WO2024086140A1 - Silicone-thermoplastic composite articles - Google Patents
Silicone-thermoplastic composite articles Download PDFInfo
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- WO2024086140A1 WO2024086140A1 PCT/US2023/035283 US2023035283W WO2024086140A1 WO 2024086140 A1 WO2024086140 A1 WO 2024086140A1 US 2023035283 W US2023035283 W US 2023035283W WO 2024086140 A1 WO2024086140 A1 WO 2024086140A1
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- WO
- WIPO (PCT)
- Prior art keywords
- silicone
- silicone elastomer
- thermoplastic
- flame
- thermoplastic composite
- Prior art date
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- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 142
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 142
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 239000000654 additive Substances 0.000 claims abstract description 96
- 239000003063 flame retardant Substances 0.000 claims abstract description 68
- 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 claims abstract description 65
- 230000000996 additive effect Effects 0.000 claims abstract description 64
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 34
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims description 295
- 229920002379 silicone rubber Polymers 0.000 claims description 238
- -1 polyoxymethylene Polymers 0.000 claims description 89
- 238000007906 compression Methods 0.000 claims description 75
- 230000006835 compression Effects 0.000 claims description 75
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 45
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 44
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 35
- 239000001095 magnesium carbonate Substances 0.000 claims description 33
- 239000000395 magnesium oxide Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 29
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 29
- JUSBJERCRFVSOW-UHFFFAOYSA-L magnesium;oxido hydrogen carbonate Chemical class [Mg+2].OC(=O)O[O-].OC(=O)O[O-] JUSBJERCRFVSOW-UHFFFAOYSA-L 0.000 claims description 28
- 235000011160 magnesium carbonates Nutrition 0.000 claims description 26
- 229920001971 elastomer Polymers 0.000 claims description 22
- 150000003254 radicals Chemical class 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 12
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 10
- 229920006324 polyoxymethylene Polymers 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- 239000000806 elastomer Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000007348 radical reaction Methods 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000006078 metal deactivator Substances 0.000 claims description 7
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 7
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims description 6
- 229920001470 polyketone Polymers 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000034 Plastomer Polymers 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- ZEYIGTRJOAQUPJ-UHFFFAOYSA-L magnesium;carbonate;dihydrate Chemical compound O.O.[Mg+2].[O-]C([O-])=O ZEYIGTRJOAQUPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920006285 olefinic elastomer Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001955 polyphenylene ether Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011227 reinforcement additive Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 26
- 239000012815 thermoplastic material Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 82
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 45
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 44
- 239000003054 catalyst Substances 0.000 description 42
- 239000000049 pigment Substances 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 32
- 239000000377 silicon dioxide Substances 0.000 description 31
- 239000004945 silicone rubber Substances 0.000 description 27
- 125000003342 alkenyl group Chemical group 0.000 description 25
- 239000012763 reinforcing filler Substances 0.000 description 24
- 239000003112 inhibitor Substances 0.000 description 21
- 125000000304 alkynyl group Chemical group 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000004615 ingredient Substances 0.000 description 17
- 229910021485 fumed silica Inorganic materials 0.000 description 16
- 238000001723 curing Methods 0.000 description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 15
- 229910052697 platinum Inorganic materials 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- 230000008859 change Effects 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000004971 Cross linker Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 12
- 239000000945 filler Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 229920002302 Nylon 6,6 Polymers 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 150000003961 organosilicon compounds Chemical class 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 241000894007 species Species 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 7
- 230000002028 premature Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 7
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 7
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 6
- 238000004438 BET method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 229920006918 PA6-GF25 Polymers 0.000 description 6
- 229920006503 PA66-GF25 Polymers 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 229910052604 silicate mineral Inorganic materials 0.000 description 6
- 229920007776 PBT GF30 Polymers 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000001419 dependent effect Effects 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 239000013536 elastomeric material Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 235000012254 magnesium hydroxide Nutrition 0.000 description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 3
- KKZSDWROKQKKPM-UHFFFAOYSA-N 1-n',12-n'-bis(2-hydroxybenzoyl)dodecanedihydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)CCCCCCCCCCC(=O)NNC(=O)C1=CC=CC=C1O KKZSDWROKQKKPM-UHFFFAOYSA-N 0.000 description 3
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 3
- 229910020485 SiO4/2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 description 3
- 235000019800 disodium phosphate Nutrition 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
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- 239000010439 graphite Substances 0.000 description 3
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- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
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- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 3
- 229910052850 kyanite Inorganic materials 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- 239000004408 titanium dioxide Substances 0.000 description 3
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 2
- 239000004608 Heat Stabiliser Substances 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- ZLHNYIHIHQEHJQ-UHFFFAOYSA-N N,N'-Diacetylhydrazine Chemical compound CC(=O)NNC(C)=O ZLHNYIHIHQEHJQ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052849 andalusite Inorganic materials 0.000 description 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
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- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- CJBOPISUMAZJPD-UHFFFAOYSA-N cyclopropane;platinum Chemical compound [Pt].C1CC1 CJBOPISUMAZJPD-UHFFFAOYSA-N 0.000 description 1
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FDKCTEWMJWRPDS-UHFFFAOYSA-N dialuminum;trimagnesium;trisilicate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] FDKCTEWMJWRPDS-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910052835 grossular Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- PQPVPZTVJLXQAS-UHFFFAOYSA-N hydroxy-methyl-phenylsilicon Chemical compound C[Si](O)C1=CC=CC=C1 PQPVPZTVJLXQAS-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000010443 kyanite Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000013627 low molecular weight specie Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- DDPOPNULNSDSKL-UHFFFAOYSA-N n'-propanoylpropanehydrazide Chemical compound CCC(=O)NNC(=O)CC DDPOPNULNSDSKL-UHFFFAOYSA-N 0.000 description 1
- URADZTVVWMDUTB-UHFFFAOYSA-N n-acetamidoformamide Chemical compound CC(=O)NNC=O URADZTVVWMDUTB-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- POVXOWVFLAAVBH-UHFFFAOYSA-N n-formamidoformamide Chemical compound O=CNNC=O POVXOWVFLAAVBH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QMRNDFMLWNAFQR-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid;styrene Chemical compound C=CC#N.OC(=O)C=C.C=CC1=CC=CC=C1 QMRNDFMLWNAFQR-UHFFFAOYSA-N 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 229910052832 pyrope Inorganic materials 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000005627 triarylcarbonium group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/267—Magnesium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A method to maintain the durability of silicone-thermoplastic composite articles, which comprise flame-retardant free thermoplastic materials and silicone elastomeric materials, with age by incorporating a stabilizing additive in the silicone elastomeric materials. The present disclosure also extends to improved silicone-thermoplastic composite articles and uses for such silicone-thermoplastic composite articles.
Description
SILICONE-THERMOPLASTIC COMPOSITE ARTICLES The present disclosure relates to a silicone-thermoplastic composite article and a method for maintaining the durability of silicone-thermoplastic composite articles, which comprise flame- retardant free thermoplastic materials and silicone elastomeric materials, with age by incorporating a stabilizing additive in the silicone elastomeric materials. The present disclosure also extends to uses for such silicone-thermoplastic composite articles. Curable silicone rubber compositions are known in the art and are used to prepare silicone elastomeric materials having a broad spectrum of physical properties including electrical insulation, resistance and stability to heat, freeze resistance, abrasion resistance, fire retardancy, and long-term flexibility. This unique combination of properties renders silicone elastomers suitable for utilisation in a wide range of electrical and/or insulative applications. For example, silicone elastomers made from either liquid silicone rubbers (LSRs) or high consistency rubbers (HCRs) have been used in a wide variety of silicone-thermoplastic composite articles which comprise thermoplastic materials and silicone elastomeric materials. The physical properties of the flame-retardant free thermoplastic materials and silicone elastomeric materials can provide composite articles with advantageous properties not present if either one or the other were used instead of the composite. However, depending on the applications for which the composites are used, the physical properties and durability of the silicone elastomers in direct contact with the flame-retardant free thermoplastic can be negatively affected, especially when the composite article is subjected to heat and when the silicone elastomer is subjected to compressive forces during use. For example, at high temperature (e.g., > 85oC or alternatively >150oC) species from the fire- retardant free thermoplastic can leach out from the plastic and diffuse into the silicone elastomer and in some cases can degrade the silicone elastomer causing a negative effect on the physical properties thereof such as an increase in compression set. Taking, for example, two thermoplastics materials regularly used in silicone-thermoplastic composite articles, it is suspected that polyamide 66 (PA66), may release species such as adipic acid or carboxylic oligomers and polybutylene terephthalate (PBT) might release esters of terephthalic acid, esters of benzoic acid, terephthalic acid, and benzoic acid, among others as a result of thermal degradation when such composites are used at high temperatures. It is also known that PBT also contains low molecular weight species which may be released even before thermal degradation events. Such species are likely to contain acidic end groups or –OH end groups inherent to the virgin material which can selectively migrate to the surface of the thermoplastic during compression heat aging and diffusing into the silicone elastomer. One of the most common applications for silicone elastomeric materials in silicone-thermoplastic composite articles are as seals in or for electrical or electronic connectors, commonly used to create closed electrical circuits in automotive, residential, and infrastructural settings due to their excellent
balance of mechanical properties, chemical and thermal stabilities and ease of processing. Such electrical or electronic connectors may be used to mate with rigid thermoplastic housing components forming a tight connection that provides both electrical and environmental isolation to connector junctions to create closed electrical circuits in e.g., automotive, residential, and infrastructural settings. Such electrical or electronic connectors may, for example, be used in automotive vehicles which are becoming increasingly dependent on electrical and electronical systems, especially with the developments in electric and hybrid vehicles. In these applications, silicone rubber seals are subjected to mechanical compression and high temperatures and are potentially exposed to the presence of moisture, oils and fuels, corrosive gases, and effluents from contacted materials (e.g., thermoplastic housings) but must retain their mechanical integrity and dimensional stability to provide proper sealing performance during service life to prevent electrical failure. Unwanted electrical failures can lead to devices such as radio, light, ventilation etc. malfunctioning or breaking down as such devices rely on the aforementioned silicone rubber materials as seals to prevent electrical failure. Silicone-thermoplastic composite articles are also useful in other applications where the cured silicone serves to seal, passivate, or protect componentry from environmental and mechanical challenges including heat, moisture, dust, and vibration, as exemplified by lid seals and adhesives for electronic module housings; gaskets or seals for radiator tank or headlamp assemblies; and pottants or encapsulants for electrical or electronic components found in automotive, marine, aeronautical, aerospace or and other industrial applications. It is important therefore for the silicone elastomeric material to maintain its physical properties to ensure the durability of both the silicone elastomeric material itself and the silicone-thermoplastic composite articles. One of the most important physical properties which the silicone rubber material needs to retain is having a low compression set for applications requiring e.g., environmental and electrical insulation and/or heat stability. Compression set is a thermally induced fatigue behavior of a silicone elastomeric material which may be defined as the loss in ability of said silicone elastomeric material to recover to its original thickness after compression for specific period of time at a set (elevated) temperature. A compression set value may be measured, for example, following the industrial standard ASTM D395 – 18 methods A, B or C and is identified as a percentage, such that if there is complete recovery, i.e., if the thickness of a test specimen is identical before and after the application of a load, the compression set is 0%; if, in contrast, a 25% compression of a silicone elastomeric material applied during a test remains unchanged when the load is removed, the compression set is 100% because it has failed to return to its original shape at all. Many silicone elastomeric materials have a substantial compression set e.g., of greater than 50% or
even greater than 60% even after compression at temperatures of 125oC and 150oC for short periods of time e.g., 22 hours and can suffer from problems caused by a consequential change in shape and/or a significant increase in hardness during long-term service in high-temperature applications unless they undergo a post-cure heating process. “Post curing” is the most straightforward way to minimise compression set where hydrosilylation or peroxide-cured silicone materials are subjected to a period of several hours e.g., four or more hours of post-cure heating at temperature of 150oC or greater. However, post-curing is not usually commercially desired or indeed viable given capital investment required due to the need for increased energy consumption and delays in manufacturing times. Many applications described above typically desire silicone elastomeric materials having a compression set value which is as low as possible e.g., no greater than 40%, across a wide spectrum of temperatures. In the United States electrical connector systems have to meet the requirements of the SAE International USCAR-2 “Performance Specification for Automotive Electrical Connector Systems” testing regime. Sealed connector assemblies are graded for their suitability for use over specified temperature ranges fulfilling a class of relevant automotive specifications for given temperature ranges. Currently there are five ranges identified as T1 – T5: T1 is for the temperature class -40° C to +85°C; T2 is for the temperature range -40° C to +100°C; T3 is for the temperature range -40° C to +125°C; T4 is for the temperature range -40° C to +150°C; and currently the highest grade is T5 for the -40° C to 175 °C. Given it is not desirable to post cure every silicone elastomer after cure, a variety of additives have been proposed as an alternative way to reduce compression set. However, industrial and vehicle components and modules are increasingly subjected to mechanical compression and exposed to increasing working temperatures of greater than 125oC. Hence, silicone elastomer materials used in combination with the flame-retardant free thermoplastics in silicone-thermoplastic composite articles, e.g., in connector seal applications, may suffer from premature seal failure after having been in direct contact with flame-retardant free thermoplastics. The intention of this disclosure is to provide a means of maintaining the durability of silicone- thermoplastic composite articles which comprise flame-retardant free thermoplastic materials and silicone elastomeric materials with age. There is provided herein, a silicone-thermoplastic composite article comprising (i) a flame-retardant free thermoplastic article wherein the flame-retardant free thermoplastic article has an available surface, and
(ii) a cured silicone elastomer part in direct contact with the available surface of the flame- retardant free thermoplastic article (i), wherein the silicone elastomer part is the cured product of a silicone elastomer composition comprising from 0.25 wt. % to a maximum of 5 wt. % of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof. There is also provided a method of fabricating a silicone-thermoplastic composite article in accordance as described above comprising (a) providing a curable silicone elastomer composition comprising from 0.25 to a maximum of 5 wt. % of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof, (b) curing said curable elastomer composition into a mold, (c) physically engaging the cured silicone elastomer with an available surface of a flame-retardant free thermoplastic article (i) to form a silicone-thermoplastic composite article. There is also provided a method of fabricating a silicone-thermoplastic composite article as hereinbefore described comprising (a) providing a curable silicone elastomer composition comprising the 0.25 wt. % to a maximum of 5 wt. % of stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof, (b) contacting the curable silicone elastomer composition with an available surface of a flame- retardant free thermoplastic article (i) (c) curing the curable silicone elastomer composition in contact with the available surface of the flame-retardant thermoplastic article, to form a silicone-thermoplastic composite article. There is also provided a method for fabricating a silicone-thermoplastic composite article, wherein the silicone-thermoplastic composite article comprises (i) a flame-retardant free thermoplastic article, wherein the flame-retardant free thermoplastic article has an available surface; and (ii) a silicone elastomer part, wherein the silicone elastomer part is physically engaged with the available surface of (i) the flame-retardant free thermoplastic; which method comprises: (1) providing a curable silicone elastomer composition comprising a hydrosilylation reaction curable silicone elastomer composition or a free radical reaction curable silicone elastomer composition, wherein the curable silicone elastomer composition further comprises 0.25 wt. % to a maximum of 5.0 wt. % of a stabilizing additive selected from the group consisting of a
magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof; (2) introducing a desired amount of the curable silicone elastomer composition into a mold, (3) curing the curable silicone elastomer composition, thereby forming (ii) the silicone elastomer part; (4) physically engaging (ii) the silicone elastomer seal and the available surface of (i) the flame-retardant free thermoplastic article, thereby forming the silicone-thermoplastic composite. In one embodiment of the latter, the silicone-thermoplastic composite article is an electrical or electronic connector, comprising (ia) one or more electrical wires; (ib) an electrical or electronic connector housing comprising a flame-retardant free thermoplastic article, wherein the electrical or electronic connector housing has a first (outer) available surface and a second (inner) surface opposite the outer surface, wherein the second (inner) surface defines a cavity, and the cavity houses the one or more electrical wires (ia) therein; and the silicone elastomer part (ii) is a silicone elastomer seal, wherein the silicone elastomer seal is physically engaged with the first (outer) available surface of the electrical or electronic connector housing (ib). There is also provided a method to maintain the durability of a silicone elastomer part in physical contact with a flame-retardant free thermoplastic which silicone elastomer part in use is subjected to mechanical compression and exposed to temperatures of greater than 85oC comprising the steps of (1’) preparing a curable silicone elastomer composition wherein the curable silicone elastomer composition further comprises 0.25 wt. % to a maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof (2’) introducing a desired amount of the curable silicone elastomer composition into a mold, (3’) curing the curable silicone elastomer composition, thereby forming the silicone elastomer part (ii);
(4’) physically engaging the silicone elastomer part (ii) and the available surface of the electrical or electronic connector housing (ib), to form the electrical or electronic connector. In the above method there may be a step (5’) comprising: connecting the electrical or electronic connector into a connector junction of an electrical circuit via (i) the one or more electrical wires, thereby providing environmental and electrical isolation for the one or more electrical wires (ia). Furthermore, the electrical connector may be heated at a temperature ≥ 125 °C for 1008 hours, wherein the silicone elastomer seal is in a compressed state, e.g., 25%. There is also provided a silicone-thermoplastic composite article prepared by the above method. It may be an automotive part, cable accessory, such as an electrical or electronic connector having a silicone elastomer seal, an electrical part, electronic part, packaging part, construction part, household part or gasket. There is also enclosed a silicone-thermoplastic composite article comprising (i) a flame-retardant free thermoplastic article, wherein the flame-retardant free thermoplastic article has an available surface; and (ii) a silicone elastomer seal, wherein the silicone elastomer seal is physically engaged with the available surface of (i) the thermoplastic article; wherein in use the silicone elastomer seal is subjected to mechanical compression and exposed to temperatures of greater than 85oC obtainable by a process comprising the steps of :- (1’) preparing a curable silicone elastomer composition selected from a hydrosilylation reaction curable silicone elastomer composition or a free radical reaction curable silicone elastomer composition, wherein the curable silicone elastomer composition further comprises 0.25 wt. % to a maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof (2’) introducing a desired amount of the curable silicone elastomer composition into a mold, (3’) curing the curable silicone elastomer composition, thereby forming the silicone elastomer seal (ii). There is also provided a method to prevent degradation of a silicone elastomer seal in physical contact with a flame-retardant free thermoplastic which silicone elastomer seal in use is subjected to mechanical compression and exposed to temperatures of greater than 125oC comprising the steps of (1’) preparing a curable silicone elastomer composition selected from a hydrosilylation reaction curable silicone elastomer composition or a free radical reaction curable silicone elastomer composition, wherein the curable silicone elastomer composition further comprises 0.25 wt. % to a
maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof (2’) introducing a desired amount of the curable silicone elastomer composition into a mold, (3’) curing the curable silicone elastomer composition, thereby forming the silicone elastomer seal (ii); (4’) physically engaging the silicone elastomer seal (ii) and the available surface of the electrical or electronic connector housing (ib), thereby forming the electrical or electronic connector. There is also provided a silicone elastomer part which in use is subjected to mechanical compression and exposed to temperatures of greater than 85oC obtainable by a process comprising the steps of (1’) preparing a curable silicone elastomer composition selected from a hydrosilylation reaction curable silicone elastomer composition or a free radical reaction curable silicone elastomer composition, wherein the curable silicone elastomer composition further comprises 0.25 wt. % to a maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof (2’) introducing a desired amount of the curable silicone elastomer composition into a mold, (3’) curing the curable silicone elastomer composition, thereby forming the silicone elastomer part (ii). Use of from 0.25 wt. % to a maximum of 5.0 wt.% of an additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof as a stabilizing additive in a silicone elastomer seal in physical contact with a flame-retardant free thermoplastic which in use is subjected to mechanical compression and exposed to temperatures of greater than 85oC wherein the silicone elastomer seal is otherwise formed from a curable silicone elastomer composition selected from a hydrosilylation reaction curable silicone elastomer composition or a free radical reaction curable silicone elastomer composition. Surprisingly it has been identified that the problem encountered when seeking to use silicone elastomer materials in combination with the flame-retardant free thermoplastics in silicone- thermoplastic composite articles, e.g., in connector seal applications, i.e., the need to avoid premature silicone elastomer seal failure after having been in direct contact with flame-retardant free thermoplastics can be overcome by introducing a stabilizing additive in the form of from 0.25 wt. % to a maximum of 5.0 wt.% of an additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof in the silicone elastomer compositions used to form e.g., a silicone elastomer seal in a silicone-thermoplastic composite article.
The addition of the stabilizing additive maintains the durability e.g., the mechanical integrity and dimensional stability of the silicone elastomer part in the silicone-thermoplastic composite article comprising a fire-retardant free thermoplastic because it appears to maintain the silicone elastomers physical properties such as compression set despite migration of additives into the silicone elastomer. For example, it prevents any significant worsening of silicone elastomer compression set in a silicone elastomer seal which in use is subjected to mechanical compression and exposed to temperatures of greater than 85°C, alternatively greater than 100°C, alternatively greater than 125 °C. The silicone-thermoplastic composite articles as described herein are made using silicone elastomers made from the compositions described herein in combination with any suitable flame- retardant free thermoplastic. The flame-retardant free thermoplastics are typically used in silicone-thermoplastic composite articles to form rigid components with the silicone elastomers molded or otherwise dispensed into desired shapes designed to form a tight connection over and/or around the thermoplastic article. Usually, the silicone elastomer is provided as a form of seal designed in conjunction with the rigid flame-retardant free component to provide both environmental and electrical isolation to the connector junctions. The flame-retardant free thermoplastic may, for example, be condensation polymers including polyamides such as nylons e.g., nylon 6 (PA6), nylon 6,6 (PA6,6), heat resistant nylon 6T/6,6 (PA6T/6,6), nylon 6/10 (PA6/10), nylon 6/12 (PA6/12), nylon 11 (PA11), nylon 12 (PA12) and the like, and polyoxymethylene, polyphenylenesulfide (PPS), polyacetals, polyamide-imides, polypthalamides, polyetherimides, polyetherketone, polyether etherketone, polyether ketone ether ketone, polyoxymethylene(acetal) homopolymer copolymers, syndiotactic polystyrene (sPS) and compatibilized blends of sPS with polyamides; condensation polymers such as polyesters including polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate (PAR), and the like; polycarbonate (PC) (including impact-modified polycarbonate); polyethers such as polyphenyleneoxide (PPO), maleic anhydride grafted polyphenyleneoxide (PPO), maleic anhydride grafted olefinic elastomers and plastomers, polysulfone, polyethersulfone, polyarylsulfone, polyphenylene ether, and the like; polypropylene, polyethylene, aliphatic polyketones (PK) thermoplastic styrene copolymers, such as acrylonitrile styrene acrylate (ASA), acrylonitrile butadiene styrene (ABS) and styrene acrylonitrile (SAN); polymethyl methacrylate (PMMA), polyoxymethylene (POM). Preferably this process is provided to be used in conjunction with PA6, PA6,6, PA6T/6,6, PBT, PC and PK, especially PA6, PA6,6, PA6T/PA6,6, and PBT. The thermoplastic can also contain about 25-35 wt. % of glass fibers (GF) as a reinforcement additive, e.g., PA6-GF25, PA6,6-GF25, PA6T/6,6-GF33, PK-GF30 and PBT-GF30.
For the avoidance of doubt the term flame-retardant free is intended to mean with respect to flame- retardant free thermoplastics that no fire-retardant additives have been intentionally added into the body of the thermoplastic. The silicone elastomers used in the silicone-thermoplastic composite articles are typically molded or otherwise dispensed into desired shapes designed to form a tight connection over and/or around the flame-retardant free thermoplastic article. It is surmised that species in the flame-retardant free thermoplastics are migrating into the silicone elastomers when fixed tightly over the flame-retardant free thermoplastics materials and this is negatively affecting the chemical structure of the silicone elastomer and consequently negatively affecting the loss in compression set in the silicone elastomers when in direct contact with the flame-retardant free thermoplastics in silicone- thermoplastic composite articles. As described herein it has now been surprisingly identified that the inclusion of from 0.25 wt. % to a maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof into the curable silicone elastomer compositions used to make the silicone elastomers maintain their durability and avoid premature failure of the silicone elastomer part such as a seal by rendering e.g., a significant improvement in physical properties such as the retention of compression set properties of silicone elastomers used in conjunction with flame-retardant free thermoplastics in the aforementioned silicone-thermoplastic composite articles. This is particularly surprising because other materials such as magnesium hydroxide (Mg(OH)2), zinc oxide (ZnO), calcium carbonate (CaCO3) exhibit no effect. Similarly, acid scavengers such as disodium phosphate (Na2HPO4) or traditional antioxidants and high temperature compression set additives, such as iron (III) oxide (Fe2O3) and copper phthalocyanine complexes, do not provide any benefits. While not being tied to this hypothesis we propose that there is a migration of species from the flame-retardant free thermoplastic into the silicone elastomer by way of solid-state diffusion and these species are causing degradation of the silicone matrix resulting in poorer physical properties including, for the sake of example, an increase in compression set. It is surmised that also believed that the stabilizing additives herein are interacting with these diffusive species in a way that they stop or slow down the degradation of the silicone elastomer. This in our view is a surprising effect particularly because other materials one might have expected to have a similar effect, e.g., acid scavengers such as calcium carbonate, magnesium hydroxide, zinc oxide don’t appear to have a similar effect. Because the silicone elastomers used in the silicone-thermoplastic composite articles are designed to form a tight connection over and/or around the flame-retardant free thermoplastic article, when the silicone-thermoplastic composite articles are electrical or electronic connectors, the silicone elastomers are designed/shaped to provide both electrical and environmental isolation to the
connector junctions. However, given their positioning within e.g., engines etc. relative to other parts the silicone elastomeric seals are under mechanical compression and exposed to high temperatures. They can also be in the presence of moisture, oils, fuels, corrosive gases, and exposed to effluents from contacted materials and as such it is critical that the silicone elastomers have a suitable compression set which enables retention of their mechanical integrity and dimensional stability to provide proper sealing performance during service life. The silicone elastomers used in the silicone-thermoplastic composite articles may be prepared by curing suitable curable silicone elastomer composition selected from a hydrosilylation reaction curable silicone elastomer composition or a free radical reaction curable silicone elastomer composition. The curable silicone elastomer composition may be made from either liquid silicone rubbers (LSRs) or high consistency rubbers (HCRs) as both, upon cure, result in silicone elastomers having an excellent balance of mechanical properties, chemical properties and thermal stability. Liquid silicone rubbers tend to be hydrosilylation curable silicone rubber composition, which comprises the following components: a) one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25oC; b) a silica reinforcing filler which is optionally hydrophobically treated; and c1) a hydrosilylation cure package comprising c1(i)) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; and c1(ii)) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; In the current disclosure the liquid silicone rubber (LSR) composition must also incorporate additional component (d) wherein: (d) is from 0.25 wt. % to a maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof. A variety of optional additives to suit the application for which the elastomer resulting from cure is to be used may also be incorporated into the composition. High consistency silicone rubbers usually contain much higher viscosity/chain length/molecular weight polymers which are typically measured on the basis of their Williams plasticity value rather than viscosity. Williams plasticity is measured in accordance with ASTM D-926-08. Because of their exceptionally high viscosities they are often referred to in the industry as “polymer gums”.
Typically, the high consistency rubber compositions differ from LSR compositions described above and comprises the following components: a”) one or more polyorganosiloxanes having a Williams plasticity of at least 100mm/100 in accordance with ASTM D-926-08 and b”) a silica reinforcing filler which is optionally hydrophobically treated. High consistency silicone rubber compositions may be hydrosilylation cured in which case polymer a’ must also contain at least two unsaturated groups, selected from alkenyl groups and alkynyl groups; and the composition comprises a hydrosilylation cure package c1”) or a free radical curative c2”) wherein c1”) is a hydrosilylation cure package comprising c1(i)”) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; and c1(ii)”) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; Alternatively, the high consistency silicone rubber compositions may be free-radical vulcanised, typically utilising organoperoxides. In the event the composition used is a high consistency silicone rubber composition in which case the at least two unsaturated groups, selected from alkenyl groups and alkynyl groups are optional in polymer (a”) and the composition additionally comprises c2”) a free radical curative. In the current disclosure the high consistency silicone rubber compositions must also incorporate additional component (d”) wherein: (d”) is 0.25 wt. % to a maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof. Again, a variety of optional additives to suit the application for which the elastomer resulting from cure is to be used may also be incorporated into the composition. In the case of a liquid silicone rubber: Component (a) Component (a) of the liquid silicone rubber composition is one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25oC. Component (a) of the liquid silicone rubber composition is a polyorganosiloxane, such as a polydiorganosiloxane having at least two unsaturated groups per molecule, which unsaturated groups are selected from alkenyl or alkynyl groups. Alternatively, component (a) has at least three unsaturated groups per molecule.
The unsaturated groups of component (a) may be terminal, pendent, or in both locations. Alkenyl groups may have 2 to 30, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, and alternatively 2 to 6 carbon atoms. Possible alkenyl groups are exemplified by, but not limited to, vinyl, allyl, methallyl, propenyl, and hexenyl and cyclohexenyl groups. Alkynyl groups may have 2 to 30, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, and alternatively 2 to 6 carbon atoms. Alkynyl groups may be exemplified by, but not limited to, ethynyl, propynyl, and butynyl groups. Component (a) of the liquid silicone rubber composition has multiple units of the formula (I): R’aSiO(4-a)/2 (I) in which each R’ is independently selected from an aliphatic hydrocarbyl, or aliphatic non- organyl group (that is any aliphatic organic substituent group, regardless of functional type, having one free valence at a carbon atom). Saturated aliphatic hydrocarbyls are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl and cycloalkyl groups such as cyclohexyl. Unsaturated aliphatic hydrocarbyls are exemplified by, but not limited to the alkenyl groups and alkynyl groups described above. The aliphatic non-halogenated organyl groups are exemplified by, but not limited to, suitable nitrogen containing groups such as amido groups, imido groups; oxygen containing groups such as polyoxyalkylene groups, carbonyl groups, alkoxy groups and hydroxyl groups. Further organyl groups may include phosphorus containing groups, boron containing groups. The subscript “a” is 0, 1, 2 or 3, typically in this instance a is mainly 2 but may contain some units where a is 1 or 3. Siloxy units may be described by a shorthand (abbreviated) nomenclature, namely - "M," "D," "T," and "Q", when R’ is as described above, alternatively an alkyl group, typically a methyl group The M unit corresponds to a siloxy unit where a = 3, that is R’3SiO1/2; the D unit corresponds to a siloxy unit where a = 2, namely R’2SiO2/2; the T unit corresponds to a siloxy unit where a = 1, namely R’1SiO3/2; the Q unit corresponds to a siloxy unit where a = 0, namely SiO4/2. The polyorganosiloxane, of component (a), is substantially linear but may contain a proportion of branching due to the presence of T units (as previously described) within the molecule, hence the average value of subscript a in structure (I) is about 2. Examples of typical R’ groups on component (a) the one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule, include mainly alkyl groups, especially methyl and ethyl, alternatively methyl groups but may also include aryl groups and/or fluoroalkyl groups such as trifluoropropyl or perfluoroalkyl groups in addition to the required at least two unsaturated groups selected from alkenyl and/or alkynyl groups, typically alkenyl groups The groups may be in pendent position (on a D or T siloxy unit) or may be terminal (on an M siloxy unit).
Hence, the polymer chain of component (a) of the liquid silicone rubber composition may be selected from polydimethylsiloxanes, alkylmethylpolysiloxanes, alkylarylpolysiloxanes or copolymers thereof (where reference to alkyl means any suitable alkyl group, alternatively an alkyl group having two or more carbons) providing each component (a) polymer comprises at least two alkenyl and or alkynyl groups, typically at least two alkenyl groups. Such polymer chains may have any suitable terminal groups, for example, they may be trialkyl terminated, alkenyldialkyl terminated alkynyldialkyl terminated or may be terminated with any other suitable terminal group combination providing each polymer contains at least two unsaturated groups selected from alkenyl and alkynyl groups per molecule. In one embodiment the terminal groups of such a polymer don’t comprise any silanol terminal groups. Hence component (a) may, for the sake of example, be: a dialkylalkenyl terminated polydimethylsiloxane, e.g., dimethylvinyl terminated polydimethylsiloxane; a dialkylalkenyl terminated dimethylmethylphenylsiloxane, e.g., dimethylvinyl terminated dimethylmethylphenylsiloxane; a trialkyl terminated dimethylmethylvinyl polysiloxane; a dialkylvinyl terminated dimethylmethylvinyl polysiloxane copolymer; a dialkylvinyl terminated methylphenylpolysiloxane, a dialkylalkenyl terminated methylvinylmethylphenylsiloxane; a dialkylalkenyl terminated methylvinyldiphenylsiloxane; a dialkylalkenyl terminated methylvinyl methylphenyl dimethylsiloxane; a trimethyl terminated methylvinyl methylphenylsiloxane; a trimethyl terminated methylvinyl diphenylsiloxane; or a trimethyl terminated methylvinyl methylphenyl dimethylsiloxane. more preferably comprising of phenylsilicone polymer in an amount of from 0.5 to 5wt. % Component a) of the liquid silicone rubber composition has a viscosity of from 1000 mPa.s to 100,000 mPa.s at 25oC, alternatively 5000 mPa.s to 75,000 mPa.s at 25oC, 10,000 mPa.s to 60,000 mPa.s at 25oC and is preferably present in an amount of from 25 to 60 wt. % of the composition, alternatively in an amount of from 30 to 60 wt. % of the composition, alternatively in an amount of from 35 to 55 wt. % of the composition. Unless otherwise indicated, viscosity may be measured at 25 °C using either a BrookfieldTM rotational viscometer with spindle LV-4 for viscosities over 15,000mPa.s (Spindle LV-4 designed for viscosities in the range between 1,000-2,000,000 mPa.s) at an appropriate rpm and using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 for viscosities up to 15, 000mPa.s at 25°C and an appropriate rpm. Component (b) Component (b) of the liquid silicone rubber composition is a silica reinforcing filler which is optionally hydrophobically treated; The reinforcing fillers of component (b) may be exemplified by fumed silica and/or a precipitated silica and/or a colloidal silica. In one alternative, the fumed silica, precipitated silica and/or colloidal silica are provided in a finely divided form.
Precipitated silica, fumed silica and/or colloidal silicas are particularly preferred because of their relatively high surface area, especially when provided in a finely divided form, which is typically at least 50 m²/g (BET method in accordance with ISO 9277: 2010). Fillers having surface areas of from 50 to 450 m²/g (BET method in accordance with ISO 9277: 2010), alternatively of from 50 to 300 m²/g (BET method in accordance with ISO 9277: 2010), are typically used. All these types of silica are commercially available. When silica reinforcing filler (b) is naturally hydrophilic (e.g., untreated silica fillers), it is typically treated with a treating agent to render it hydrophobic. These surface modified silica reinforcing fillers (b) do not clump and can be homogeneously incorporated into polydiorganosiloxane polymer (a), described below, as the surface treatment makes the fillers easily wetted by component (a). Typically, silica reinforcing filler (b) of the liquid silicone rubber composition maybe surface treated with any low molecular weight organosilicon compounds disclosed in the art applicable to prevent creping of liquid silicone rubber (LSR) compositions during processing. For example, organosilanes, polydiorganosiloxanes, or organosilazanes e.g., hexaalkyl disilazane, short chain siloxane diols to render the silica reinforcing filler (b) hydrophobic and therefore easier to handle and obtain a homogeneous mixture with the other ingredients. Specific examples include, but are not restricted to, silanol terminated trifluoropropylmethylsiloxane, silanol terminated vinyl methyl (ViMe) siloxane, silanol terminated methyl phenyl (MePh) siloxane, liquid hydroxyldimethyl- terminated polydiorganosiloxane containing an average from 2 to 20 repeating units of diorganosiloxane in each molecule, hydroxyldimethyl terminated Phenylmethyl Siloxane, hexaorganodisiloxanes, such as hexamethyldisiloxane, divinyltetramethyldisiloxane; hexaorganodisilazanes, such as hexamethyldisilazane (HMDZ), divinyltetramethyldisilazane and tetramethyldi(trifluoropropyl)disilazane; hydroxyldimethyl terminated polydimethylmethylvinyl siloxane, octamethyl cyclotetrasiloxane, and silanes including but not limited to methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, chlorotrimethyl silane, dichlorodimethyl silane, trichloromethyl silane. In one embodiment, the treating agent may be selected from silanol terminated vinyl methyl (ViMe) siloxane, liquid hydroxyldimethyl-terminated polydiorganosiloxane containing an average from 2 to 20 repeating units of diorganosiloxane in each molecule, hexaorganodisiloxanes, such as hexamethyldisiloxane, divinyltetramethyldisiloxane; hexaorganodisilazanes, such as hexamethyldisilazane (HMDZ), divinyltetramethyldisilazane and; hydroxyldimethyl terminated polydimethylmethylvinyl siloxane, octamethyl cyclotetrasiloxane, and silanes including but not limited to methyltriethoxysilane, dimethyldiethoxysilane and/or vinyltriethoxysilane. A small amount of water can be added together with the silica treating agent(s) as processing aid. The surface treatment of untreated silica reinforcing filler (b) of the liquid silicone rubber composition may be undertaken prior to introduction in the composition or in situ (i.e., in the
presence of at least a portion of the other ingredients of the composition herein by blending these ingredients together at room temperature or above until the filler is completely treated. Typically, untreated silica reinforcing filler (b) is treated in situ with a treating agent in the presence of component (a) which results in the preparation of a silicone rubber base material which can subsequently be mixed with other ingredients. Silica reinforcing filler (b) of the liquid silicone rubber composition is optionally present in an amount of up to 40 wt. % of the composition, alternatively from 1.0 to 40wt. % of the composition, alternatively of from 5.0 to 35wt. % of the composition, alternatively of from 10.0 to 35wt. % of the composition. Component (c1) Component (c1) of the liquid silicone rubber composition is a hydrosilylation cure package comprising (c1(i)) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; and (c1(ii)) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; Component (c1(i)) functions as a cross-linker and is provided in the form of an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule. Component (c1(i)) of the liquid silicone rubber composition normally contains three or more silicon-bonded hydrogen atoms so that the hydrogen atoms can react with the unsaturated alkenyl and/or alkynyl groups of component (a) to form a network structure therewith and thereby cure the composition. Some or all of Component (c1(i)) may alternatively have two silicon bonded hydrogen atoms per molecule when polymer (a) has greater than two unsaturated groups per molecule. The molecular configuration of the organosilicon compound having at least two, alternatively at least three Si-H groups per molecule (c1(i)) is not specifically restricted. It may be a polyorganosiloxane which can have a straight chain, be branched (a straight chain with some branching through the presence of T groups), cyclic or be a silicone resin based. While the molecular weight of component (c1(i)) is not specifically restricted, the viscosity is typically from 5 to 50,000 mPa.s at 25ºC using the test methodology as described for component (a). Silicon-bonded organic groups used in component (c1(i)) may be exemplified by alkyl groups such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl; aryl groups such as phenyl tolyl, xylyl, or similar aryl groups; 3-chloropropyl, 3,3,3-trifluoropropyl, or similar halogenated alkyl group, preferred alkyl groups having from 1 to 6 carbons, especially methyl ethyl or propyl groups or phenyl groups. Preferably the silicon-bonded organic groups used in component (c1(i)) are alkyl groups, alternatively methyl, ethyl or propyl groups.
Examples of the organosilicon compound having at least two, alternatively at least three Si-H groups per molecule (c1(i)) include but are not limited to: (a’) trimethylsiloxy-terminated methylhydrogenpolysiloxane, (b’) trimethylsiloxy-terminated polydimethylsiloxane-methylhydrogensiloxane, (c’) dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymers, (d’) dimethylsiloxane-methylhydrogensiloxane cyclic copolymers, (e’) copolymers and/or silicon resins consisting of (CH3)2HSiO1/2 units, (CH3)3SiO1/2 units and SiO4/2 units, (f’) copolymers and/or silicone resins consisting of (CH3)2HSiO1/2 units and SiO4/2 units, (g’) Methylhydrogensiloxane cyclic homopolymers having between 3 and 10 silicon atoms per molecule; alternatively, component (c1(i)), the cross-linker, may be a filler, e.g., silica treated with one of the above, and mixtures thereof. In one embodiment the component (c1(i)) of the liquid silicone rubber composition is selected from a methylhydrogenpolysiloxane capped at both molecular terminals with trimethylsiloxy groups; a copolymer of a methylhydrogensiloxane and a dimethylsiloxane capped at both molecular terminals with trimethylsiloxy groups; dimethylsiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups; a copolymer of a methylhydrogensiloxane and a dimethylsiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups. The cross-linker (c1(i)) is generally present in the liquid silicone rubber composition in an amount such that the molar ratio of the total number of the silicon-bonded hydrogen atoms in component (b) to the total number of alkenyl and/or alkynyl groups in component (a) is from 0.5:1 to 10:1. When this ratio is less than 0.5:1, a well-cured composition will not be obtained. When the ratio exceeds 10:1, there is a tendency for the hardness of the cured composition to increase when heated. Preferably component (c1(i)) is in an amount such that the molar ratio of silicon-bonded hydrogen atoms of component (b) to alkenyl/alkynyl groups, alternatively alkenyl groups of component (a) ranges from 0.7 : 1.0 to a maximum of 5.0 : 1.0, alternatively from 0.9 : 1.0 to 2.5 : 1.0, and further alternatively from 0.9 : 1.0 to 2.0 : 1.0. The silicon-bonded hydrogen (Si-H) content of component (c1(i)) is determined using quantitative infra-red analysis in accordance with ASTM E168. In the present instance the silicon-bonded hydrogen to alkenyl (vinyl) and/or alkynyl ratio is important when relying on a hydrosilylation cure process. Generally, this is determined by calculating the total weight % of alkenyl groups in the composition, e.g., vinyl [V] and the total weight % of silicon bonded hydrogen [H] in the composition and given the molecular weight of hydrogen is 1 and of vinyl is 27 the molar ratio of silicon bonded hydrogen to vinyl is 27[H]/[V].
Typically, dependent on the number of unsaturated groups in component (a) as well as the number of Si-H groups in component (c1(i)), component (c1(i)) will be present in an amount of from 0.1 to 10 wt. % of the hydrosilylation curable silicone rubber composition, alternatively 0.1 to 7.5wt. % of the hydrosilylation curable silicone rubber composition, alternatively 0.5 to 7.5wt. %, further alternatively from 0.5% to 5 wt. % of the hydrosilylation curable silicone rubber composition. Component (c1(ii)) Component (c1(ii)) of the liquid silicone rubber composition is a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof. These are usually selected from catalysts of the platinum group of metals (platinum, ruthenium, osmium, rhodium, iridium and palladium), or a compound of one or more of such metals. Alternatively, platinum and rhodium compounds are preferred due to the high activity level of these catalysts in hydrosilylation reactions, with platinum compounds most preferred. In a hydrosilylation (or addition) reaction a hydrosilylation catalyst such as component (c1(ii)) herein catalyses the reaction between an unsaturated group, usually an alkenyl group e.g., vinyl with Si-H groups. The catalyst (c1(ii)) of the liquid silicone rubber composition can be a platinum group metal, a platinum group metal deposited on a carrier, such as activated carbon, metal oxides, such as aluminum oxide or silicon dioxide, silica gel or powdered charcoal, or a compound or complex of a platinum group metal. Preferably the platinum group metal is platinum. Examples of preferred hydrosilylation catalysts (c1(ii)) are platinum based catalysts, for example, platinum black, platinum oxide (Adams catalyst), platinum on various solid supports, chloroplatinic acids, e.g., hexachloroplatinic acid (Pt oxidation state IV) (Speier catalyst), chloroplatinic acid in solutions of alcohols e.g., isooctanol or amyl alcohol (Lamoreaux catalyst), and complexes of chloroplatinic acid with ethylenically unsaturated compounds such as olefins and organosiloxanes containing ethylenically unsaturated silicon-bonded hydrocarbon groups, e.g., tetra-vinyl- tetramethylcyclotetrasiloxane-platinum complex (Ashby catalyst). Soluble platinum compounds that can be used include, for example, the platinum-olefin complexes of the formulae (PtCl2.(olefin)2 and H(PtCl3.olefin), preference being given in this context to the use of alkenes having 2 to 8 carbon atoms, such as ethylene, propylene, isomers of butene and of octene, or cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene, and cycloheptene. Other soluble platinum catalysts are, for the sake of example a platinum-cyclopropane complex of the formula (PtCl2C3H6)2, the reaction products of hexachloroplatinic acid with alcohols, ethers, and aldehydes or mixtures thereof, or the reaction product of hexachloroplatinic acid and/or its conversion products with vinyl- containing siloxanes such as methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanolic solution. Platinum catalysts with phosphorus and amine ligands can be used as well, e.g., (Ph3P)2PtCl2; and complexes of platinum with vinylsiloxanes, such as sym- divinyltetramethyldisiloxane.
Hence, specific examples of suitable platinum-based catalysts include (i) complexes of chloroplatinic acid with organosiloxanes containing ethylenically unsaturated hydrocarbon groups are described in US 3,419,593; (ii) chloroplatinic acid, either in hexahydrate form or anhydrous form; (iii) a platinum-containing catalyst which is obtained by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane; (iv) alkene-platinum-silyl complexes as described in US Pat. No.6,605,734 such as (COD)Pt(SiMeCl2)2 where “COD” is 1,5-cyclooctadiene; and/or (v) Karstedt's catalyst, a platinum divinyl tetramethyl disiloxane complex typically containing about 1 wt. % of platinum typically in a vinyl siloxane polymer with a viscosity of from about 200 to 750 using the test methodology as described for component (a). Solvents such as toluene and the like organic solvents have been used historically as alternatives but the use of vinyl siloxane polymers by far the preferred choice. These are described in US3,715,334 and US3,814,730. In one preferred embodiment component (c1(ii)) may be selected from co-ordination compounds of platinum. In one embodiment hexachloroplatinic acid and its conversion products with vinyl-containing siloxanes, Karstedt's catalysts and Speier catalysts are preferred. Component (c1(ii)) of the liquid silicone rubber composition is typically present in a quantity of platinum atom that provides from 0.1 to 500ppm (parts per million) with respect to the weight of the reactive ingredients, components (a) and (c1(ii)). The catalyst may be added as a single species or as a mixture of two or more different species. Typically, dependent on the form/concentration in which the catalyst (c1(ii)) is provided the amount of catalyst present will be within the range of from 0.05–1.5 wt. % of the composition, alternatively from 0.05–1.0 wt. %, alternatively from 0.1–1.0 wt. %, alternatively 0.1 to 0.5 wt. %, of the composition, wherein the platinum catalyst is provided in a masterbatch of polymer such as (a) described above. (d) stabilizing additive Component (d) of the liquid silicone rubber composition is 0.25 wt. % to a maximum of 5.0 wt.% of the composition, alternatively 0.5 wt. % to 5 wt. % of the composition, alternatively 0.5 wt. % to 3 wt. % of the composition, alternatively 0.5 wt. % to 2 wt. % of the composition, alternatively 0.5 wt. % to 1.5 wt. % of the composition, alternatively 0.75 wt. % to 1.5 wt. % of a stabilizing additive of the composition selected from the group consisting of one or more magnesium carbonates, one or more magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof. Alternatively the stabilizing additive comprises one or more magnesium carbonates or one or more magnesium hydroxy carbonates selected from magnesite (MgCO3), barringtonite (MgCO3.2H2O), nesquihonite (MgCO3.3H2O), lansfordite (MgCO3.5H2O); and one or more magnesium hydroxy carbonates such as pokrovskite (Mg2(CO3)(OH)2.0.5H2O), artinite (Mg2(CO3)(OH)2.3H2O), hydromagnesite (Mg5(CO3)4(OH)2.4H2O) which is sometimes referred to as light magnesium carbonate, dypingite
(Mg5(CO3)4(OH)2.5H2O) which is sometimes referred to as heavy magnesium carbonate, giorgiosite (Mg5(CO3)4(OH)2.5-6H2O) and shelkovite (Mg7(CO3)5(OH)4.24H2O). High consistency silicone rubber composition In the case of a high consistency rubber composition components (b”), (c1”) and (d”) are the same as (b), (c1) and (d) respectively for the liquid silicone rubber composition described above, however, component (a”) is different and component (c2”) a free radical curative replaces component (c1”), wherein: (a”) is chemically in accordance with component (a) of the LSR composition but contains the following differences, in that it has a much greater viscosity having a Williams plasticity of at least 100mm/100 measured in accordance with ASTM D-926-08; and the at least two unsaturated groups per molecule, which unsaturated groups are selected from alkenyl or alkynyl groups are essential when component (c1”) is being used as the catalyst package and is optional when component c is a free radical curative (c2”); and Component (c2”) Component (c2”) a free radical curative of the high consistency rubber composition is selected from a suitable azo compound or an organic peroxide or a selection thereof. Any suitable peroxide catalysts may be utilised. Suitable organic peroxides include substituted or unsubstituted dialkyl-, alkylaroyl-, diaroyl-peroxides, e.g., benzoyl peroxide and 2,4- dichlorobenzoyl peroxide, ditertiarybutyl peroxide, dicumyl peroxide, t- butyl cumyl peroxide, Bis(tert-butyldioxy)diisopropylbenzene bis(t-butylperoxy)-2,5-dimethyl hexyne 2,4-dimethyl-2,5- di(t- butylperoxy) hexane, di-t-butyl peroxide and 2,5-bis(tert-butyl peroxy)-2,5-dimethylhexane. Mixtures of the above may also be used. Typically, the amount of free radical curative (c2”) used in a high consistency rubber composition as described herein is from 0.2 to 3 wt. %, alternatively 0.2 to 2 wt. % in each case based on the weight of the composition. Optional Additives In each case, i.e., irrespective of whether the composition is a liquid silicone rubber composition or a high consistency rubber composition, a variety of optional additives to suit the application for which the elastomer resulting from cure is to be used may also be incorporated into the composition. Examples include cure inhibitors, mold releasing agents, non-reinforcing fillers, adhesion catalysts, electrically conductive fillers, thermally conductive fillers, pot life extenders, lubricants, heat stabilisers, compression set additives, UV light stabilizers, bactericides, wetting agents and the like. When present said optional additives may function as more than one type of additive. Cure Inhibitors Cure inhibitors are used, when required, in hydrosilylation (addition) cure systems e.g., when the composition comprises components C1, to prevent or delay the addition-reaction curing process
especially during storage. The optional addition-reaction inhibitors of platinum-based catalysts are well known in the art and include hydrazines, triazoles, phosphines, mercaptans, organic nitrogen compounds, acetylenic alcohols, silylated acetylenic alcohols, maleates, fumarates, ethylenically or aromatically unsaturated amides, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon monoesters and diesters, conjugated ene-ynes, hydroperoxides, nitriles, and diaziridines. Alkenyl-substituted siloxanes as described in US3989667 may be used, of which cyclic methylvinylsiloxanes are preferred. One class of known hydrosilylation reaction inhibitors are the acetylenic compounds disclosed in US3445420. Acetylenic alcohols such as 2-methyl-3-butyn-2-ol constitute a preferred class of inhibitors that will suppress the activity of a platinum-containing catalyst at 25 ºC. Compositions containing these inhibitors typically require heating at temperature of 70 ºC or above to cure at a practical rate. Examples of acetylenic alcohols and their derivatives include 1-ethynyl-1-cyclohexanol (ETCH), 2- methyl-3-butyn-2-ol, 3-butyn-1-ol, 3-butyn-2-ol, propargyl alcohol, 1-phenyl-2-propyn-1-ol, 3,5- dimethyl-1-hexyn-3-ol, 1-ethynylcyclopentanol, 3-methyl-1-penten-4-yn-3-ol, and mixtures thereof. Derivatives of acetylenic alcohol may include those compounds having at least one silicon atom. When present, inhibitor concentrations as low as 1 mole of inhibitor per mole of the metal of catalyst will in some instances impart satisfactory storage stability and cure rate. In other instances, inhibitor concentrations of up to 500 moles of inhibitor per mole of the metal of catalyst are required. The optimum concentration for a given inhibitor in a given composition is readily determined by routine experimentation. Dependent on the concentration and form in which the inhibitor selected is provided/available commercially, when present in the composition, the inhibitor is typically present in an amount of from 0.0125 to 10% by weight of the composition. In one embodiment the inhibitor when present is selected from 1-ethynyl-1-cyclohexanol (ETCH) and/or 2-methyl-3-butyn-2-ol and is present in an amount of greater than zero to 0.1 % by weight of the composition. Mold release agent Any suitable mold release agent may be utilised. It may, for example, be a hydroxydimethyl terminated polydimethylsiloxane having viscosity of approximately 21 mPa.s at 25oC measured using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 12rpm. Non-reinforcing fillers Non-reinforcing fillers may include such as crushed quartz, diatomaceous earths, barium sulphate, iron oxide, titanium dioxide and carbon black, talc, wollastonite. Other fillers which might be used alone or in addition to the above include aluminite, calcium sulphate (anhydrite), gypsum, calcium sulphate, clays such as kaolin, aluminium trihydroxide, graphite, copper carbonate, e.g., malachite,
nickel carbonate, e.g., zarachite, barium carbonate, e.g., witherite and/or strontium carbonate e.g., strontianite. Other fillers may include, aluminium oxide, silicates from the group consisting of olivine group; garnet group; aluminosilicates; ring silicates; chain silicates; and sheet silicates. The olivine group comprises silicate minerals, such as but not limited to, forsterite and Mg2SiO4. The garnet group comprises ground silicate minerals, such as but not limited to, pyrope; Mg3Al2Si3O12; grossular; and Ca2Al2Si3O12. Aluminosilicates comprise ground silicate minerals, such as but not limited to, sillimanite; Al2SiO5; mullite; 3Al2O3.2SiO2; kyanite; and Al2SiO5. Ring silicates may be utilised as non-reinforcing fillers, these include silicate minerals, such as but not limited to, cordierite and Al3(Mg,Fe)2[Si4AlO18]. The chain silicates group comprises ground silicate minerals, such as but not limited to, wollastonite and Ca[SiO3]. Sheet silicates may alternatively or additionally be used as non-reinforcing fillers where appropriate group comprises silicate minerals, such as but not limited to, mica; K2AI14[Si6Al2O20](OH)4; pyrophyllite; Al4[Si8O20](OH)4; talc; Mg6[Si8O20](OH)4; serpentine for example, asbestos; Kaolinite; Al4[Si4O10](OH)8; and vermiculite. For the avoidance of doubt component (d) is not considered a non-reinforcing filler. Further additives include silicone fluids, such as trimethylsilyl or OH terminated siloxanes. Such trimethylsiloxy or OH terminated polydimethylsiloxanes typically have a viscosity < 150 mPa.s at 25oC measured using a measured using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 12rpm. When present such silicone fluid may be present in the liquid curable silicone rubber composition in an amount ranging of from 0.1 to 5% by weight (wt. %), based on the total weight of the composition and may function as mold release agents. Pigments and other colourants Examples of pigments include titanium dioxide, chromium oxide, bismuth vanadium oxide, iron oxides and mixtures thereof. Examples of colouring agents for which may be used in the hydrosilylation curable silicone coating composition include pigments, vat dyes, reactive dyes, acid dyes, chrome dyes, disperse dyes, cationic dyes and mixtures thereof. The two-part moisture cure organopolysiloxane composition as described herein may further comprise one or more pigments and/or colorants which may be added if desired. The pigments and/or colorants may be coloured, white, black, metal effect, and luminescent e.g., fluorescent and phosphorescent. Pigments are utilized to colour the composition as required. Any suitable pigment may be utilized providing it is compatible with the composition herein. In two-part moisture cure organopolysiloxane compositions pigments and/or coloured (non- white) fillers e.g., carbon black may be utilized in the catalyst package to colour the end sealant product. Suitable white pigments and/or colorants include titanium dioxide, zinc oxide, lead oxide, zinc sulfide, lithophone, zirconium oxide, and antimony oxide.
Suitable non-white inorganic pigments and/or colorants include, but are not limited to, iron oxide pigments such as goethite, lepidocrocite, hematite, maghemite, and magnetite black iron oxide, yellow iron oxide, brown iron oxide, and red iron oxide; blue iron pigments; chromium oxide pigments; cadmium pigments such as cadmium yellow, cadmium red, and cadmium cinnabar; bismuth pigments such as bismuth vanadate and bismuth vanadate molybdate; mixed metal oxide pigments such as cobalt titanate green; chromate and molybdate pigments such as chromium yellow, molybdate red, and molybdate orange; ultramarine pigments; cobalt oxide pigments; nickel antimony titanates; lead chrome; carbon black; lampblack, and metal effect pigments such as aluminium, copper, copper oxide, bronze, stainless steel, nickel, zinc, and brass. Suitable organic non-white pigments and/or colorants include phthalocyanine pigments, e.g., phthalocyanine blue and phthalocyanine green; monoarylide yellow, diarylide yellow, benzimidazolone yellow, heterocyclic yellow, DAN orange, quinacridone pigments, e.g., quinacridone magenta and quinacridone violet; organic reds, including metallized azo reds and nonmetallized azo reds and other azo pigments, monoazo pigments, diazo pigments, azo pigment lakes, β-naphthol pigments, naphthol AS pigments, benzimidazolone pigments, diazo condensation pigment, isoindolinone, and isoindoline pigments, polycyclic pigments, perylene and perinone pigments, thioindigo pigments, anthrapyrimidone pigments, flavanthrone pigments, anthanthrone pigments, dioxazine pigments, triarylcarbonium pigments, quinophthalone pigments, and diketopyrrolo pyrrole pigments. Typically, the pigments and/or colorants, when particulates, have average particle diameters in the range of from 10 nm to 50 µm, preferably in the range of from 40 nm to 2 µm. Lubricants As previously indicated compositions of the sort described herein are often used as electrical or electronic connectors. Often such electrical or electronic connectors are made from self-lubricating silicone elastomers which are designed to gradually exude over time from the cured seals and lubricate cable and connector assemblies. Typically, polyphenylmethylsiloxanes and copolymers thereof such as trimethylsilyl terminated phenylmethylsiloxane dimethylsiloxane copolymers having a viscosity of from 100mPa.s to 200mPa.s at 25oC using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 12rpm and mixtures or derivatives thereof. are used as the lubricants in such situations. Examples of other lubricants which might be alternatively or additionally utilised include tetrafluoroethylene, resin powder, graphite, fluorinated graphite, talc, boron nitride, fluorine oil, molybdenum disulfide, and mixtures or derivatives thereof. When present such lubricants may be present in an amount of from 1 to 7 wt. % of the composition. Heat Stabilisers The composition herein may also comprise one or more inorganic heat stabilizers, such as hydrated cerium oxide, cerium hydroxide, cerium carboxylates and/or cerium esters, e.g., cerium
ethylhexanoate, hydrated aluminum oxide, red iron oxide, yellow iron oxide, carbon black, graphite and zinc oxide used alone or in combination. Metal Deactivators The composition may incorporate one or more metal deactivators selected from a diacylhydrazide- based compound, an aminotriazole-based compound, and an amino-containing triazine-based compound. Alternatively, the metal deactivator has a molecular weight of 120 to 700 and is an amino group-containing triazine compound or a compound having a phenol group in the backbone and an amide bond. Typically, the metal deactivator has a melting point of 80 °C or more, and 300 °C or less, wherein the melting point is measured by means of a differential scanning calorimetry (DSC). The melting point can be measured by a differential scanning calorimeter (DSC) according to JIS K 7121-1978 “Testing Methods for Transition Temperatures of Plastics.” In this apparatus, a pan for DSC measurement in which a polyester resin (A) sample was sealed was set, heated to 320 °C at a heating rate of 10 °C/min in a nitrogen atmosphere, and held at that temperature for 5 minutes. The temperature is decreased to 30 °C by measuring the temperature decrease at 10 °C/min. The temperature at the top of the endothermic peak at the time of temperature rise is defined as the “melting point.” The diacylhydrazide-based compound is represented by the following general formula: R 1 C N N C R2 H H
be the same or different and may be represented by hydrogen atoms, hydroxyl groups, alkyl groups, substituted alkyl groups, aryl groups, phenol groups or similar substituted aryl groups, aralkyl groups, or substituted aralkyl groups. It is preferable that R1 and R2 comprise monovalent hydrocarbon groups that contain aryl groups, a phenol or a similar substituted aryl group. Specific examples of the aforementioned diacylhydrazide-based compounds are the following: N,N’-diformyl hydrazine, N,N’-diacetyl hydrazine, N,N’-dipropionyl hydrazine, N,N’- butylyl hydrazine, N-formyl-N’-acetyl hydrazine, N,N’-dibenzoyl hydrazine, N,N’-ditolyoyl hydrazine, N,N’-disalicyloyl hydrazine, N-formyl-N’- disalicyloyl hydrazine, N-formyl-N’-butyl- substituted salicyloyl hydrazine, N-acetyl-N’- salicyloyl hydrazine, N,N’-bis [3-(3,5-di-t-butyl-4- hydroxyphenyl) propyonyl] hydrazine, adipic acid di-(N’-salicyloyl) hydrazine, or dodecane dioyl- di-(N’-salicyloyl) hydrazine. Commercially produced compounds of the aforementioned include, for the sake of example are N,N’-bis –[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine), sold as IrganoxTM MD1024 from BASF, dodecanedioyl-di-(N′-salicyloyl)hydrazine, a synonym for which is 1-N',12-N'-bis(2- hydroxybenzoyl)dodecanedihydrazide, which is sold commercially as ADK STABTM CDA-6 from Adeka Corporation (referred to hereafter as CDA-6); N'1,N'12-Bis(2- hydroxybenzoyl)dodecanedihydrazide which is sold commercially as ADK STABTM CDA-6S from
Adeka Corporation, and N,N'-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine which is sold commercially as ADK STABTM CDA-10 from Adeka Corporation, and N,N'-bis-3-(3,5-di-tert-butyl-4 hydroxyphenyl)propionylhexamethylenediamine which is sold commercially as ANTAGE HP-300 from Kawaguchi Chemical Industry. The aminotriazole-based compound is expressed by the following general formula (2): R 5 N C N 4
where R4 and R5 are the same or different and are represented by hydrogen atoms, alkyl groups, substituted alkyl groups, substituted aryl groups, carboxyl groups, acyl groups, alkyl-ester groups, aryl-ester groups, halogens, or alkali metals; R3 may represent a hydrogen atom or an acyl group; R5 may be an acyl group, preferably, a salicyloyl group, benzoyl group, or a similar acyl group having an aromatic ring. Examples of the aforementioned compounds may include 3-amino-1,2,4-triazole, 3-amino-1,2,4-triazole-carboxylic acid, 3-amino-5-methyl-1,2,4-triazol, 3-amino-5-heptyl-1,2,4- triazol, etc.; or an acid amide derivative of an amino-triazole-based compound where the hydrogen atoms of a triazole-bonded amino groups are substituted with acyl groups, e.g., 3-(N-salicyloyl) amino-1,2,4-triazole or 3-(N-acetyl) amino-1,2,4-triazol-5-carboxylic acid. Most preferable among the above compounds is the acid amide derivative of the aminotriazole-based compound since this compound does not delay speed of curing of the addition-reaction-curable silicone rubber composition. An example of a commercially produced compound of this type is 3- (n-Salicyloyl)Amino-1,2,4- Triazole (a synonym for which is 2-Hydroxy-N-1H-1,2,4-triazol-3-ylbenzamide) which is sold commercially as ADK STABTM CDA-1 and in a blend as ADK STAB CDA-1M from Adeka Corporation. A further commercial example is AdekastabTM ZS-27 from Adeka Corporation the main component of which is understood to be 2,4,6-triamino-1,3,5-triazine. In one embodiment the composition contains a metal deactivator as described above. In one alternative component (e) (ii) is dodcadioyl-di-(N’-salicyloyl) hydrazine or 3-(N-salicyloyl) amino-1,2,4-triazole. When present, component (e) (ii) is added in an amount of 0.001 to 1.0 wt. % of the composition, alternatively an amount of 0.001 to 0.5 wt. % of the composition, alternatively in an amount of 0.01 to 0.5 wt. % of the composition, alternatively in an amount of 0.05 to 0.5 wt. % of the composition.
Hence, the liquid silicone rubber composition used to produce the silicone elastomers herein may comprise any suitable combination of the following components: a) one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25oC; alternatively 5000 mPa.s to 75,000 mPa.s at 25oC, 10,000 mPa.s to 60,000 mPa.s at 25oC, an is preferably present in an amount of from 25 to 60 wt. % of the composition, alternatively in an amount of from 30 to 60 wt. % of the composition, alternatively in an amount of from 35 to 55 wt. % of the composition. Viscosity may be measured at 25 °C as described above; b) a silica reinforcing filler which is preferably in a finely divided form and is optionally hydrophobically treated; high surface area, which is typically at least 50 m²/g (BET method in accordance with ISO 9277: 2010). Silica reinforcing filler (c) s having surface areas of from 50 to 450 m²/g (BET method in accordance with ISO 9277: 2010), alternatively of from 50 to 300 m²/g (BET method in accordance with ISO 9277: 2010) and are typically present in an amount of up to 40 wt. % of the composition, alternatively from 1.0 to 40wt. % of the composition, alternatively of from 5.0 to 35wt. % of the composition, alternatively of from 10.0 to 35wt. % of the composition; Component (c1) of the liquid silicone rubber composition is a hydrosilylation cure package comprising (c1(i)) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; and (c1(ii)) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; The organosilicon compound having at least two, alternatively at least three Si-H groups per molecule (c1(i)) as hereinbefore described, may be present in an amount of from 0.1 to 10 wt. % of the liquid silicone rubber composition, alternatively 0.1 to 7.5wt. % of the hydrosilylation curable silicone rubber composition, alternatively 0.5 to 7.5wt. %, further alternatively from 0.5% to 5 wt. % of the composition; Component (c1(ii)) of the liquid silicone rubber composition is a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof as hereinbefore described; in an amount dependent on the form/concentration in which the catalyst is provided, within the range of from 0.001 to 3.0 wt. % of the composition, alternatively from 0.001 to 1.5 wt. % of the composition, alternatively from 0.01–1.5 wt. %, alternatively 0.01 to 0.1.0 wt. %, of the silicone rubber composition, Component (d) is 0.25 wt. % to a maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof; providing the total wt. % of the composition is 100 wt. %.
The composition may also contain one or more of the above optional additives in amounts indicated again providing the total wt. % of the composition is 100 wt. %. Hence, the high consistency rubber composition which may be used to produce the silicone elastomers herein may comprise any suitable combination of the following components: a”) one or more polyorganosiloxanes having a Williams plasticity of at least 100mm/100 in accordance with ASTM D-926-08 wherein when hydrosilylation curable polymer a” must also contain at least two unsaturated groups, selected from alkenyl groups and alkynyl groups whilst when the high consistency rubber composition is free-radical cured the at least two unsaturated groups, selected from alkenyl groups and alkynyl groups are optional in polymer a”; which component a” is preferably present in an amount of from 25 to 60 wt. % of the composition, alternatively in an amount of from 30 to 60 wt. % of the composition, alternatively in an amount of from 35 to 55 wt. % of the composition. b”) a silica reinforcing filler which is the same as component (b) above with respect to the liquid silicone rubber composition; Component (c1”) of the high consistency rubber is a hydrosilylation cure package and is used when the high consistency rubber is a hydrosilylation (addition) curable composition ed and has the same composition and amounts as component (c1) for the liquid silicone rubber composition above; position, Component c2” a free radical curative of the high consistency rubber composition is selected from a suitable azo compound or an organic peroxide or a selection thereof; in an amount of free radical curative (c2”) utilised in a high consistency rubber composition as described herein is from 0.2 to 3 wt. %, alternatively 0.2 to 2 wt. % in each case based on the weight of the composition; Again, component (d) is 0.25 wt. % to a maximum of 5.0 wt.% of the composition, alternatively 0.5 wt. % to 5 wt. %, alternatively 0.5 wt. % to 3 wt. %, alternatively 0.5 wt. % to 2 wt. %, alternatively 0.5 wt. % to 1.5 wt. %, alternatively 0.75 wt. % to 1.5 wt. % of the composition is a stabilizing additive selected from the group consisting of one or more magnesium carbonates, one or more magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof; providing the total wt. % of the composition is 100 wt. %. The composition may also contain one or more of the above optional additives in amounts indicated again providing the total wt. % of the composition is 100 wt. %. When the silicone elastomers used herein are prepared from liquid silicone rubber compositions as hereinbefore described such compositions are hydrosilylation curable and are usually stored before use in two or more parts. In the case of a two-part composition, the two parts are usually referred to as part (A) and part (B): Part (A) typically contains the catalyst (c1(ii)) in addition to polyorganosiloxane (a) and silica reinforcing filler (b) when present, and
Part (B) usually includes cross-linker component (c1(ii)) and when present optional inhibitor as well as remaining polyorganosiloxane (a) and/or the silica reinforcing filler (b). It is important for the catalyst (c1(ii)) to be stored separately from cross-linker (c1(ii)) to prevent premature cure during storage. Components (d), the 0.25 wt. % to a maximum of 5.0 wt.% of stabilizing additive is selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof. It may be stored in either part (A) or part (B) or in both parts providing they do not negatively affect the storage of any of the essential ingredients present in the respective part. Alternatively, if desired component (d) may be added into the remaining composition i.e., to the combination of the part (A) and part (B) compositions during or after the part (A) composition and the part (B) compositions are mixed together prior to use. Any optional additives, other than the inhibitor described above, may be incorporated into either part (A) or part (B) or in both parts providing they do not negatively affect the storage of any of the essential ingredients present in the respective part. The compositions can be designed to be mixed in any suitable weight ratio e.g., part (A) : part (B) may be mixed together in ratios of from 10:1 to 1:10, alternatively from 5:1 to 1:5, alternatively from 2:1 to 1:2, but most preferred is a weight ratio of 1:1. Ingredients/components in each of Part (A) and/or Part (B) may be mixed together individually in their respective part or may be introduced into the composition in pre-prepared in combinations for, e.g., ease of mixing the final composition. For Example, components (a) and (b) are often mixed together to form an LSR polymer base or masterbatch prior to introduction of other ingredients. These may then be mixed with the other ingredients of the Part being made directly or may be used to make pre-prepared concentrates commonly referred to in the industry as masterbatches. In this instance, for ease of mixing ingredients, one or more masterbatches may be utilized to successfully mix the ingredients to form Part (A) and/or Part (B) compositions. For example, a “fumed silica” masterbatch may be prepared. This is effectively an LSR silicone rubber base with the silica reinforcing filler (c) treated in situ. Parts A and B of the composition may be prepared by combining all of their respective components at ambient temperature. Any mixing techniques and devices described in the prior art can be used for this purpose. The particular device to be used will be determined by the viscosities of components and the final composition. A suitable mixer may include but are not limited to kneader mixer, a static mixer in a liquid injection molding machine, a Z-blade mixer, a two-roll mill (open mill), a three-roll mill, a Haake® Rheomix OS Lab mixer, a screw extruder or a twin-screw extruder or the like. Speed mixers as sold by e.g., Hauschild and as DC 150.1 FV, DAC 400 FVZ or DAC 600 FVZ, may alternatively be used. Cooling of components during mixing may be desirable to avoid premature curing of the composition.
The part (A) and part (B) compositions can be designed to be mixed in any suitable ratio e.g., part (A) : part (B) may be mixed together in weight ratios of from 10:1 to 1:10, alternatively from 5:1 to 1:5, alternatively from 2:1 to 1:2, but most preferred is a weight ratio of 1:1. Prior to use the respective Part (A) and Part (B) compositions are mixed together in the desired ratio. Curing of the hydrosilylation curable silicone rubber composition on the substrate can, for example, take place in a mold to form a molded part, by injection molding, using e.g., a Liquid injection molding system (LIMS) press moulding, extrusion moulding, transfer moulding, press vulcanization, or calendaring. In the case of a process for the manufacture of a two-part silicone rubber composition as hereinbefore described the process may comprise the steps (i) preparation of a silicone base composition comprising components (a) polymer and (c) silica reinforcing filler, (ii) dividing the resulting base into two parts, part (A) and part (B) and introducing the catalyst (d) into part (A) and the cross-linker (b) and inhibitor (if present) in the part (B) composition. (iii) Introducing the other components any other optional additives into either or both part (A) and part (B); and (iv) Storing the part (A) and part (B) compositions separately. Typically, when used the part (A) and part (B) compositions are thoroughly mixed in a suitable weight ratio as described above, immediately before use in order to avoid premature cure. The curing stage cure is then undertaken. The hydrosilylation curable silicone rubber composition is cured at any suitable temperature e.g., at a temperature of from 80oC to 200oC, alternatively from about 100oC to 180oC, alternatively from about 120oC to 180oC. As indicated above one of the standard ways of reducing compression set historically has been post curing with a view to reducing the number curable groups which might cure under compression during use as gaskets. The hydrosilylation curable high consistency rubber option may be prepared in an analogous fashion as the above if desired. However, given component (a”) is a silicone gum having a having a Williams plasticity of at least 100mm/100 in accordance with ASTM D-926-08 generally the composition is prepared by combining all of components together at ambient temperature into a one-part composition in cases where the composition is to be used immediately. Typically, a base is prepared first to enable the reinforcing silica fillers (b”) to be treated in-situ with a hydrophobing treating agent simultaneously with the mixing of the polymer and filler and any other additional treating agents when additionally present and then the remaining ingredients can be introduced into the mixture in any suitable order. Any mixing techniques and devices described in the prior art can be used for this purpose. The particular device to be used will be determined by the viscosities of components and the final curable coating composition. Suitable mixers include but are not limited to paddle type mixers e.g., planetary mixers and
kneader type mixers. However, when component (a”) is a gum mixing is preferably undertaken, as previously indicated using a kneader mixer. Cooling of components during mixing may be desirable to avoid premature curing of the composition. There is also a process described herein for the preparation of a high consistency silicone rubber elastomer comprising the steps of (i) preparing a silicone rubber base composition comprising components (a), (b) and (c) as hereinbefore described, (ii) mixing into the silicone rubber base of step (i) components (d), (e) and simultaneously or subsequently component (f); and (iii) curing the composition. Step (i) may be achieved by mixing together components polymer (a”) and filler (b”) together with treating agent at a temperature in the range of from 80oC to 250oC, alternatively from 100 oC to 220 oC, alternatively 120 oC to 200 oC for a period of from 30 minutes to 2 hours, alternatively 40 minutes to 2 hours, alternatively of from 45 minutes to 90 minutes, to ensure the reinforcing silica filler is in-situ treated with the hydrophobing treating agent and they are all thoroughly mixed into component (a”). The resulting base may then be cooled to approximately room temperature (23oC to 25oC). The remaining components may then be simultaneously or subsequently added as well as optional inhibitor (e.g., Ethynyl Cyclohexanol (ETCH)) and any other optional additives in any suitable order, or simultaneously and mixing to homogeneity. Once prepared because of the reactivity of the polymer, hydrosilylation cross-linker and hydrosilylation catalyst the composition will cure. Typically, cure will take place at a temperature between 80oC and 180 oC, alternatively between 100 oC and 170 oC, alternatively between 120 oC and 170 oC. This may take place in any suitable manner for example, the composition may be introduced into a mold and is then press cured for a suitable period of time, e.g., from 2 to 10 minutes or as otherwise desired or required. The present hydrosilylation curable heat stabilised silicone rubber composition may alternatively be further processed by injection moulding, encapsulation moulding, press moulding, dispenser moulding, extrusion moulding, transfer moulding, press vulcanization, centrifugal casting, calendaring, bead application or blow moulding. As and when required samples may be additionally post-cured by heating to a temperature of 130oC to 200oC for up to 4 hours. Once prepared the silicone elastomeric article can be placed in its functional position on and/or around the flame-retardant free thermoplastic article to provide a final silicone-thermoplastic composite article. Subsequently the silicone-thermoplastic composite article is placed/fitted in position for use as and when required as part of a manufacturing process or the like.
The silicone-thermoplastic composite articles may be used for a wide range of applications in industrial situations, the home and increasingly in automobiles. In automotive applications they may be used as battery components, in charging components and powertrain components for electric vehicles, and in noise and vibration applications but are particularly well-known for being the rigid housing components for electrical or electronic connector housings used to create closed electrical circuits in automotive, residential, and infrastructural settings. They are also utilised in a wide range of electrical and/or insulative applications e.g., for cable accessories such as electrical or electronic connectors, terminations and wire seals. Electrical or electronic connectors are commonly used to create closed electrical circuits in automotive, residential, and infrastructural settings due to their excellent balance of mechanical properties, chemical and thermal stabilities, processing ease, and availability of self-lubricating formulations. They may be used to mate rigid flame-retardant free thermoplastic housing components to provide both electrical and environmental isolation to the connector junctions from, for example, the potential presence of moisture, oils and fuels, and corrosive gases. The silicone elastomers made using the compositions herein have a suitably low compression set at high temperatures to provide mechanical integrity and dimensional stability electrical or electronic connectors etc. as described above to provide excellent sealing performance during service life. Hence, they are used in or for the manufacture of automotive parts, cable accessories; electrical and electronic parts; packaging parts; construction parts such as sealants; household parts. In one embodiment the cable accessory is an electrical or electronic connector having a silicone elastomer seal. The following examples are intended to illustrate and not to limit the disclosure herein. EXAMPLES All viscosities were measured at 25oC unless otherwise indicated. Viscosities of individual components in the following examples were measured using a BrookfieldTM rotational viscometer with spindle LV-4 for viscosities over 15,000mPa.s (Spindle LV-4 designed for viscosities in the range between 1,000-2,000,000 mPa.s) at an appropriate rpm and using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 for viscosities up to 15, 000mPa.s at an appropriate rpm unless otherwise indicated. The stability of physical properties caused by the introduction of the stabilising additive herein is exemplified by assessing the change in compression set in the following examples which it is believed is caused by the stabilising additive negating the debilitating effect on the silicone elastomers assessed by species migrating therein from the flame-retardant free thermoplastic. The compression set results provided were undertaken in accordance with industrial standard norm ASTM D395 – 18 method B in which a cylindrical disc of diameter 29.0 mm ± 0.5mm and thickness 12.5 mm ± 0.5mm was compressed by 25% to about 9.38 mm thickness. Under compression the LSR buttons (cured by compression molding directly into a button mold at 171 °C for 20 minutes)
were sandwiched on both top and bottom with substrate (metal or flame-retardant free thermoplastic) and placed in the normal compression fixture. When needed, a thin metal shim plate was used to adjust for variability of substrate thickness. Unless otherwise indicated samples were placed in a convection oven at 25% compression and a specified oven temperature set to for a specified period of time (hours (h)). Subsequently, compression was released and the test pieces were allowed to recover for 30 min prior to taking compression set measurements. A series of 2-part liquid silicone rubber elastomer compositions were prepared as indicated in Tables 1a, 2a and 6a below The flame-retardant free thermoplastics utilised in the examples were:- Unfilled PA66: Tecamid made by Ensinger, available from McMaster Carr of Elmhurst Illinois, USA as Part #8539K311 PA66 GF25: thermoplastic PA66-GF25 is a commercially available 25% glass fibre reinforced (GF25) PA6,6 known as DURETHANTMAKV25 from Lanxess. PA6-GF25: thermoplastic PA6-GF25 is a commercially available 25% glass fibre reinforced (GF25) PA6, known as DURETHANTM BKV25 from Lanxess. PBT GF30: thermoplastic PBT GF30, which is a commercially available 30% glass fibre reinforced (GF30) PBT, known as ULTRADURTM B 4300 G6 NAT from Dupont. In the above, for the avoidance of doubt, PA = polyamide and PBT = polybutylene terephthalate. The following components are referred to where pertinent in the compositions used:- Fumed Silica 1: Treated fumed silica in the form of dimethylvinylated and trimethylated treated fumed silica having a BET surface area of approximately 250 m2/g (untreated). Fumed Silica 2: Treated fumed silica in the form of dimethylvinylated and trimethylated treated fumed silica having a BET surface area of approximately 400 m2/g (untreated). Polymer 1: vinyldimethyl terminated polydimethylsiloxane having a viscosity of 53,000 mPa.s at 25 °C measured using a BrookfieldTM rotational viscometer with spindle LV-4 at 6rpm. Polymer 2: vinyl terminal poly(dimethylsiloxane-co-methylvinylsiloxane) having a viscosity of 370 mPa.s at 25°C using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 12rpm. Silica Masterbatch 1: dispersion of 66.6 wt. % dimethylvinylsiloxy-terminated polydimethylsiloxane having a viscosity of about 53,000 mPa.s at 25° C with a total vinyl content of 0.17 wt.% and 33.4 wt.% of dimethylvinylated and trimethylated treated fumed silica having a BET surface area of approximately 250 m2/g (untreated). Silica Masterbatch 2: dispersion of 70.8 wt. % dimethylvinylsiloxy-terminated polydimethylsiloxane having a viscosity of about 53,000 mPa.s at 25° C with a total vinyl content of 0.062 wt.% and 29.2 wt.% of trimethylated treated fumed silica having a BET surface area of approximately 250 m2/g (untreated).
Crosslinker 1: trimethyl terminated polymethylhydrogen dimethylsiloxane having a viscosity of 30mPa.s at 25°C using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 12rpm. Crosslinker 2: Dimethyl, methylhydrogen siloxane with methyl silsesquioxane having a viscosity of 15 mPa.s at 25°C using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 12rpm. Inhibitor: 1-Ethynyl-cyclohexanol (ETCH). Additive 1: tetravinyl-tetramethyl-cyclotetrasiloxane. Additive 2: hydroxydimethyl terminated polydimethylsiloxane having viscosity of approximately 21 mPa.s at 25 °C measured using a BrookfieldTM rotational viscometer with spindle LV-2 at 12rpm. Additive 3: trimethylsilyl terminated phenylmethylsiloxane dimethylsiloxane copolymer having a viscosity of 125 mPa.s at 25°C using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 12rpm. Additive 4: dodecanedioyl-di-(N′-salicyloyl)hydrazine, a synonym for which is 1-N’,12-N’-bis(2- hydroxybenzoyl)dodecanedihydrazide, which is sold commercially as ADK STABTM CDA-6 from Adeka Corporation. Additive 5: Hydroxydimethyl terminated polydimethylsiloxane having viscosity of approximately 42 mPa.s at 25 °C using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 12rpm. Stabilizing additive 1: dispersion of 85 wt.% of dimethylvinylsiloxy-terminated polydimethylsiloxane having a viscosity of about 2000 mPa.s at 25° C using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 3rpm and 15 wt.% copper phthalocyanine commercially sold as LIONOL BLUE FG-7330 from Toyocolor. Stabilizing additive 2: dispersion of 50 wt.% of dimethylvinylsiloxy-terminated polydimethylsiloxane having a viscosity of about 2000 mPa.s at 25° C using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 at 3rpm and 50 wt.% iron (III) oxide commercially sold as BAYFERROXTM 110 M from Lanxess. Stabilizing additive 3: Magnesium hydroxide commercially sold as Versamag™ from Akrochem. Stabilizing additive 4: ground calcium carbonate with a mean particle size of 3 μm commercially sold as AtomiteTM from Imerys. Stabilizing additive 5: ammonium stearate surface treated ground calcium carbonate with a mean particle size of 3 μm commercially sold as Gama-SperseTM CS-11 from Imerys. Stabilizing additive 6: zinc oxide, catalog No.96479 from Sigma Aldrich. Stabilizing additive 7: Sodium phosphate dibasic, catalog No. S9763 from Sigma Aldrich.
Stabilizing additive 8: magnesium carbonate hydrate commercially sold as AkrochemTM Light Magnesium Carbonate from Akrochem. Stabilizing additive 9: magnesium oxide commercially sold as MAGOXTM 98 HR from Premier Magnesia, LLC. In the following examples, utilising the above, the compositions depicted in Tables 1a, 2a and 6a were all prepared as follows: In the case of the compositions in Table 1a and 2a, two-part compositions were prepared: Treated fumed silica 1, polymers 1 and 2, catalyst, additives 1, 2, and 3 and stabilizing additive were blended into a first part, part A and treated fumed silica 1, polymers 1 and 2, cross-linker 1, inhibitor, additives 2, 3, and 4 and stabilizing additive were blended together into a second part, part B. In the compositions in Table 6a, a two-part LSR composition was prepared as follows: treated fumed silica 2, polymers 1 and 2, catalyst, additives 1 and 5 and stabilizing additive were blended into a first part, part A and treated fumed silica 2, polymers 1 and 2, crosslinker 2, inhibitor, additive 5 and stabilizing additive were blended together into a second part, part B. In each composition the respective Parts A and B were mixed together to homogeneity in a 1:1 weight ratio to yield the liquid curable silicone elastomer compositions which were then cured as indicated above by compression molding directly into a button mold at 171 °C for 20 minutes. The compositions for Ref.1 and Comparatives 1 to 7 (Comp.1 to 7) are depicted in Table 1a Comparative examples 1 to 7 were tested to assess the suitability of “stabilizing additives” 1 to 7 in stabilizing silicone rubber when in direct contact with flame-retardant free thermoplastic materials. In most instances it was hoped that the selected “stabilizing additives” would help stabilize the silicone elastomers. Ref.1 contained no proposed stabilizing agent.
Table 1a: Compositions of Ref.1 and Comparative compositions C.1 to C.7 (wt. %) Ingredients Ref.1 C.1 C.2 C.3 C.4 C.5 C.6 C.7 Silica 1 30.41 29.19 29.80 30.10 30.10 30.10 30.10 30.10
n or er to assess t e capa ty o eac sta z ng agent ut se n t e compos t ons use , samples of the Reference 1 (Ref.1) and comparatives 1 to 7 were in each instance (a) in a first test sandwiched on both top and bottom with aluminum substrate (Al) and (b) in a second test an equivalent sample was sandwiched on both top and bottom with one of the previously mentioned flame-retardant free thermoplastics as indicated. The samples were compressed at 25% for 168 hours at 175 °C in accordance with ASTM D395 – 18 method B. Each of C.1 to C.7 were assessed to determine how many of the “stabilizing agents” functioned to stabilize the silicone elastomer samples tested. The results are depicted in Table 1b below. The percentage change in compression set of unfilled PA66 to Al was determined by working out the difference between the compression set values when aluminium was the substrate and when the unfilled PA66 was the substrate which for Ref.1 was 44.1 -34.7 = 9.4 and then determining this value as a percentage of the aluminium value e.g., (9.4/34.7) x 100 = 27.1%
Table 1b: Compression set (%) results for cured samples of Ref.1 and C.1 – C.7 after compression for 168 hours at 175 °C in accordance with ASTM D395 – 18 method B Ref.1 C.1 C.2 C.3 C.4 C.5 C.6 C.7 Aluminum 34.7 19.2 26.8 27.7 31.8 32.1 39.9 37.9 2 9
prior art for improving compression set of silicone elastomers such as copper phthalocyanine (C.1), and iron oxide (C.2) show higher percent change in compression set than the Ref.1. Similar findings were observed for compositions containing acid scavengers reported in prior art such as magnesium hydroxide (C.3), which shows a percent change of 39.7%. Comparative examples ( C.4 to C.7) correspond to liquid curable silicone elastomer compositions containing stabilizing additives acting as acid scavengers. Percent change in compression set of these comparative examples when in contact with unfilled PA66 substrates was higher than the Ref.1. For example, percent change of C.4 composition containing calcium carbonate was 34% when in contact with unfilled PA66. The above was considered surprising as it had been expected to determine several of the above would stabilize the compression set results and therefore be deemed suitable stabilizing additives to help maintain the durability of silicone elastomers in direct contact with flame-retardant free thermoplastics, e.g., in a silicone-thermoplastic composite with time. The above was considered surprisingly poor as it had been expected to that one or two of the above proposed stabilization additives would have successfully assisted in maintaining the durability of the silicone elastomer but in most cases significantly worse compression set results were achieved. Indeed. even more surprisingly despite the introduction of the additive, the results were at best only slightly improved when compared to Ref.1 but in the main were significantly worse. In the end none of the above were considered suitable stabilizing additives to help maintain the durability of silicone elastomers in direct contact with thermoplastics, e.g., in a silicone-thermoplastic composite with time. A further series of samples were prepared and tested for compression set in the same way. The compositions used to generate the elastomer samples are detailed in Table 2a below with respect to Ref.1 and Ex.1 to 3. Inventive examples 1 to 3, disclosed in Table 2a, correspond to liquid curable silicone elastomer compositions containing a stabilizing additive selected from the group consisting of a magnesium carbonate, magnesium hydroxy carbonate and magnesium oxide such as light magnesium carbonate (hydromagnesite) (Akrochem) and MagoxTM 98 HR magnesium oxide (Premier Magnesia, LCC).
Table 2a: Compositions of Ref.1 and Ex.1 to 3 (wt. %) Ingredients Ref.1 Ex.1 Ex.2 Ex.3 Silica 1 30.41 30.10 29.95 30.10 Samples were cured
nd the compression set results for 168 hours at 175 °C are provided in Table 2b below. Table 2b: Compression set (%) results for cured samples of Ref.1 and Ex.1 – 3 after compression for 168 hours at 175 °C in accordance with ASTM D395 – 18 method B Ref.1 Ex.1 Ex.2 Ex.3 Examp
les 1 and 2 contain 1.0 and 1.5 wt.% of stabilizing additive 8 (light magnesium carbonate, otherwise known as hydromagnesite), respectively. They show a percent change in compression set of 6.2 and -20.1, respectively, when in contact with unfilled PA66 substrate which are significantly lower than Ref.1 (27.1%). The negative percent change in Ex.2 means that the compression set of Ex.2 containing 1.5 wt.% of light magnesium carbonate in unfilled PA66 was lower (40.5%) than in Al (45.3%). Similarly, a lower percent change in compression set (-6.2%) was obtained for Ex.3 containing stabilizing additive 9 (MagoxTM 98 HR magnesium oxide). The LSR compositions identified above in Table 2a as Ex.1 and 3 were used again as the LSR compositions in Ex.4 and Ex.5 respectively. They were used in contact with flame retardant-free
glass-fiber reinforced thermoplastic PA66-GF25. The results for Ref.1 and Ex.4 and 5 when in contact with PA66-GF25 for 168 hours at 175 °C are provided in Table 3 below. Table 3: Compression set (%) results for cured samples of Ref.1 and Ex.4 and 5 after compression for 168 hours at 175 °C in accordance with ASTM D395 – 18 method B Ref.1 Ex.4 Ex.5 Aluminium 34.7 35.2 40.3 Ex.4 and 5
ng additive 8 and 9, respectively. The percent change in compression set of Ex.4 and 5 in PA66-GF25 is -8.2 and -9.2 respectively, which is lower than Ref.1 (12.7%), thus confirming the benefit of stabilizing additives 8 and 9 in another type of flame-retardant free thermoplastic. The LSR compositions identified above in Table 2a as Ex.1 and 3 were also used again as the LSR compositions in Ex.6 and 7 respectively. They were used in contact with flame retardant-free glass- fiber reinforced thermoplastic PA6-GF25. The results for Ref.1 and Ex.6 and 7 when in contact with PA6-GF25 for 1008 hours at 125 °C are provided in Table 4 below. Table 4: Compression set (%) results for cured samples of Ref.1 and Ex.6 and 7 after compression for 1008 hours at 125 °C in accordance with ASTM D395 – 18 method B Ref.1 Ex.6 Ex.7
The compression set change of examples 6 (46.4%) and 7 (47.9%) when in contact with PA6-GF25 were much improved when compared to the results seen using the Ref.1 (74.4%), thus demonstrating the benefit of stabilizing additives 8 and 9 in another type of flame-retardant free thermoplastic and at a different test condition. The LSR compositions identified above in Table 2a as Ex.1 and 3 were also used again as the LSR compositions in Ex.8 and 9 respectively. They were used in contact with flame retardant-free glass- fiber reinforced thermoplastic PBT GF30. The results for Ref.1 and Ex.8 and 9 when in contact with PBT GF30 for 1008 hours at 125 °C are provided in Table 5 below.
Table 5: Compression set (%) results for cured samples of Ref.1 and Ex.8 and 9 after compression for 1008 hours at 125 °C in accordance with ASTM D395 – 18 method B Ref.1 Ex.8 Ex.9 Aluminium 22.7 16.8 16.3 The com
125o C is lower than the Ref.1 material, demonstrating once again the benefit of stabilizing additives 8 and 9 in another type of flame-retardant free thermoplastic. A further comparison was made using the compositions in Table 6a. In Ref.2 and Ex.10. in which no additive 3 (trimethylsilyl terminated phenylmethylsiloxane dimethylsiloxane copolymer) or 4 (ADK STABTM CDA-6) are present. Hence, Example 10 contains no additive 3 or 4 but it does comprise stabilizing additive 8 (light magnesium carbonate). Table 6a. Compositions of Ref 2 and Ex.10 (wt. %). Ingredients Ref.2 Ex.10
Ref.2 and Ex.10 were tested for compression set after having been in contact with PA66-GF25 for 168 hours at 175 °C and the results are depicted in Table 6b below.
Table 6b. Compression set (%) results for cured samples after compression for 168 hours at 175°C in accordance with ASTM D395 – 18 method B. Ref.2 Ex.10 Aluminium 51.7 47.1 It will be
5 is -13.8%, which is lower than the Ref.2 (7.9%). In summary, all ten examples gave results which are dramatically better than the respective reference examples 1 and 2 and indeed all the comparatives. The improvement was dramatic and positively surprising, given failure had been anticipated before conducting the examples in view of the results for the compositions in Table 1. It would seem that there is some form of synergistic effect caused by using magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide or a mixture and such materials are successful in interacting with the species migrating into the silicone elastomer in the composite preventing worsening of compression set and as such maintaining the durability of the silicone in the composite articles despite their physical interactions with the thermoplastics. In a further series of Examples, Examples 11, 12 and 13 correspond to liquid curable silicone elastomer compositions made of silica masterbatches 1 and 2 and containing stabilizing additives 8 (light magnesium carbonate (hydromagnesite, Akrochem), 9 (MagoxTM 98 HR magnesium oxide, Premier Magnesia, LCC), and 10 (magnesium carbonate basic, light, catalog No. AC211070010, Thermo Scientific™). The compositions are shown in Table 7a below. In the case of Ex.11 to 13 in Table 7a, the liquid curable silicone elastomer compositions were prepared using masterbatches to prepare two-part composition: MB1 and MB2, polymer 2, catalyst, additives 1, 2, and 3 and stabilizing additive were blended into a first part, (part A) and masterbatches MB1 and MB2, polymer 2, cross-linker 1, inhibitor, additives 2, 3, and 4 and stabilizing additive were blended into a second part, part B. Once prepared, the two parts were mixed together to homogeneity in a 1:1 weight ratio to yield the liquid curable silicone elastomer compositions which were then cured as indicated above by compression molding directly into a button mold at 171 °C for 20 minutes.
Table 7a: Compositions of Ex.11, 12 and 13 (wt. %) Ingredients Ex.11 Ex.12 Ex.13 Silica Masterbatch 1 84.12 83.13 85.12
ompression set results are provided in Table 7b below. Table 7b: Compression set (%) results for cured samples of Ex.11, 12 and 13 after compression for 168 hours at 175 °C in accordance with ASTM D395 – 18 method B Ex.11 Ex.12 Ex.13
The compression set change of examples 11, 12 and 13 was -24.1%, -15.7%, and -26.4% when in contact with PA66-GF25 which is lower than the defined criteria.
Claims
WHAT IS CLAIMED IS: 1. A silicone-thermoplastic composite article comprising (i) a flame-retardant free thermoplastic article wherein the flame-retardant free thermoplastic article has an available surface, and (ii) a cured silicone elastomer part in direct contact with the available surface of the flame- retardant free thermoplastic article (i), wherein the silicone elastomer part is the cured product of a silicone elastomer composition comprising from 0.25 wt. % to a maximum of 5 wt. % of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof.
2. A silicone-thermoplastic composite article in accordance with claim 1 wherein the flame- retardant free thermoplastic article (i) is selected from a polyamide, polyoxymethylene, polyphenylenesulfide (PPS), polyacetals, polyamide-imides, polypthalamides, polyetherimides, polyetherketone, polyether etherketone, polyether ketone ether ketone, polyoxymethylene(acetal) homopolymer copolymer, syndiotactic polystyrene (sPS), a compatibilized blend of sPS with polyamide; polyesters, polycarbonate (PC), polyethers, maleic anhydride grafted polyphenyleneoxide (PPO), maleic anhydride grafted olefinic elastomers and plastomers, polysulfone, polyethersulfone, polyarylsulfone, polyphenylene ether, polypropylene, polyethylene, aliphatic polyketones (PK) thermoplastic styrene copolymers, polymethyl methacrylate (PMMA), polyoxymethylene (POM).
3. A silicone-thermoplastic composite article in accordance with claim 2 wherein the flame- retardant free thermoplastic article (i) comprises PA6, PA6,6, PA6T/6,6, PBT, PC and PK, especially PA6, PA6,6, PA6T/PA6,6, and PBT and optionally may comprises up to about 25-35 wt. % of glass fibers (GF) as a reinforcement additive.
4. A silicone-thermoplastic composite article in accordance with any preceding claim wherein the stabilizing additive is selected from magnesite (MgCO3), barringtonite (MgCO3.2H2O), nesquihonite (MgCO3.3H2O), lansfordite (MgCO3.5H2O); and one or more magnesium hydroxy carbonates such as pokrovskite (Mg2(CO3)(OH)2.0.5H2O), artinite (Mg2(CO3)(OH)2.3H2O), hydromagnesite (Mg5(CO3)4(OH)2.4H2O), dypingite (Mg5(CO3)4(OH)2.5H2O), giorgiosite (Mg5(CO3)4(OH)2.5-6H2O) and shelkovite (Mg7(CO3)5(OH)4.24H2O) and optionally may comprise one or more metal deactivator(s).
5. A silicone-thermoplastic composite article in accordance with claim 4 wherein the metal deactivator(s) are selected from a diacylhydrazide-based compound, an aminotriazole-based compound, an amino-containing triazine-based compound or a mixture thereof.
6. A silicone-thermoplastic composite article in accordance with any preceding claim wherein in use the silicone elastomer part is sandwiched between two articles at least one of which is a thermoplastic article which is flame-retardant free.
7. A silicone-thermoplastic composite article in accordance with any preceding claim wherein in use the silicone elastomeric part is subjected to mechanical compression and exposed to temperatures of greater than 85oC.
8. A silicone-thermoplastic composite article in accordance with any preceding claim wherein the silicone elastomer part is the cured product of a hydrosilylation reaction curable silicone elastomer composition or a free radical reaction curable silicone elastomer composition.
9. A silicone-thermoplastic composite article in accordance any preceding claim which is an automotive part, cable accessory, electrical part, electronic part, packaging part, construction part, household part or gasket.
10. A silicone-thermoplastic composite article in accordance with claim 9 which is an electrical or electronic connector having a silicone elastomer seal or an electrical module housing optionally with a sealed lid or electronic module housing optionally with a sealed lid, a radiator tank, a valve cover assembly, a sealed headlamp assembly, a potted electronic component or an encapsulated electronic component.
11. A method of fabricating a silicone-thermoplastic composite article in accordance with any preceding claim comprising (a) providing a curable silicone elastomer composition comprising from 0.25 to a maximum of 5 wt. % of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof, (b) curing said curable elastomer composition into a mold, (c) physically engaging the cured silicone elastomer with an available surface of a flame-retardant free thermoplastic article (i) to form a silicone-thermoplastic composite article.
12. A method of fabricating a silicone-thermoplastic composite article in accordance with any one of claims 1 to 8 comprising (a) providing a curable silicone elastomer composition comprising the 0.25 wt. % to a maximum of 5 wt. % of stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof, (b) contacting the curable silicone elastomer composition with an available surface of a flame- retardant free thermoplastic article (i) (c) curing the curable silicone elastomer composition in contact with the available surface of the flame-retardant thermoplastic article, to form a silicone-thermoplastic composite article.
13. A method for fabricating a silicone-thermoplastic composite article, wherein the silicone- thermoplastic composite article comprises (i) a flame-retardant free thermoplastic article, wherein the flame-retardant free thermoplastic article has an available surface; and
(ii) a silicone elastomer part, wherein the silicone elastomer part is physically engaged with the available surface of (i) the flame-retardant free thermoplastic; which method comprises: (1) providing a curable silicone elastomer composition comprising a hydrosilylation reaction curable silicone elastomer composition or a free radical reaction curable silicone elastomer composition, wherein the curable silicone elastomer composition further comprises 0.25 wt. % to a maximum of 5.0 wt. % of a stabilizing additive selected from the group consisting of a magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof; (2) introducing a desired amount of the curable silicone elastomer composition into a mold, (3) curing the curable silicone elastomer composition, thereby forming (ii) the silicone elastomer part; (4) physically engaging (ii) the silicone elastomer seal and the available surface of (i) the flame-retardant free thermoplastic article, thereby forming the silicone-thermoplastic composite article.
14. A method for fabricating a silicone-thermoplastic composite article in accordance with claim 13 wherein the silicone-thermoplastic composite article is an electrical or electronic connector comprising (ia) one or more electrical wires; (ib) an electrical or electronic connector housing comprising a flame-retardant free thermoplastic article, wherein the electrical or electronic connector housing has a first available surface and a second surface opposite the outer surface, wherein the second surface defines a cavity, and the cavity houses the one or more electrical wires (ia) therein; and the silicone elastomer part (ii) is a silicone elastomer seal, wherein the silicone elastomer seal is physically engaged with the first available surface of the electrical or electronic connector housing (ib).
15. A method to maintain the durability of a silicone elastomer part in physical contact with a flame-retardant free thermoplastic which silicone elastomer part in use is subjected to mechanical compression and exposed to temperatures of greater than 85oC comprising the steps of (1’) preparing a curable silicone elastomer composition wherein the curable silicone elastomer composition further comprises 0.25 wt. % to a maximum of 5.0 wt.% of a stabilizing additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof
(2’) introducing a desired amount of the curable silicone elastomer composition into a mold, (3’) curing the curable silicone elastomer composition, thereby forming the silicone elastomer part (ii); (4’) physically engaging the silicone elastomer part (ii) and the available surface of the electrical or electronic connector housing (ib), to form the electrical or electronic connector.
16. Use of from 0.25 wt. % to a maximum of 5.0 wt.% of an additive selected from the group consisting of magnesium carbonates, magnesium hydroxy carbonates, magnesium oxide, and a mixture thereof as a stabilizing additive in a silicone elastomer part in physical contact with a flame- retardant free thermoplastic in a silicone-thermoplastic composite article.
17. Use in accordance with claim 16 wherein the magnesium carbonates and magnesium hydroxy carbonates are selected from MgCO3, MgCO3.2H2O, MgCO3.3H2O, MgCO3.5H2O, Mg2(CO3)(OH)2.0.5H2O, Mg2(CO3)(OH)2.3H2O, Mg5(CO3)4(OH)2.4H2O, Mg5(CO3)4(OH)2.5H2O, Mg5(CO3)4(OH)2.5-6H2O and Mg7(CO3)5(OH)4.24H2O.
18. Use in accordance with claim 16 or 17 which silicone elastomer part in use is subjected to mechanical compression and exposed to a temperature of greater than or equal to 85oC.
19. Use in accordance with claim 16, 17 or 18 wherein the silicone-thermoplastic composite article is an automotive part, cable accessory, electrical part, electronic part, packaging part, construction part, household part or gasket.
20. Use in accordance with claim 16, 17, 18 or 19 wherein the silicone-thermoplastic composite article is an electrical or electronic connector having a silicone elastomer seal or an electrical module housing optionally with a sealed lid or electronic module housing optionally with a sealed lid, a radiator tank, a valve cover assembly, a sealed headlamp assembly, a potted electronic component or an encapsulated electronic component.
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WO (1) | WO2024086140A1 (en) |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3419593A (en) | 1965-05-17 | 1968-12-31 | Dow Corning | Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation |
US3445420A (en) | 1966-06-23 | 1969-05-20 | Dow Corning | Acetylenic inhibited platinum catalyzed organopolysiloxane composition |
US3715334A (en) | 1970-11-27 | 1973-02-06 | Gen Electric | Platinum-vinylsiloxanes |
US3814730A (en) | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
US3989667A (en) | 1974-12-02 | 1976-11-02 | Dow Corning Corporation | Olefinic siloxanes as platinum inhibitors |
US6605734B2 (en) | 2001-12-07 | 2003-08-12 | Dow Corning Corporation | Alkene-platinum-silyl complexes |
US20100144933A1 (en) * | 2006-12-27 | 2010-06-10 | Dow Corning Toray Co., Ltd. | Addition-Reaction-Curable Silicone Rubber Composition and a Molded Article Therefrom |
US20160289416A1 (en) * | 2013-06-27 | 2016-10-06 | Bluestar Silicones France Sas | Hot-vulcanisable polyorganosiloxane compositions for use in particular for the production of electrical wires or cables |
US20170342295A1 (en) * | 2011-01-20 | 2017-11-30 | Dow Corning Toray Co., Ltd. | Use Of Magnesium Compound For Improving Water Resistance Of Cured Silicone Rubber |
US20200255663A1 (en) * | 2017-07-31 | 2020-08-13 | Dow Silicones Corporation | Process and apparatus to make liquid silicone rubber compositions |
US20210002526A1 (en) * | 2018-03-08 | 2021-01-07 | Dow Silicones Corporation | Self-adhesive silicone elastomer |
US20210032470A1 (en) * | 2019-07-30 | 2021-02-04 | Elkem Silicones USA Corp. | Process and a device assembly useful for producing a molded silicone rubber product from liquid silicone rubber composition via injection molding |
-
2023
- 2023-10-17 WO PCT/US2023/035283 patent/WO2024086140A1/en unknown
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3419593A (en) | 1965-05-17 | 1968-12-31 | Dow Corning | Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation |
US3445420A (en) | 1966-06-23 | 1969-05-20 | Dow Corning | Acetylenic inhibited platinum catalyzed organopolysiloxane composition |
US3814730A (en) | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
US3715334A (en) | 1970-11-27 | 1973-02-06 | Gen Electric | Platinum-vinylsiloxanes |
US3989667A (en) | 1974-12-02 | 1976-11-02 | Dow Corning Corporation | Olefinic siloxanes as platinum inhibitors |
US6605734B2 (en) | 2001-12-07 | 2003-08-12 | Dow Corning Corporation | Alkene-platinum-silyl complexes |
US20100144933A1 (en) * | 2006-12-27 | 2010-06-10 | Dow Corning Toray Co., Ltd. | Addition-Reaction-Curable Silicone Rubber Composition and a Molded Article Therefrom |
US20170342295A1 (en) * | 2011-01-20 | 2017-11-30 | Dow Corning Toray Co., Ltd. | Use Of Magnesium Compound For Improving Water Resistance Of Cured Silicone Rubber |
US20160289416A1 (en) * | 2013-06-27 | 2016-10-06 | Bluestar Silicones France Sas | Hot-vulcanisable polyorganosiloxane compositions for use in particular for the production of electrical wires or cables |
US20200255663A1 (en) * | 2017-07-31 | 2020-08-13 | Dow Silicones Corporation | Process and apparatus to make liquid silicone rubber compositions |
US20210002526A1 (en) * | 2018-03-08 | 2021-01-07 | Dow Silicones Corporation | Self-adhesive silicone elastomer |
US20210032470A1 (en) * | 2019-07-30 | 2021-02-04 | Elkem Silicones USA Corp. | Process and a device assembly useful for producing a molded silicone rubber product from liquid silicone rubber composition via injection molding |
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