufweisen, sowie deren Gemische und Teil- bzw. Mischhydrolysate. Bevorzugt handelt es sich bei den Alkoxygruppen mit 1 bis 6 Kohlenstoffatomen, insbesondere um Methoxy-, Ethoxy- und Propoxygruppen. Bei den Kohlenwasserstoffresten sind Alkyl- und Alkenylreste, und insbesondere der Vinyl- und 2-Propynylrest bevorzugt. Bevorzugt ist der Kohlenwasserstoffrest ein Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen, die optional mit Epoxy, (Poly)Glykol- oder Säureanhydridresten oder Resten der Formel - 0(CO)-R7 substituiert sind, wobei R7 ein Wasserstoffatom oder Kohlenwasserstoffrest ist.More preferably, adhesion promoters are added to the composition. The adhesion promoters are preferably alkoxysilanes, aminosilanes and / or alkoxyaminosilanes which, in addition to alkoxy groups and / or amino groups, radicals selected from the group consisting of hydrogen atom, SiC-bonded hydrocarbon radicals, and SiC-bonded, substituted hydrocarbon radicals, and mixtures thereof and partial or mixed hydrolysates. The alkoxy groups having 1 to 6 carbon atoms are preferred, in particular methoxy, ethoxy and propoxy groups. In the case of the hydrocarbon radicals, alkyl and alkenyl radicals, and in particular the vinyl and 2-propynyl radicals, are preferred. Preferably, the hydrocarbyl group is a hydrocarbyl group having from 1 to 18 carbon atoms optionally substituted with epoxy, (poly) glycol or acid anhydride groups or groups of the formula --O (CO) - R 7 wherein R 7 is hydrogen or hydrocarbyl.
Der Haftvermittler ist bezogen auf das Gesamtgewicht der Zusammensetzung vorzugsweise in einem Anteil von 0,1 bis 10 Gew.-% und weiter bevorzugt von 1 bis 5 Gew.-% in der Zusammensetzung enthalten.The coupling agent is preferably contained in a proportion of 0.1 to 10% by weight, and more preferably 1 to 5% by weight, in the composition, based on the total weight of the composition.
Je nach Mischungsverfahren kann es bevorzugt sein, dass vor einem eventuellen Homogenisieren und/oder nach einem eventuellen Homogenisieren der Haftvermittler zugegeben wird.Depending on the mixing method, it may be preferred that the adhesion promoter is added before possible homogenization and / or after possible homogenization.
Vorzugsweise werden alle Inhaltsstoffe der Zusammensetzung vor dem Vermischen getrocknet. In einer weiteren bevorzugten Ausführungsform werden im Wesentlichen wasserfreie oder wasserfreie Inhaltsstoffe zur Herstellung der Zusammensetzung eingesetzt.Preferably, all ingredients of the composition are dried before mixing. In a further preferred embodiment, essentially anhydrous or anhydrous ingredients are used to prepare the composition.
Überraschenderweise zeigt die Zusammensetzung der vorliegenden Erfindung eine sehr gute Schwerentflammbarkeit. Die Schwerentflammbarkeit kann gemäß der DIN 4102 im Brandschacht bestimmt werden. Die verbesserte Schwerentflammbarkeit wird wahr- scheinlich, ohne jedoch an diese Theorie gebunden zu sein, durch die Kombination des Metalls ausgewählt aus der Gruppe der Platinmetalle mit dem Kondensationskatalysator erzielt. Zusammensetzungen, die nicht die Kombination aus beiden Substanzen enthalten, zeigen eine deutlich höhere Entflammbarkeit und sind für die Anwendung in Berei- chen, in denen schwerentflammbare Dichtmaterialien vorgeschrieben sind, nicht geeignet.Surprisingly, the composition of the present invention exhibits very good flame retardancy. The low flammability can be determined according to DIN 4102 in the fire shaft. The improved flame retardancy is likely, but without being bound by theory, achieved by the combination of the metal selected from the group of platinum metals with the condensation catalyst. Compositions which do not contain the combination of both substances show a significantly higher flammability and are suitable for use in in which flame retardant sealing materials are prescribed are not suitable.
Ein weiterer Aspekt zu der vorliegenden Erfindung ist ein Verfahren zur Herstellung der vorgenannten Zusammensetzung enthaltend die Schritte:A further aspect of the present invention is a process for the preparation of the aforementioned composition comprising the steps:
a) Vorlegen eines Polymers der allgemeinen Formel 1a) presentation of a polymer of the general formula 1
R1 nR23-nSi(CR3R4)m-(0-CR3R4-CR5R6)o-0-(CR3R4)mSiR1 nR23-n (1 ), wobeiR 1 n R 2 3-n Si (CR 3 R 4 ) m - (O-CR 3 R 4 -CR 5 R 6 ) o-O- (CR 3 R 4 ) m SiR 1 n R 2 3-n (1 ), in which
R1 und R2 unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Alkylgruppe mit 1 bis 8 Kohlenstoffatomen und Alkyloxygruppe mit 1 bis 8 Kohlenstoffatomen, n eine Zahl von 0 bis 3 ist,R 1 and R 2 are independently selected from the group consisting of alkyl group having 1 to 8 carbon atoms and alkyloxy group having 1 to 8 carbon atoms, n is a number from 0 to 3,
R3, R4, R5 und R6 unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und Alkylgruppe mit 1 bis 8 Kohlenstoffatomen, m eine Zahl von 0 bis 10 und o eine Zahl von 1 bis 1000 ist, wobei das Polymer der allgemeinen Formel 1 optional mit Acrylsäure modifiziert worden ist, b) einem Metall, einer Verbindung oder einem Komplex aus der Gruppe der PlatinmetalleR 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of hydrogen and alkyl group having 1 to 8 carbon atoms, m is a number from 0 to 10 and o is a number from 1 to 1000, wherein the polymer of the is optionally modified with acrylic acid, b) a metal, a compound or a complex from the group of platinum metals
c) einem Kondensationskatalysator, undc) a condensation catalyst, and
d) einem Härtungsmittel erhalten wird.d) a curing agent is obtained.
In einem bevorzugten erfindungsgemäßen Verfahren erfolgt nach dem Schritt b) eine Homogenisierung, bevorzugt in der weiter oben angegebenen Weise.In a preferred process according to the invention, homogenization takes place after step b), preferably in the manner indicated above.
Vorzugsweise sind R1 und R2 des Polymers der allgemeinen Formel 1 unabhängig vo- neinander ausgewählt aus der Gruppe bestehend aus Methylgruppe, Ethylgruppe, Me- thoxygruppe und Ethoxygruppe.Preferably, R 1 and R 2 of the polymer of general formula 1 are independently selected from the group consisting of methyl group, ethyl group, methoxy group and ethoxy group.
Weiter bevorzugt ist R1 eine Methylgruppe und R2 eine Methoxygruppe, wobei n 1 ist.More preferably, R 1 is a methyl group and R 2 is a methoxy group, where n is 1.
In einer bevorzugten Ausführungsform werden R3, R4, R5 und R6 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus Wasserstoff, Methylgruppe und Ethylg- ruppe. Es ist weiter bevorzugt, dass m jeweils 1 , 2 3 und/oder ist und/oder o eine Zahl von 1 bis 100 ist. Vorzugsweise sind R3, R4 und R5 Wasserstoff und R6 ist eine Methylgruppe.In a preferred embodiment, R 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of hydrogen, methyl group and ethyl group. It is further preferred that each m is 1, 2 3 and / or and / or o is a number from 1 to 100. Preferably, R 3, R 4 and R 5 are hydrogen and R 6 is a methyl group.
Das eingesetzte Metall ist vorzugsweise Platin oder Palladium, wobei die vorgenannten spezifischen Metallverbindungen bevorzugt eingesetzt werden können.The metal used is preferably platinum or palladium, wherein the aforementioned specific metal compounds can be preferably used.
Weiterhin ist der Kondensationskatalysator vorzugsweise eine organische Verbindung von Zinn, Zirkonium, Titan und/oder Aluminium. Die vorgenannten Kondensationskatalysatoren können bevorzugt verwendet werden.Furthermore, the condensation catalyst is preferably an organic compound of tin, zirconium, titanium and / or aluminum. The aforementioned condensation catalysts may preferably be used.
Für das einzusetzende Härtungsmittel gilt das oben zu diesem Bestandteil Gesagte analog.For the curing agent to be used, the statements made above on this component apply analogously.
Optional können in dem Verfahren Füllstoffe, Weichmacher und/oder Haftvermittler eingesetzt werden.Optionally, fillers, plasticizers and / or adhesion promoters can be used in the process.
Teil der Erfindung ist selbstverständlich auch eine Zusammensetzung, die nach einem erfindungsgemäßen Verfahren herstellbar ist. Ebenfalls Bestandteil der Erfindung ist eine Verbindung einer erfindungsgemäßen Zusammensetzung als Dichtmittel, Kleber und/oder Versiegelungsmittel.Of course, part of the invention is also a composition which can be prepared by a process according to the invention. Also part of the invention is a compound of a composition according to the invention as a sealant, adhesive and / or sealant.
Wie oben bereits erläutert, zeigen die erfindungsgemäßen Zusammensetzungen eine ausgeprägte Schwerentflammbarkeit. Die Schwerentflammbarkeit lässt sich über eine Prüfung des Brandverhaltens nach DIN 4102-1 : 1998-05 bestimmen. Auf dem Wege der Verweisung wird diese Norm Bestandteil dieser Anmeldung. Bevorzugte erfindungsgemäße Mischungen sind demgemäß nach der genannten Norm bestimmt schwer ent- flammbar. Hierbei hat sich herausgestellt, dass das oben beschriebene Homogenisieren nach Zugabe eines Metalls, einer Verbindung oder eines Komplexes aus der Gruppe der Platinmetalle sich positiv auf den Grad der Schwerentflammbarkeit auswirkt. Auch die Kombination eines Metalls, einer Verbindung oder eines Komplexes aus der Gruppe der Platinmetalle mit einem Kondensationskatalysator scheint sich positiv auf die Schwerent- flammbarkeit auszuwirken. Zusammensetzungen, die nicht eine Kombination aus den beiden letzt genannten Substanzgruppen enthalten, zeigen eine deutlich höhere Entflammbarkeit und sind für die Anwendung in Bereichen, in denen schwerentflammbare Dichtmaterialien vorgeschrieben sind, nicht geeignet. Dabei erwies es sich als bevorzugt, eine Homogenisierung wie oben beschrieben stattfinden zu lassen, bevor der Kondensa- tionskatalysator und/oder das Härtungsmittel zu der Zusammensetzung gegeben wurde. Bθispiθl 1As already explained above, the compositions according to the invention show a pronounced low flammability. The low flammability can be determined by a test of the fire behavior according to DIN 4102-1: 1998-05. By way of reference, this standard becomes part of this application. Accordingly, according to the invention, preferred mixtures according to the invention are hardly inflammable. It has been found that the homogenization described above after addition of a metal, a compound or a complex from the group of platinum metals has a positive effect on the degree of flame retardancy. The combination of a metal, a compound or a complex from the group of platinum metals with a condensation catalyst also seems to have a positive effect on the flame retardancy. Compositions which do not contain a combination of the last two groups of substances show a significantly higher flammability and are not suitable for use in areas where flame-retardant sealing materials are prescribed. It proved to be preferable to let a homogenization take place as described above before the condensation catalyst and / or the curing agent was added to the composition. Bθispiθl 1
Herstellung einer DichtungsmasseProduction of a sealant
20,00 g trockenes AI(OH)3 (Martinal 01-104), 0,80 g trockenes TiO2, 2,20 g Polyamidwachs (Crayvallac), 9,00 g Polymer S303H (Kaneka Corp., entspricht einem Polymer gemäß der allgemeinen Formel 1 der vorliegenden Anmeldung) und 6,70 g eines Alkyla- rylphosphates (Weichmacher) werden gemischt. Nachfolgend werden zu der Mischung 0,20 g Aminopropyltrimethoxysilan (Silan A1 110), 0,20 Pt-Kat512 (Hansechemie, Hamburg), 0,060 g Vinyltrimethoxysilan (Härtungsmittel und 0,40 g Dibutylzinndiketanoat (TEGOKAT 226, Fa. Goldschmidt) gegeben. Die erhaltene Zusammensetzung wird homogen vermischt, um eine Dichtungszusammensetzung zu erhalten.20.00 g of dry Al (OH) 3 (Martinal 01-104), 0.80 g of dry TiO 2 , 2.20 g of polyamide wax (Crayvallac), 9.00 g of polymer S303H (Kaneka Corp., corresponds to a polymer according to the general formula 1 of the present application) and 6.70 g of an alkyl aryl phosphate (plasticizer) are mixed. 0.20 g of aminopropyltrimethoxysilane (silane A1 110), 0.20 of Pt-Kat512 (Hansechemie, Hamburg), 0.060 g of vinyltrimethoxysilane (curing agent and 0.40 g of dibutyltin diketanoate (TEGOKAT 226, Goldschmidt)) are subsequently added to the mixture The obtained composition is homogeneously mixed to obtain a sealing composition.
Die erhaltene Dichtungszusammensetzung zeigt nach Aushärten eine sehr gute Schwerentflammbarkeit. Gemäß der DIN 4102-1 : 1998-05 ist die Schwerentflammbarkeit im Brandschacht ausreichend.The resulting sealant composition exhibits a very good flame retardancy after curing. According to DIN 4102-1: 1998-05, the low flammability in the fire shaft is sufficient.
Außerdem sind die Dichtungseigenschaften der Dichtungszusammensetzung mit den Dichtungszusammensetzungen des Standes der Technik vergleichbar.In addition, the sealing properties of the sealant composition are comparable to the prior art sealant compositions.
Beispiel 2Example 2
Herstellung einer größeren Menge einer DichtungsmasseProducing a larger amount of a sealant
250 kg trockenes AI(OH)3 (Martinal OL-104, Bezug über Firma Brenntag, Wien), 10 kg trockenes TiO2 und 27,5 kg Polyamidwachs (Crayvallac, Bezug über Firma Biesterfeld, Wien) wurden bis zur Homogenität gemischt. Nachfolgend wurden 1 15 kg Polymer S303H (Kaneka Corp., entspricht einem Polymer gemäß der allgemeinen Formel 1 der vorliegenden Anmeldung) und 100 kg eines Weichmachers (Disflamoll DPK, Alkyl-Aryl- Phosphat, Lanxess) zugemischt und zehn Minuten bei 6O0C gehalten.250 kg of dry Al (OH) 3 (Martinal OL-104, purchased from Brenntag, Vienna), 10 kg of dry TiO 2 and 27.5 kg of polyamide wax (Crayvallac, purchased from Biesterfeld, Vienna) were mixed until homogeneous. Subsequently, 15 kg 1 Polymer S303H (Kaneka Corp., corresponds to a polymer according to general formula 1 of the present application) and 100 kg of a plasticizer (Disflamoll DPK, alkyl-aryl phosphate, Lanxess) were mixed and ten minutes at 6O 0 C held ,
Danach wurden 1 ,5 kg Aminopropyltrimethoxysilan (Silan A1 110, Bezug über Firma SWOP-Chemie, Berchtoldsdorf) und 3 kg Platinkatalysator (Pt-Kat512, Hansechemie, Hamburg) hinzudosiert. Zum Homogenisieren des Gemisches wurde 24 Stunden bei Raumtemperatur stehengelassen. Dann wurden 10 kg Vinyltrimethoxysilan (VTMO, Bezug über Firma Momentiv, Leverkusen) und 2 kg Dibutylzinndiketanoat (TEGOKAT 226, Firma Goldschmitdt, Mannheim) hinzudosiert. Beispiel 3Thereafter, 1.5 kg of aminopropyltrimethoxysilane (silane A1 110, obtained from SWOP-Chemie, Berchtoldsdorf) and 3 kg of platinum catalyst (Pt-Kat512, Hansechemie, Hamburg) were added. To homogenize the mixture was allowed to stand for 24 hours at room temperature. Then, 10 kg of vinyltrimethoxysilane (VTMO, available from Momentive, Leverkusen) and 2 kg of dibutyltin diketanoate (TEGOKAT 226, Goldschmittt, Mannheim) were added. Example 3
Analog zum Beispiel 2 wurde eine Dichtungsmasse hergestellt, wobei allerdings auf die Zudosierung des Platinkatalysators verzichtet wurde.Analogously to Example 2, a sealant was prepared, although dispensed with the metered addition of the platinum catalyst.
Beispiel 4Example 4
Vergleich der Brennbarkeit der in Beispiel 2 und Beispiel 3 hergestellte DichtungsmassenComparison of the combustibility of the sealants prepared in Example 2 and Example 3
Nach Entflammung brannten die in Beispiel 3 hergestellten Dichtungsmassen ohne Selbstverlöschung ab, während die gemäß Beispiel 2 hergestellte Dichtungsmassen eine schnelle Selbstverlöschung zeigten.After firing, the sealants prepared in Example 3 burned without self-extinguishing, while the sealants prepared according to Example 2 exhibited rapid self-extinguishment.
Beispiel 5Example 5
Prüfung der gemäß Beispiel 2 hergestellten DichtungsmasseTesting the sealant prepared according to Example 2
Mit der gemäß Beispiel 2 hergestellten Dichtungsmasse wurde eine Brandprüfung soweit im Folgenden nicht anders angegeben gemäß DIN 4102-1 : 1998-05 durchgeführt.With the sealant prepared according to Example 2, a fire test was carried out as far as not otherwise specified below according to DIN 4102-1: 1998-05.
A) Prüfungen im BrennkastenA) Tests in the fuel box
Die Brandprüfung erfolgte nach DIN 4102-1 Abschnitt 6.2.5. Es wurden fünf Kanten- beflammungen nach Abschnitt 6.2.5.2 (Proben Nr. 1 bis 5) und fünf Flächenbeflam- mungen nach Abschnitt 6.2.5.3 (Proben Nr. 6 bis 10) durchgeführt. Die Prüfergebnisse sind in der nachfolgenden Tabelle aufgeführt: The fire test was carried out according to DIN 4102-1 section 6.2.5. Five edge flames according to Section 6.2.5.2 (Samples Nos. 1 to 5) and five surface flames according to Section 6.2.5.3 (Samples Nos. 6 to 10) were performed. The test results are listed in the following table:
Tabelle i:Table i:
B) BrandschachtprüfungenB) Fire shaft tests
Es wurde eine Fugendichtungsmasse in eine 15 mm breite Fuge zwischen zwei Faser-Zementträgern eingebracht und bündig zu den Trägern abgezogen. Die Fugentiefe betrug 10 mm. Vier auf diese Weise präparierte Proben ergaben je einen Probekörper für die Brandschachtprüfungen. Die Prüfergebnisse sind in der nachfolgenden Tabelle enthalten. A jointing compound was placed in a 15 mm wide joint between two fiber cement carriers and pulled flush with the carriers. The joint depth was 10 mm. Four samples prepared in this way each gave a test specimen for the fire shaft tests. The test results are included in the following table.
Tabelle 2:Table 2:
Der Verlauf der Rauchgastemperaturen ist in Fig. 1 wiedergegeben.The course of the flue gas temperatures is shown in Fig. 1.
10 min Die Integralwerte I = J S*dt wurden aus den in Fig. 2 dargestellten10 min. The integral values I = J S * dt were selected from those shown in FIG
00
Lichtschwächungskurven ermittelt.Light attenuation curves determined.
Fig. 1 stellt den Verlauf der Rauchgastemperatur dar.Fig. 1 illustrates the course of the flue gas temperature.
Fig. 2 stellt den Verlauf der Lichtschwächung dar. Nachfolgend sind in Tabelle 3 Prüfergebnisse tabellarisch zusammengefasst:Fig. 2 illustrates the course of the light attenuation. Table 3 below summarizes test results in tabular form:
Tabelle 3:Table 3:
Ergebnis:Result:
Die gemäß Beispiel 2 hergestellte Dichtungsmasse entspricht den Anforderungen der Baustoffklasse B1 (schwerentflammbar) nach DIN 4102-1 : 1998-05. Die Dichtungsmasse gilt gemäß DIN 4102-16: 1998-05 als nicht brennend abfallend/abtropfend. The sealant produced according to Example 2 meets the requirements of building material class B1 (flame retardant) according to DIN 4102-1: 1998-05. The sealant is according to DIN 4102-16: 1998-05 as non-burning falling / dripping.
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP08836532A EP2195387A2 (en) | 2007-09-26 | 2008-09-25 | Flame-resistant sealing material |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP07018909 | 2007-09-26 | ||
PCT/EP2008/062877 WO2009043808A2 (en) | 2007-09-26 | 2008-09-25 | Flame-resistant sealing material |
EP08836532A EP2195387A2 (en) | 2007-09-26 | 2008-09-25 | Flame-resistant sealing material |
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EP2195387A2 true EP2195387A2 (en) | 2010-06-16 |
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EP08836532A Withdrawn EP2195387A2 (en) | 2007-09-26 | 2008-09-25 | Flame-resistant sealing material |
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US (1) | US20100298489A1 (en) |
EP (1) | EP2195387A2 (en) |
JP (1) | JP2010540707A (en) |
KR (1) | KR20100085072A (en) |
CN (1) | CN101932658A (en) |
AU (1) | AU2008306979A1 (en) |
CA (1) | CA2700697A1 (en) |
WO (1) | WO2009043808A2 (en) |
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CN103215010B (en) * | 2013-04-28 | 2014-09-03 | 深圳市新亚新材料有限公司 | Single-component dealcoholized heat-conducting flame retardant fixing glue and preparation method thereof |
KR20190108737A (en) | 2018-03-15 | 2019-09-25 | 주식회사 지에이치아이 | Flame retardant sealant composition |
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JP3913859B2 (en) * | 1997-09-10 | 2007-05-09 | 株式会社カネカ | Curable composition |
JPH11116686A (en) * | 1997-10-09 | 1999-04-27 | Kanegafuchi Chem Ind Co Ltd | Hardening composition |
JP2000302976A (en) * | 1999-04-21 | 2000-10-31 | Kanegafuchi Chem Ind Co Ltd | Curable resin composition and expandable resin composition |
JP2000302975A (en) * | 1999-04-21 | 2000-10-31 | Kanegafuchi Chem Ind Co Ltd | Curable resin composition and expandable resin composition |
DE10007977B4 (en) * | 2000-02-22 | 2004-07-29 | Hilti Ag | Additive mixture to increase the fire resistance of plastic moldings, plastic moldings and a two-component system for their manufacture |
JP4287162B2 (en) * | 2003-01-27 | 2009-07-01 | 株式会社カネカ | Two-component curable composition |
DE102004008668A1 (en) * | 2004-02-21 | 2005-09-08 | Degussa Ag | Silane-containing preparation for moisture-curing hybrid adhesives and hybrid sealants |
-
2008
- 2008-09-25 EP EP08836532A patent/EP2195387A2/en not_active Withdrawn
- 2008-09-25 WO PCT/EP2008/062877 patent/WO2009043808A2/en active Application Filing
- 2008-09-25 CA CA2700697A patent/CA2700697A1/en not_active Abandoned
- 2008-09-25 US US12/679,845 patent/US20100298489A1/en not_active Abandoned
- 2008-09-25 AU AU2008306979A patent/AU2008306979A1/en not_active Abandoned
- 2008-09-25 JP JP2010526296A patent/JP2010540707A/en active Pending
- 2008-09-25 CN CN2008801141832A patent/CN101932658A/en active Pending
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WO2009043808A2 (en) | 2009-04-09 |
WO2009043808A3 (en) | 2009-06-25 |
US20100298489A1 (en) | 2010-11-25 |
CN101932658A (en) | 2010-12-29 |
AU2008306979A1 (en) | 2009-04-09 |
KR20100085072A (en) | 2010-07-28 |
CA2700697A1 (en) | 2009-04-09 |
JP2010540707A (en) | 2010-12-24 |
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