GB2509128A - Process for improving fire resistance of an organic polymer - Google Patents
Process for improving fire resistance of an organic polymer Download PDFInfo
- Publication number
- GB2509128A GB2509128A GB1223170.0A GB201223170A GB2509128A GB 2509128 A GB2509128 A GB 2509128A GB 201223170 A GB201223170 A GB 201223170A GB 2509128 A GB2509128 A GB 2509128A
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- United Kingdom
- Prior art keywords
- organic polymer
- silane
- process according
- siloxane
- compound
- Prior art date
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title claims abstract description 22
- -1 siloxane compound Chemical class 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- 230000009970 fire resistant effect Effects 0.000 claims abstract description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000003063 flame retardant Substances 0.000 claims description 10
- 229920002050 silicone resin Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 8
- 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 description 7
- 229920003244 diene elastomer Polymers 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- QHGSGZLLHBKSAH-UHFFFAOYSA-N hydridosilicon Chemical compound [SiH] QHGSGZLLHBKSAH-UHFFFAOYSA-N 0.000 claims description 5
- 238000007348 radical reaction Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000002318 adhesion promoter Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims 1
- 239000008187 granular material Substances 0.000 description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 11
- 230000006870 function Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000003141 primary amines Chemical class 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001451 organic peroxides Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DXAQJSDEJGVDQP-UHFFFAOYSA-N 1,7-diaminoheptan-4-yl trimethyl silicate Chemical compound CO[Si](OC)(OC)OC(CCCN)CCCN DXAQJSDEJGVDQP-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- FWTMTMVDOPTMQB-UHFFFAOYSA-N 2-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CC(C)CN FWTMTMVDOPTMQB-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UIJDAGBZCJCLNO-UHFFFAOYSA-N [dimethoxy(methyl)silyl]methyl prop-2-enoate Chemical compound CO[Si](C)(OC)COC(=O)C=C UIJDAGBZCJCLNO-UHFFFAOYSA-N 0.000 description 1
- CDVLARZRMIEPMF-UHFFFAOYSA-N [methoxy(dimethyl)silyl]methyl prop-2-enoate Chemical compound CO[Si](C)(C)COC(=O)C=C CDVLARZRMIEPMF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical group CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- GGRIQDPLLHVRDU-UHFFFAOYSA-M potassium;2-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 GGRIQDPLLHVRDU-UHFFFAOYSA-M 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- 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 process for improving fire resistance of an organic polymer having unsaturated groups comprising addition to the organic polymer silane or siloxane compound being free of phosphorous and containing at least one of the following function: vinyl unsaturation, acrylate, primary, secondary amine, SiH which function will react with the unsaturation of the organic polymer in the presence of radical initiator means. Also disclosed is a fire resistant polymer composition comprising an organic polymer having unsaturated groups and a silane or siloxane compound free of phosphorous and containing at least one of the following function: vinyl unsaturation, acrylate, primary, secondary amine, SiH; and use of the fire resistant composition.
Description
PROCESS FOR IMPROVING THE FIRE RESISTANCE OF AN ORGANIC POLYMER
[0001] The invention is directed towards a process for improving the fire resistance of an organic polymer, a fire resistant polymer composition and the use of a silane or siloxane to improve the fire resistance of a composition.
[0002] It is known that the fire resistance of organic polymers can be enhanced by the addition of compounds able to reduce the flammability or provide other desirable properties in case of fire for example anti-dripping properties. An organic polymer is a polymer which contains carbon/carbon bonds. in the polymer backbone [0003] For example, the paper Thermal degradation behaviours and flame retardancy of PC/ABS with novel silicon-containing flame retardant' by Hanfang Zhong et al. in Fire.
Mater. Vol. 31, 411-423 (2007) describes a novel flame retardant containing silicon, phosphorus and nitrogen synthesised from the reaction of 9,1 0-dihydro-oxa-1 0- phosphaphenanthrene-lO-oxide (DOPO), vinylmethyldimethoxysilane and N-p- (aminoethyl)--aminopropyl methyl dimethoxy silane.
[0004] W0201 1/143930 describes a process foF improving the fire resistance of a thermoplastic or thermoset organic polymer composition, characterised in that an alkoxysilane containing at east one organic nitrogen-containing group and an alkoxysilane or silicone resin containing at least one group selected from phosphonate and phosphinate groups are added to a thermoplastic or thermosetting organic polymer composition and heated in the presence of moisture to cause hydrolysis and siloxane condensation of the alkoxysilane or alkoxysilanes. The alkoxysilanes, or alkoxysilane(s) and silicone resin, of the invention are particularly effective in increasing the lire resistance of polycarbonates and blends of polycarbonate with other resins such as polycarbonate/ABS blends.
[0005] It is desirable to provide a process for improving the fire resistance of an organic polymer containing unsaturated groups by adding to the organic polymer a compound which is free of phosphorous. Phosphorous-containing compounds are sometimes expensive and may have a detrimental effect on the electrical properties of the formed material.
[0006] Therefore, in one of its aspects, the invention provides a process for improving the *r": 30 fire resistance of an organic polymer containing unsaturated groups wherein a silane or ". : siloxane compound is added to the organic polymer said silane or siloxane compound being free of phosphorous and containing at least one of the following function: vinyl unsaturation, acrylate, primary amine, secondary amine, SiH which function will react with * the unsaturations of the organic polymer in the presence of means able to initiate radical * 35 reactions.
[0007] The silane or siloxane compound added to the organic polymer (henceforth referred to as the additional compound) may be a silane containing Si-C bond(s) or a siloxane containing Si-O bond(s). When it is a siloxane it can be a simple siloxane containing only one Si atom or a polysiloxane containing several Si-O-Si bonds especially an organopolysiloxane (silicone). It can be a silicone resin containing T (RSiO,,) and/or Q units (5104,2) where R is especially an aliphatic or aromatic moiety.
[0008] Said organic polymer containing unsaturated groups may be thermoset or thermoplastia It is preferably thermoplastic as thermoset polymers can be degraded in case of heating.
(0009] The organic polymer must contain unsaturated groups able to react with the functional silane or siloxane. Preferably, the organic polymer contains C=C and/or CN unsaturations. Preferably the carbon/carbon unsaturations are not contained in an aromatic moiety such as for example an aromatic ring as those kind of unsaturated groups will not be able to react with silane or siloxane.
(0010] The organic polymer is preferably selected from ABS. SBS and diene elastomer.
ABS (acrylonitrile styrene butadiene) is a thermoplastic terpolymer made by polymerizing styrene and acrylonitrile in the presence of polybutadiene.
(0011] These polymers are elastomeric and improve the mechanical properties of materials made thereof. Similar product is Styrene-Butadiene-Styrene (SBS) -same structure without acrylonitrile.
(0012] As conversion of the polymerization is not 100%, a high amount of double bonds in the polybutadiene of ABS and SBS remain unsaturated.
(0013] In another preferred embodiment, the organic polymer is a diene elastomer. By a diene elastomer we mean a polymer having elastic properties at room temperature, mixing temperature or at the usage temperature, which can be polymerized from a diene monomer Typically, a diene elastomer is a polymer containing at least one ene (carbon-carbon double bond, C=C) having a hydrogen atom on the alpha carbon next to the C=C bond. The diene elastomer can be a natural polymer such as natural rubber or can be a synthetic polymer derived at least in part from a diene.
The organic polymer containing unsaturations can be part of a polymer matrix containing at * least 2 different polymers, for example an ABS/polycarbonate matrix.
(0014] There are several possible ways to initiate radical reactions. The means for initiating radical reactions can be the addition of a radical initiator compound such as, preferably, a peroxide. It can be the application of heat, for example in case of a fire. It can further be formed by ultraviolet radiations or electron beam irradiation.
(0015] The silane or siloxane compound may contain a primary or secondary amino * 35 function. Such amino functions can for example react with unsaturated C=C or or CeC *** functions following Michael's addition.
[0016] The compound containing at least one primary amine group can for example be 3- aminopropyltrimethoxysilane, 3-amino-2-methyl-propyltrimethoxysilane or 3- aminopropyltriethoxysilane, or can be a disiloxane such as bis(3-aminopropyl)-tetramethoxysilane. A compound containing at least one secondary amine group can for S example be N-methyl-3-aminopropyltrimethoxysilane or N-phenyl-3-aminopropyltrimethoxysilane. A compound containing a primary amine group and a secondary amine group can fpr example be N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. The aminoalkylalkoxysilane can alternatively be a dialkoxysilane or monoalkoxysilane. A compound containing at least one primary amine group can for example be 3-aminopropylmethyldimethoxysilane or 3-aminopropylmethyldimethoxysilane [0017] In one preferred embodiment, the compound is a siloxane, more precisely an amino functional silicone resin. Several aminosiloxanes are available for example it can be an aminosiloxane according to US7501473 the content of which being incorporated herein by reference. US7501473 describes an amino functional silicone resin containing aryl functionalities, RR'SiO2 and amine content.
[0018] In other preferred embodiments, the compound is an aminoalkylsilane.
(0019] In other preferred embodiment, the compound is a siloxane or a silane containing an acrylate function, for example an acrylate alkyl silane.
100201 It can include an acrylate-functional alkoxysilane such as acryloxyalkylsilanes for example y-acryloxypropyltrimethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethylmethyldimethoxysilane, acryloxymethyldimethylmethoxysilane, y-acryloxypropylmethyldimethoxysilane or y-acryloxypropyldimethylmethoxysilane.
(0021J In some preferred embodiments, the siloxane compound is a vinyl siloxane or a vinyl silicone resin. Unsaturated functions of the organic polymer may react with unsaturated C=C linkages following a poly-addition reaction, especially in the presence of free radicals generators. For example the added compound can be a linear organopolysiloxane chain comprising pendant vinyl groups, for example hexenyl groups. It can be a silicone resin containing T and/or Q units and some terminal or pendant vinyl * 30 unsaturations.
10022] In some preferred embodiments, the siloxane compound is a siloxane containing SIH function(s). For example the SiH siloxane is dimethylmethyl hydrogen siloxane. SiH functions can react with other unsaturated linkages by the hydrosilylation reaction, in the presence of free radical generators and/or Pt catalysts.
[0023] In still other preferred embodiments, the compound is a mixture of at least 2 different silane or siloxane compounds.
[0024] The invention also provides a fire resistant polymer composition containing a mixture or a reaction product obtained from (1) an organic polymer containing unsaturations and (2) a silane or siloxane compound being free of phosphorous and which contains at least S one of the following function: vinyl unsaturation, acrylate, primary amine, secondary amine, Sift [0025] The fire resistant composition according to the invention can be a physical mixture of an organic polymer containing unsaturations and a silane or siloxane compound. In other preferred embodiments, the composition is a reaction product of an organic polymer containing unsaturations with a silane or siloxane compound.
[0026] Preferably, the silane or siloxane compound (2) is present in an amount ranging from 0.1 to 40% by weight of the composition containing (1) and (2).
[0027] Preferably, the fire resistant polymer composition according to the invention is halogen free. Halogen containing flame retardants have performed well in terms of flame is retardancy properties, processability, cost, etc, however there is an urgent need for halogen-free flame retardants (HFFR) as polymer additives, which comply with environmental regulations, OEM perception, customers requirements, etc. Fire safety is now based on preventing ignition and reducing flame spread through reducing the rate of heat release, as well as on reducing fire toxicity. Flame retardant additives must be safe in what concerns health and environment, must be cost efficient and maintain/improve plastics or rubbers performance.
[0028] The halogenated flame retardant compounds act mostly in the gas phase by a radical mechanism to interrupt the exothermic processes and to suppress combustion.
Examples are the bromine compounds, such as tetrabromobisphenol A, chlorine compounds, halogenated phosphate ester, etc. [0029] In some preferred embodiments, the composition further contains a flame retardant additive. Among the halogen-free flame retardants one can find the metal hydroxides, such as magnesium hydroxide (Mg(OH)2) or aluminium hydroxide (Al(OH)3), which act by heat :. absorbance, i.e. endothermic decomposition into the respective oxides and water when : 30 heated, however they present low flame retardancy efficiency, low thermal stability and significant deterioration of the physical/chemical properties of the polymer matrices. Other ° compounds act mostly on the condensed phase, such as expandable graphite, zinc borate, and nanoclays are other examples of halogen-free flame retardants. Silicon-containing * additives are known to significantly improve the flame retardancy, acting both through char * 35 formation in the condensed phase and by the trapping of active radicals in the vapour * phase. Sulfur-containing salts, such as potassium diphenylsulfone sulfonate (KSS), are effective flame retardant additives for thermoplastics.
[0030] The invention further provides a fire resistant composition wherein the composition further contains pigment and/or filler. The fire resistant composition of the invention can contain additives such as fillers, pigments, dyes, plasticisers, adhesion promoters, coupling agents, antioxidants, impact resistants, hardeners (e.g. for anti-scratch) and/or light S stabilisers.
10031] The composition can further contain an anti-dripping agent such as for example polytetrafluoroethylene to prevent dripping of the material in case of fire.
(0032] In particular the polymer compositions of the invention can contain a reinforcing filler such as silica. The silica is preferably blended with the compound (2), before the compound (2) is added to the organic polymer containing unsaturations. The silica can for example be present at 0.1 or 0.5% by weight up to 40 or 60% by weight of the polymer composition, and can be present at ito 500% based on the total weight of compound (2).
[0033] The invention further extends to the use of a silane or siloxane compound being free of phosphorous and which contains at least one of the following function: vinyl unsaturation, acrylate, primary amine, secondary amine, SiH to improve the fire resistance of an organic polymer containing unsaturations.
[0034] The invention is illustrated by the following examples, in which parts and percentages are by weight.
Prophetic examples
Prophetic example I
[0035] 10% of amino siloxane resin DC3055 will be added to ABS granules and mixed through extrusion process (temperature between 220-290°C). The extrudate will then be cooled down and (re)-pelletized to form modified ABS granules. These granules will then moulded into their end-use shape.
[0036] The granules will be also extruded and injected into UL94-bars for fire resistance evaluation. In the UL-94 test, a flame is applied to a vertically disposed sample of a 120mm x 12mm x 1.6mm. The sample self-extinguishing time will be evaluated by observing the flaming time. One will also observe if the sample exhibits dripping or not. One will also : examine the behaviour of the material according to the cone calorimeter test where a * r 30 radiant heater of conical shape produces a heat flux over the sample under study. The . : smoke density under fire conditions can also be observed.
[0037] During the fire test, the amino groups of amino siloxane resin can further react with the unsaturated bonds of ABS to re-build a network while the product is degraded and hence reduce dripping and fire evolution. The amino groups already reacted during sample * 35 preparation will give additional heat resistance to ABS because they already created a * resistant network based on Si-O-Si bond with ABS polymeric chains.
Prophetic example 2
[00381 20% of acryloxymethyltrimethoxysilane and 3 phr Luperox ® 230 organic peroxide parts will be added to 100 pts ABS granules and will be mixed through extrusion process (between 220-290°C). The extrudate will then be cooled dawn and (re)-pelletized to form modified ABS granules. These granules will then be moulded into their end-use shape.
The granules will also be extruded and injected into UL94-bàrs for fire resistance evaluation.
Prophetic Example 3
[0039] 10% by weight of linear vinyl siloxane DC7690 and 2 phr Luperox @801 organic peroxide will be added to ABS granules and will be mixed through extrusion process (between 220-290°C). The extrudate will then be cooled down and (re)-pelletized to form modified ABS granules. These granules will then be moulded into their end-use shape.
[0040] The granules will also be extruded and will be injected into UL94-bars for fire resistance evaluation.
[0041] During the fire test, the unsaturated bonds can further react with the unsaturated bonds of ABS to re-build a network while the product is degraded and hence reduce dripping and fire evolution. The unsaturated groups already reacted during sample preparation give additional heat resistance to ABS because they already created a resistant network based on Si-O-Si bond with ABS polymeric chains.
Prophetic Example 4
[0042] 25% of dimethyl methyl hydrogen silane DC2-7672 and 3 pbr Luperox @230 organic peroxide will be added to ABS granules and will be mixed through extrusion process (between 220-290°C). The extrudate will be then cooled down and (re)-pelletized to form modified ABS granules. These granules will be moulded into their end-use shape.
[00431 The granules will also be extruded and injected into UL94-bars for fire resistance evaluation.
[00441 During the fire test, the unsaturated bonds can further react with the unsaturated bonds of ABS to re-build a network while the product is degraded and hence reduce dripping and fire evolution. The unsaturated groups already reacted during sample * * preparation give additional heat resistance to ABS because they already created a * r * 30 resistant network based on Si-O-Si bond with ABS polymeric chains. ** * * * * * S.
S 0
S
S
Claims (17)
- CLAIMS1. A process for improving the fire resistance clan organic polymer containing unsaturated groups wherein a silane or siloxane compound is added to the organic polymer said silane or siloxane compound being free of phosphorous and containing at least one of the following function: vinyl unsaturation, acrylate, primary amine, secondary amine, SiH which function wilt react with the unsaturations of the organic polymer in the presence of means able to initiate radical reactions.
- 2. The process according to claim 1 wherein the organic polymer is thermoplastic.
- 3. The process according to claim 1 or 2 wherein the organic polymer contains CC and/or CN unsaturations.
- 4. The process according to claim 2 wherein the organic polymer is selected from ABS, SBS and diene elastomer.
- 5. The process according to any preceding claim, wherein the means able to initiate radical reactions are addition of radical initiator compound preferably a peroxide or application of heat or ultraviolet radiations or electron beam irradiation.
- 6. The process according to any preceding claim, wherein the siloxane compound is an amino functional silicone resin.
- 7. The process according to any preceding claim, wherein the silane compound is an aminoalkylsilane.
- 8. The process according to any preceding claim, wherein the silane compound is an acrylate alkyl silane.
- 9. The process according to any preceding claim, wherein the siloxane compound is a vinyl siloxane or a vinyl silicone resin.
- 10. The process according to any preceding claim, wherein the siloxane compound is a SiH siloxane.
- 11. 11. A fire resistant polymer composition containing a mixture or a reaction product obtained from (1) an organic polymer containing unsaturated groups and (2) a silane or siloxane compound. being free of phosphorous and which contains at least one of the following function: vinyl unsaturation, acrylate, primary amine, secondary amine, * . SiH.
- 12. Afire resistant polymer composition according to claim 11 wherein the silane or siloxane compound (2) is present in an amount ranging from 0.1 to 40% by weight ofthe composition. Is this in description?
- 13. A fire resistant polymer composition according to claim 11 or 12 which is halogen free.
- 14. A fire resistant composition according to any of claims 11 to 13 wherein the composition further contains a flame retardant additive.S
- 15. A fire resistant composition according to any of claims 11 to 14 wherein the composition further contains additives such as fillers, pigments, dyes, plasticisers, adhesion promoters, coupling agents, antioxidants, impact resistants, hardeners and/or light stabilisers.
- 16. The fire resistant composition according to any of claims 11 to 14 wherein the composition further contains an anti-dripping agent preferably polytetrafluoroethylene.
- 17. Use of a silane or siloxane compound being free of phosphorous and which contains at least one of the following function: vinyl unsaturation, acrylate, primary amine, secondary amine, SiH to improve the fire resistance of an organic polymer containing unsaturatio ns. *. .* * * . * . * * * . * S * **5*S** * *
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| GB1223170.0A GB2509128A (en) | 2012-12-20 | 2012-12-20 | Process for improving fire resistance of an organic polymer |
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| GB1223170.0A GB2509128A (en) | 2012-12-20 | 2012-12-20 | Process for improving fire resistance of an organic polymer |
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|---|---|---|---|---|
| GB1460128A (en) * | 1974-06-10 | 1976-12-31 | Dow Corning | Carboxyfunctional silicone containing thermoplastics |
| US4387176A (en) * | 1982-02-04 | 1983-06-07 | General Electric Company | Silicone flame retardants for plastics |
| US5391594A (en) * | 1992-06-29 | 1995-02-21 | Dow Corning Corporation | Method for imparting fire retardancy to organic resins |
| US5508323A (en) * | 1992-06-29 | 1996-04-16 | Dow Corning Corporation | Method for imparting fire retardancy to organic resins |
| WO2005035604A1 (en) * | 2003-10-14 | 2005-04-21 | National Institute Of Advanced Industrial Science And Technology | Flame-retardant abs resin and process for producing the same |
| US20110092660A1 (en) * | 2008-01-15 | 2011-04-21 | Tadashi Okawa | Polyorganosiloxane Containing Methacryloxy Group Or Acryloxy Group And Method For Producing The Same |
| CN102558750A (en) * | 2012-01-29 | 2012-07-11 | 厦门大学 | Organosilicon fire retardant for ABS and preparation method thereof |
| CN102775754A (en) * | 2012-07-25 | 2012-11-14 | 杭州师范大学 | Halogen-free composite flame retardant poly carbonates (PC)/acrylonitrile butadiene styrene copolymers (ABS) alloy and preparation method thereof |
-
2012
- 2012-12-20 GB GB1223170.0A patent/GB2509128A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1460128A (en) * | 1974-06-10 | 1976-12-31 | Dow Corning | Carboxyfunctional silicone containing thermoplastics |
| US4387176A (en) * | 1982-02-04 | 1983-06-07 | General Electric Company | Silicone flame retardants for plastics |
| US5391594A (en) * | 1992-06-29 | 1995-02-21 | Dow Corning Corporation | Method for imparting fire retardancy to organic resins |
| US5508323A (en) * | 1992-06-29 | 1996-04-16 | Dow Corning Corporation | Method for imparting fire retardancy to organic resins |
| WO2005035604A1 (en) * | 2003-10-14 | 2005-04-21 | National Institute Of Advanced Industrial Science And Technology | Flame-retardant abs resin and process for producing the same |
| US20110092660A1 (en) * | 2008-01-15 | 2011-04-21 | Tadashi Okawa | Polyorganosiloxane Containing Methacryloxy Group Or Acryloxy Group And Method For Producing The Same |
| CN102558750A (en) * | 2012-01-29 | 2012-07-11 | 厦门大学 | Organosilicon fire retardant for ABS and preparation method thereof |
| CN102775754A (en) * | 2012-07-25 | 2012-11-14 | 杭州师范大学 | Halogen-free composite flame retardant poly carbonates (PC)/acrylonitrile butadiene styrene copolymers (ABS) alloy and preparation method thereof |
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| GB201223170D0 (en) | 2013-02-06 |
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