WO2015066138A1 - Flame retardant thermoplastic polymer compositions - Google Patents
Flame retardant thermoplastic polymer compositions Download PDFInfo
- Publication number
- WO2015066138A1 WO2015066138A1 PCT/US2014/062838 US2014062838W WO2015066138A1 WO 2015066138 A1 WO2015066138 A1 WO 2015066138A1 US 2014062838 W US2014062838 W US 2014062838W WO 2015066138 A1 WO2015066138 A1 WO 2015066138A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flame retardant
- halogen
- silicone resin
- amino
- polymer composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 90
- 239000003063 flame retardant Substances 0.000 title claims abstract description 51
- 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 title claims abstract description 35
- 229920002050 silicone resin Polymers 0.000 claims abstract description 63
- 229920000620 organic polymer Polymers 0.000 claims abstract description 61
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 61
- 239000012757 flame retardant agent Substances 0.000 claims abstract description 46
- 239000004952 Polyamide Substances 0.000 claims description 30
- 229920002647 polyamide Polymers 0.000 claims description 30
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 239000003365 glass fiber Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 125000000962 organic group Chemical group 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 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 claims description 8
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 150000007974 melamines Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- -1 polysiloxane Polymers 0.000 description 39
- 229920000642 polymer Polymers 0.000 description 21
- 125000003277 amino group Chemical group 0.000 description 15
- 229920002292 Nylon 6 Polymers 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000000454 talc Substances 0.000 description 10
- 229910052623 talc Inorganic materials 0.000 description 10
- 229920006345 thermoplastic polyamide Polymers 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000012744 reinforcing agent Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229920013822 aminosilicone Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical class O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000004103 aminoalkyl group Chemical group 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 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 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000004951 kermel Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical class OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- YKPQUSLRUFLVDA-UHFFFAOYSA-N $l^{2}-azanylmethane Chemical compound [NH]C YKPQUSLRUFLVDA-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000643374 Homo sapiens Serrate RNA effector molecule homolog Proteins 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- 102100035712 Serrate RNA effector molecule homolog Human genes 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 229920003367 Teijinconex Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 229920003655 Vestamid® L Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000005001 aminoaryl group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 101150088657 asR3 gene Proteins 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- 239000004765 teijinconex Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K3/38—Boron-containing compounds
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
Definitions
- This invention relates to flame retardant agents for thermoplastic organic polymer compositions, and to flame retardant thermoplastic polymer compositions containing them.
- the invention is particularly applicable to polyamides, but is also useful for other thermoplastic polymers such as for example polyesters.
- the invention provides a flame retardant thermoplastic polymer composition.
- the composition contains a thermoplastic organic polymer and at least one flame retardant agent.
- the flame retardant agent is an amino-functional silicone resin.
- a composition is typically a mixture of at least two chemically different compounds.
- a thermoplastic organic polymer composition is a composition containing a thermoplastic organic polymer and, usually, other ingredients sometimes called additives.
- the thermoplastic organic polymer typically forms a polymeric matrix.
- the other ingredients or additives may contain, for example, flame retardant agent(s), filler(s), reinforcing agent, mineral powder etc.
- a flame retardant agent is a compound which is able to provide flame retardant properties.
- a flame retardant agent provides flame retardancy properties when added to a composition containing a thermoplastic organic polymer. Flame retardant properties are said to be obtained when the composition containing the flame retardant agent shows increased resistance to burning or other degradation by a flame compared to a composition which does not contain the flame retardant agent.
- a composition containing a flame retardant agent resists longer to a flame than the same composition but not containing the flame retardant agent.
- a flame-retardant composition may contain a thermoplastic polymer usually forming a matrix and one or more flame retardant agent(s).
- a polysiloxane or silicone is a silicon containing compound containing repeating Si-O-Si bonds.
- a silane is a silicon containing compound which does not contain repeating Si-O-Si bonds.
- a polymer is a compound containing repeating units, typically forming one or more chains.
- An organic polymer is a polymer containing repeating C-C bonds.
- An organic polymer is sometimes defined as a polymer in which at least 50% of the atoms in the polymer backbone are carbon atoms.
- a thermoplastic polymer is a polymer which has thermoplastic properties. A thermoplastic polymer allows plastic deformation when it is heated.
- a silicone is typically a material based on a polymer chain containing repeating Si-O-Si bonds.
- a silicone may comprise mono-functional (M), di- functional (D), tri-functional (T) and/or tetra-functional siloxane (Q) unit(s).
- M mono-functional
- D di- functional
- T tri-functional
- Q tetra-functional siloxane
- the Si atom of a M unit is bonded to 1 O atom.
- the Si atom of a D unit is bonded to 2 O atoms.
- the Si atom of a T unit is bonded to 3 O atoms.
- the Si atom of a Q unit is bonded to 4 O atoms.
- a silicone resin contains at least one T unit and/or at least one Q unit.
- a silicone resin contains two or more T units and/or Q units.
- a M unit typically has the formula R 3 S1O1/2.
- a D unit typically has the formula R 2 Si02 2.
- a T unit typically has the formula RS1O 3 /2.
- a Q unit typically has the formula S1O4/2.
- Each R is a substituent (also called a group) linked to the silicon atom. Where the unit contains more than one R, the Rs can be the same or can be different on one silicon atom. Furthermore the Rs can be different on different silicon atoms.
- R is often an organic substituent i.e. a substituent containing at least one C atom, preferably several C atoms forming C-C bonds.
- thermoplastic organic polymer can be formed of one or more polymers.
- one of these polymers forming the thermoplastic organic polymer is polyamide.
- at least 50% by weight based on the total weight of all thermoplastic organic polymers present in the composition is formed of polyamide.
- the thermoplastic organic polymer is essentially formed of polyamide.
- amino- silicone resins are particularly suitable to provide flame retardant properties to polyamide.
- the thermoplastic organic polymer contains polyester.
- preferably at least 50% by weight based on the total weight of thermoplastic organic polymers present in the composition is formed of polyester. More preferably, the thermoplastic organic polymer is essentially formed of polyester.
- the aminosilicone resin is incorporated within the thermoplastic matrix without reaction between the amino functions of the additive and the matrix.
- the thermoplastic matrix is free of reactive unsaturations that could otherwise potentially react with the aminofunctions of the flame retardant agent. It is believed that the amino functions of the flame retardant agent are only susceptible to possibly react in case the composition is exposed to flame.
- a reactive unsaturation is an unsaturation able to react in contrast with an unreactive unsaturation.
- unsaturations contained in aryl groups, for example phenyl have very few reactivity because of their aromatic character. Those unsaturations are thus considered as non reactive unsaturations.
- the polymer(ic) matrix used in the present invention is preferably a polymer, a copolymer or a mixture of polymers which is /are free of reactive unsaturations. If present, the unsaturations of the polymer, copolymer or mixture of polymers are preferably only non reactive unsaturations.
- thermoplastic polymer is free from polymer containing reactive unsaturations.
- thermoplastic polymer is free from ABS (acrylonitrile butadiene styrene), SBS (poly(styrene-butadiene-styrene)) and/or or diene elastomer.
- thermoplastic polymer is free from polyphenylene ester.
- thermoplastic polymer is free of EPDM (ethylene propoylene diene rubber).
- the thermoplastic polymer can be a saturated polymer, substantially free of unsaturations.
- the thermoplastic polymer may be PE (polyester), PA (polyamide), polyolefin like PP (polypropylene) or PE (polyethylene), PC (polycarbonate), PS (polystyrene), PET (polyethylene terephtalate), PBT (polybutylene terephtalate), PMMA (poly(methylmethacrylate)), POM (polyoxymethylene), PEEK (polyether ether ketone), PES (polyether sulfone), PPO (oly(phenylene oxide)).
- PE polyyester
- PA polyamide
- polyolefin like PP polypropylene
- PE polyethylene
- PC polycarbonate
- PS polystyrene
- PET polyethylene terephtalate
- PBT polybutylene terephtalate
- PMMA poly(methylmethacrylate)
- the thermoplastic polymer may be a mixture of polymers or a copolymer.
- Thermoplastic polyamides are widely used for many applications in which the polyamide is shaped, for example by injection moulding, blow moulding or extrusion.
- thermoplastic polyamide compositions are frequently used for casings for electrical equipment or wiring.
- the thermoplastic polyamide composition is required to have a certain level of fire resistance, but polyamides are not inherently flame retardant.
- Flame retardant polyamide compositions have been produced comprising halogen-containing flame retardant agents such as brominated polystyrene, polybromodiphenyl or polybromodiphenyl oxide. Such halogen- containing flame retardant agents may be hazardous to health and there is a need for flame retardant thermoplastic polyamide compositions which do not contain halogen- containing flame retardant agents.
- CN- 102604377- A describes a flame retardant thermoplastic polyamide composition
- a flame retardant thermoplastic polyamide composition comprising 30-90% by weight thermoplastic polyamide resin, 5-40% bromine-containing flame retardant, 0.5-15% auxiliary flame retardant and 0-50% reinforcing material.
- the auxiliary flame retardant comprises zinc borate and organosilicone resin in weight ratio 9: 1 to 1 : 1.
- JP-2004-115582-A describes preparing a flame retardant polyamide composition by kneading 80-99.9% by weight polyamide resin with 0.1-20% liquid silicone.
- JP-2004-115651-A describes a flame retardant polyamide composition comprising a polyamide resin containing aromatic units and a metal borate compound.
- JP-2003-192923-A describes a flame retardant thermoplastic resin composition comprising 20-94.9% by weight thermoplastic resin, 0.1-20% silicone compound containing a vinyl group and 5-60% reinforcement.
- silicone resins are particularly effective as flame retardant agents in halogen-free polyamide compositions and other thermoplastic organic polymer compositions. It is believed an amino silicone compound containing only M and D units will not provide the flame retardancy effect. At least one T and/or at least one Q unit is needed. A linear aminosilicone compound is not appropriate for the present invention.
- a halogen-free flame retardant thermoplastic organic polymer composition according to the invention comprises a thermoplastic organic polymer and is characterised in that the composition contains an amino-functional silicone resin as flame retardant agent
- a flame retardant agent according to one aspect of the invention for a thermoplastic organic polymer composition is characterised in that the flame retardant agent comprises 5 to 90%, preferably 50 to 90%, by weight of an amino-functional silicone resin, from 5 to 30% by weight of an auxiliary flame retardant selected from borate salts, melamine compounds and phosphinate salts, and from 0 to 45% by weight of a mineral powder based on the weight of all flame retardant agents with the total being 100%.
- the invention also includes the use of a flame retardant agent comprising an amino-functional silicone resin for improving the flame retardance of a thermoplastic organic polymer composition.
- the amino group or the amino groups present in the silicone resin is or are usually present in at least one R substituent which R is linked to a silicon atom as explained above.
- R is preferably an amino-substituted alkyl, aryl or aralkyl substituent.
- R is an aminoalkyl substituent.
- the amino-functional silicone resin may comprise siloxane units selected from M units of the formula R 3 S1O1 / 2, D units of the formula R2S1O2 / 2 or R2S1O1 / 2 OZ, T units of the formula RS1O 3/ 2 , RS1O2 / 2 OZ or RSiOi / 2(OZ) 2 , and Q units of the formula S1O4 / 2 , S1O 3/ 2OZ, SiC>2 / 2(OZ)2, or SiOi 2(OZ)3, where each R represents an organic group bonded to silicon or an amino group bonded to silicon and Z represents hydrogen or an alkyl group.
- the amino groups of the silicone resin then are usually present in organic groups R which can be amino-substituted alkyl, aryl or aralkyl groups, for example aminoalkyl groups. At least some of the siloxane units of the silicone resin are T units or Q units.
- the amino functional silicone resin thus has the formula M x D y T z Q w in which x, y, z and w can each be 0-100% in mole percent provided that z+w is different from 0, preferably at least 1%.
- a and/or A' is an alkylene group
- the alkylene group can for example have 1 to 6 carbon atoms.
- R' and /or R" is an alkyl group
- the alkyl group can for example have 1 to 8 carbon atoms, usually 1 to 4 carbon atoms.
- preferred aminoalkyl groups include:
- the amino-substituted organic group can alternatively contain only a secondary amine group, for example -(CH2)3-NH-(C6Hs) or -(CH2)3NH(CH3), or a tertiary amine group, for example -(CH2)3-N-(CH 3 )2
- aminoaryl groups examples include aminophenyl such as 4-aminophenyl.
- preferred aminoaralkyl groups include aminobenzyl groups such as - CH2C6H4-NH2 and -CH(C6H5)NH2.
- the amino-substituted organic group can be present in M, D and/or T siloxane units.
- the amino-functional silicone resin preferably has an amine equivalent weight of 200 to 2000 g/amine nitrogen, more preferably 300 to 1000 g/ amine nitrogen.
- Organic groups R in the amino-functional silicone resin other than amino- substituted organic groups can for example be alkyl and/or alkenyl groups having 1 to 6 carbon atoms and/or aryl or aralkyl groups having 6 to 10 carbon atoms.
- Alkyl groups R bonded to silicon are preferably methyl groups but can for example be ethyl groups.
- Alkenyl groups are not usually present in the amino-functional silicone resin but if present can be vinyl groups.
- amino-functional silicone resins containing aryl groups can be more effective flame retardants for polyamide compositions than amino-functional silicone resins which do not contain aryl groups.
- the amino-functional silicone resin may for example comprise at least 50% by weight aryl groups based on the total weight of organic groups R in the amino-functional silicone resin, more preferably at least 60% aryl groups, and may for example contain 70 or 75 up to 80% or more aryl groups, preferably phenyl groups.
- One preferred type of silicone resin is thus an amino-functional phenyl methyl silicone resin.
- the amino-functional resin used as flame retardant agent may contain other functionalities than the amino functionalities.
- the resin also contains aryl functionalities, for example phenyl functionalities. It is meant that such additional functionalities are present in the resin at positions not directly linked to the aminofunctions. Those aryl functionalities can enhance compatibility with polymeric matrix, and/or the Tg and or thermal resistance.
- the amino-functional silicone resin contains T and/or Q units. It preferably contains T units of the formula RS1O 3/ 2 in combination with M units of the formula R 3 S1O1 / 2 and/or D units of the formula R 2 Si022- Amino-substituted organic groups are usually present in D units.
- Such D units can be (methyl)aminoalkylsiloxane units, for example (methyl)aminopropylsiloxane units NH2(CH2)3(CH3)Si022, (methyl)N- methylaminopropylsiloxane units, CH3NH(CH2)3(CH3)Si022, (methyl)N- phenylaminopropylsiloxane units, C6HsNH(CH2)3(CH3)Si02/2, or (methyl)-N- benzylaminopropylsiloxane units C6H5(CH2)NH(CH2)3(CH3)Si022 ⁇
- the amino- substituted groups can alternatively be present in M units.
- Such M units can be (dimethyl)aminoalkylsiloxy units, for example NH2(CH2)3(CH 3 )2SiOi 2 or aminoalkylsiloxane T units NH2(CH2) 3 SiC>3 / 2.
- Amino groups bonded to silicon can be present in D units such as (methyl)aminosiloxane units (H3C)(NH2)SiC>2/2-
- Aryl groups can be present in D units such as diphenylsiloxane units or methylphenylsiloxane units and/or in T units such as phenylsiloxane T units.
- Aralkyl groups can be present in D units such as for example methylbenzylsiloxane units and/or in T units such as benzylsiloxane T units.
- Alkyl groups can be present in D units such as (methyl)aminoalkylsiloxane units as described above or in (methyl)aminoarylsiloxane or (methyl)aminobenzylsiloxane units, and optionally in methylphenylsiloxane units and/or dimethylsiloxane units, and/or in M units such as trimethylsiloxy units and/or T units such as methylsiloxane units CH 3 S1O 3/ 2.
- the amino-functional silicone resin preferably contains less than 25% by weight hydroxy and/or alkoxy groups, for example 0 to 12% or 0 to 8% by weight combined hydroxy and/or alkoxy groups.
- the amino-functional silicone resin is free of residual alkoxy groups.
- Any hydroxy and/or alkoxy groups can be present in T units for example methylmethoxysilicone units CH3(OCH3)SiC>2/2 , methylhydroxysilicone units CH 3 (HO)SiC>2 / 2 or phenylhydroxysilicone units C6H5(HO)SiC>2/2, or D units for example dimethylmethoxysilicone units (CH 3 )2(CH 3 0)SiOi 2 or in Q units for example ROS1O 3/ 2 where R is alkyl or H .
- the amino-functional silicone resin can be a liquid or solid resin.
- a liquid amino-functional silicone resin can for example have a kinetic viscosity of 200 to 50,000 centiStokes at 25°C.
- a solid resin can be preferred for ease of incorporation into the polymer matrix, which is usually in solid form too before forming the composition.
- the thermoplastic organic polymer composition in which the amino-functional silicone resin flame retardant agent is incorporated comprises a thermoplastic organic polymer and optionally one or more fillers and/or reinforcing agents.
- the thermoplastic organic polymer is often the major component of the thermoplastic organic polymer composition i.e. it forms at least 50% by weight of the total thermoplastic organic polymer composition.
- the thermoplastic organic polymer can for example be a polyamide or alternatively can be a polyester.
- a polyamide is often designated by the term nylon.
- Suitable thermoplastic polyamides include for example polycaprolactam (nylon-6), polyhexamethyleneadipamide (nylon-6,6), polyhexamethylenesebacamide (nylon-6, 10), polytetramethyleneadipamide (nylon-4,6), poly(metaxylylyene adipamide), polyhexamethylenephthalamide, polyhexamethyleneisophthalamide, Polyricin Polyamide 11 derived from vegetable oils: polyundecanolactam (such as Rilsan (trade mark) by Arkema), polyamide 12 (polydodecanolactam such as Vestamid L (trade mark) by Evonik).
- thermoplastic polyamide can contain aromatic moieties, for example polyhexamethyleneisophtalamide (nylon 61) or polyhexamethyleneterephtalamide (nylon 6T), or can be a fully aromatic polyamide such as Kevlar (trade mark) or Nomex (trade mark) from Dupont, Teijinconex, Twaron or Technora (trade marks) from Teijin, Kermel (trade mark) from Kermel or Sepctra from Honeywell.
- the thermoplastic polyamide can be a copolymer such as nylon-6, 66 made from caprolactam, hexamethylenediamine and adipic acid or nylon-66,610 made from hexamethylenediamine, adipic acid and sebacic acid.
- the thermoplastic polyamide can be a blend of any of the above polymers to achieve more balanced set of performances.
- polyesters include polyethylene terephthalate and polybutylene terephthalate, and blends and copolymers thereof.
- the amino-functional silicone resin flame retardant agent can for example be incorporated in the thermoplastic organic polymer composition at 10 to 50% by weight amino-functional silicone resin, preferably 15 to 50%, for example 20 to 40% by weight, based on the weight of the thermoplastic organic polymer.
- Examples of reinforcing agents which can be used in the thermoplastic organic polymer composition include fibrous compounds such as glass fibres, carbon fibres, metal fibres, natural fibres or ceramic fibres.
- Glass fibres can for example be in the form of continuous glass fibres, glass fibres cut to staple fibre length, milled glass fibre or a nonwoven or woven glass fire fabric.
- a fibrous reinforcing agent can for example be present at 0 to 150% by weight based on the weight of the thermoplastic organic polymer.
- glass fibres can be present in a polyamide composition at 10 to 150% by weight based on the weight of the thermoplastic organic polymer, preferably 15-100%, particularly from 15 up to 50 or 60% by weight.
- the glass fibres can be present at 0 to 60% by weight of the composition based on the weight of the organic polymer and the glass fibres.
- fillers which can be used in the thermoplastic organic polymer composition include talc, silica, calcium carbonate, mica, kaolin, titanium oxide, carbon black, metals, ceramic powder, borosilicate and/or clays such as wollastonite. Fillers can for example be present at 0 or 5 up to 50 or 95% by weight based on the weight of the thermoplastic organic polymer.
- the amino-functional silicone resin can be used as the only flame retardant in the thermoplastic organic polymer composition but is most effectively used in combination with an auxiliary flame retardant which can for example be selected from borate salts, melamine compounds and phosphinate salts.
- the amino-functional silicone resin preferably comprises the major proportion by weight of the total flame retardants in the thermoplastic organic polymer composition.
- the amino-functional resin preferably forms at least 50% by weight of the weight of all flame retardant agents present in the composition.
- a suitable flame retardant borate salt is zinc borate such as that sold by U.S. Borax as 'Zinc Borate 500'.
- Zinc borate can for example be used at 1 to 20% by weight based on the thermoplastic organic polymer.
- Melamine cyanurate a hydrogen-bonded complex of melamine and cyanuric acid
- a suitable melamine compound is available for example from BASF as 'Melapur MC 25' .
- Melamine cyanurate can for example be used at 1 to 20% by weight based on the thermoplastic organic polymer.
- Other examples of melamine compounds are melamine phosphates such as melamine polyphosphate.
- An example of a suitable phosphinate salt is the metal phosphinate sold by Clariant as 'Exolit PO-1230' .
- the metal phosphinate can for example be used at 1 to 50% by weight based on the thermoplastic organic polymer, for example 1 to 20%.
- the invention thus includes a halogen-free flame retardant agent for a thermoplastic organic polymer composition, characterised in that the flame retardant agent comprises 50 to 90% by weight of an amino-functional silicone resin, from 5 to 30% by weight of an auxiliary flame retardant selected from borate salts, melamine compounds and phosphinate salts, and from 0 to 45% by weight of a mineral powder, all based on the weight of total of all flame retardant agents.
- the mineral powder can for example be talc.
- the flame retardant agent may contain an intumescent additive such as for example ammonium polyphosphate. No halogen containing compound is added.
- the flame retardant agent is thus halogen- free, that is it contains less than 1 % by weight halogen and preferably has no measurable halogen content.
- the thermoplastic organic polymer composition is halogen-free in the sense that it contains less than 1% by weight halogen.
- the composition is phosphorus free, although in other embodiments a phosphorus compound can be present for a particular purpose, for example a melamine phosphate or metal phosphinate as auxiliary flame retardant or ammonium polyphosphate as an intumescent additive.
- the thermoplastic organic polymer composition can be shaped by moulding, for example by injection moulding, extrusion or blow moulding, to form a variety of products such as casings, containers, profiles or fibres.
- the amino-functional silicone resin, or a flame retardant agent comprising the amino-functional silicone resin can conveniently be incorporated in the thermoplastic organic polymer composition by extrusion, for example in a twin screw extruder. If the amino-functional silicone resin is a liquid, the twin screw extruder may be equipped with a liquid injection line for the silicone compounds and also a side feeder for feeding the thermoplastic organic polymer and any powder form co-additives such as an auxiliary flame retardant or mineral powder.
- thermoplastic organic polymer and co-additives may be physically mixed before introduction to the side feeder. It may be convenient to premix the thermoplastic organic polymer with any fibrous reinforcing agent such as glass fibres before mixing with other ingredients. If the amino-functional silicone resin is a solid, all components of the thermoplastic organic polymer composition may be physically mixed before introduction to the extruder.
- the amino-functional silicone resin, or a flame retardant agent comprising the amino-functional silicone resin can alternatively be incorporated in the thermoplastic organic polymer composition in an internal mixer such as a Brabender Plastograph (Trade Mark) mixer equipped with roller blades, or a Banbury mixer, or on a roll mill.
- the amino-functional silicone resin, or a flame retardant agent comprising the amino- functional silicone resin can be incorporated in the thermoplastic organic polymer composition by extrusion as described above and the extrudate can be pelletized and then moulded in an injection moulding machine.
- Polyamide compositions are widely used for casings for electrical and electronic products and wiring and are required to be flame retardant because of the risk of fire started by an electrical fault.
- the main benchmark test for compositions for such casings is the UL-94 test of Underwriters Laboratories Inc., particularly the Vertical Burning Test. In this test a total of 5 specimens each of length 125mm and width 13mm and of thickness 0.7mm or 1.5 mm or 3.0mm are tested per thickness. Each specimen is mounted with long axis vertical and supported such that its lower end is 10 mm above a Bunsen burner. A blue 20 mm high flame is applied to the center of the lower edge of the specimen for 10 seconds and removed. If burning ceases within 30 seconds, the flame is reapplied for an additional 10 seconds. If the specimen drips, particles are allowed to fall onto a layer of dry absorbent surgical cotton placed 300 mm below.
- the requirements for a UL94 rating of V-0 are that the specimens must not burn with flaming combustion for more than 10 s after application of the test flame.
- the total flaming combustion time must not exceed 50 s for the 5 flame applications.
- the burning and glowing time after the second flame application must not exceed 30 s.
- the specimens must not burn with flaming or glowing combustion up to the holding clamp and must not drip flaming particles that ignite the dry absorbent surgical cotton located 300 mm below.
- the requirements for a UL94 rating of V- 1 are that the specimens must not burn with flaming combustion for more than 30 s after application of the test flame.
- the total flaming combustion time must not exceed 250 s for the 5 flame applications.
- the burning and glowing time after the second flame application must not exceed 60 s.
- the specimens must not burn with flaming or glowing combustion up to the holding clamp and must not drip flaming particles that ignite the dry absorbent surgical cotton located 300 mm below.
- the halogen-free and phosphorus-free flame retardant polyamide compositions of the present invention are capable of achieving a UL94 rating of V-l for specimens of thickness 1.5mm.
- ASR 1 amino-functional silicone resin comprising NH2(CH 2 )3(CH 3 )Si022 D units, diphenylsiloxane D units, phenylsiloxane T units and trimethylsiloxy M units, having an alkoxy content of less than 0.5%, an amine hydrogen equivalent weight of 500 g/mole amine nitrogen, a phenyl content of 64.6% and a viscosity of 3750 centiStokes at 25°C
- ASR2 amino-functional silicone resin comprising NH2(CH2)3(CH3)SiC>2/2 D units, phenylsiloxane T units, diphenylsiloxane D units, trimethylsiloxy M units and dimethylsiloxy D units, having an alkoxy content of 4%, an amine hydrogen equivalent weight of 890 g/ mole amine nitrogen , a phenyl content of 70.0% and a viscosity of 5000 centiStokes at 25°C
- ASR3 amino-functional silicone resin comprising NH2(CH2)3(CH3)SiC>2/2 D units, phenylsiloxane T units and trimethylsiloxy M units, having a viscosity of 2000 centiStokes at 25°C
- compositions were made starting from a masterbatch containing 70% PA-6 and 30% glass fibres, sold by Albis Plastics, as Altech ® PA6 A 2030/109 GF30.
- the Altech polyamide masterbatch was dried at 100°C for 6 hours in an desiccant hot air blowing dryer.
- the dried polyamide was mixed physically with the solid additives zinc borate, talc and melamine cyanurate (if used).
- the solid additives mixed with polyamide were fed to the main inlet of a Brabender co-rotating twin screw extruder of screw diameter D 20mm and L/D 40 equipped with a liquid injection head and when the polymer came out of the die, amino-functional silicone resin was started to be injected.
- the amino-functional silicone resin was heated at 68°C to lower its viscosity and was pumped through a metal piping line kept at 62°C to the injection head in the extruder.
- the total throughput to the extruder was 1.6 kg/h.
- the extruder temperature profile was 260-245-240-240-240°C from hopper to the die section.
- the screw speed was 180 rpm.
- the flame retardant polyamide composition extruded was passed through a water bath for cooling and then pelletized.
- Pelletized material was injected moulded into rectangular bars of dimensions 135 mm x 12.5 mm x 1.5 mm for UL-94 testing. Prior to injection moulding, the polymer pellets were dried again to avoid any degradation due to moisture present in the pellets.
- the sample bars were tested according to the UL-94 Vertical Burning Test as described above. The results are shown in Table 2 below.
- the 30 wt.% glass filled nylon-6 polyamide was blended with talc and extruded with a methoxy-terminated dimethyl, methoxyphenyl siloxane phenyl silsesquioxane resin to form a composition comprising 56% nylon-6, 24% glass fibre, 16% silsesquioxane resin and 4% talc.
- the composition was pelletized and injection moulded into sample bars as described above. The sample bars failed the UL-94 Vertical Burning Test, burning totally up to the holding clamp and ignite the dry absorbent surgical cotton located 300 mm below.
- the 30 wt.% glass filled nylon-6 polyamide was blended with talc, melamine cyanurate and zinc borate and extruded with a mixture of aminopropyltriethoxysilane and a diphenyl methylphenyl silicone resin to form a composition comprising 47.25% nylon-6, 20.25% glass fibre, 15% aminopropyltriethoxysilane, 7.5% diphenyl methylphenyl silicone resin, 4% talc, 5% melamine cyanurate and 1% zinc borate.
- the composition was pelletized and injection moulded into sample bars as described above. The sample bars failed the UL-94 Vertical Burning Test, burning totally up to the holding clamp and ignite the dry absorbent surgical cotton located 300 mm below.
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
The invention provides a flame retardant thermoplastic polymer composition. The composition contains a thermoplastic organic polymer and at least one flame retardant agent. The flame retardant agent is an amino-functional silicone resin.
Description
FLAME RETARDANT THERMOPLASTIC POLYMER COMPOSITIONS
[0001] This invention relates to flame retardant agents for thermoplastic organic polymer compositions, and to flame retardant thermoplastic polymer compositions containing them. The invention is particularly applicable to polyamides, but is also useful for other thermoplastic polymers such as for example polyesters.
[0002] The invention provides a flame retardant thermoplastic polymer composition. The composition contains a thermoplastic organic polymer and at least one flame retardant agent. The flame retardant agent is an amino-functional silicone resin.
[0003] A composition is typically a mixture of at least two chemically different compounds. A thermoplastic organic polymer composition is a composition containing a thermoplastic organic polymer and, usually, other ingredients sometimes called additives. The thermoplastic organic polymer typically forms a polymeric matrix. The other ingredients or additives may contain, for example, flame retardant agent(s), filler(s), reinforcing agent, mineral powder etc.
[0004] A flame retardant agent is a compound which is able to provide flame retardant properties. Typically a flame retardant agent provides flame retardancy properties when added to a composition containing a thermoplastic organic polymer. Flame retardant properties are said to be obtained when the composition containing the flame retardant agent shows increased resistance to burning or other degradation by a flame compared to a composition which does not contain the flame retardant agent. A composition containing a flame retardant agent resists longer to a flame than the same composition but not containing the flame retardant agent. A flame-retardant composition may contain a thermoplastic polymer usually forming a matrix and one or more flame retardant agent(s).
[0005] A polysiloxane or silicone is a silicon containing compound containing repeating Si-O-Si bonds. A silane is a silicon containing compound which does not contain repeating Si-O-Si bonds. A polymer is a compound containing repeating units, typically forming one or more chains. An organic polymer is a polymer
containing repeating C-C bonds. An organic polymer is sometimes defined as a polymer in which at least 50% of the atoms in the polymer backbone are carbon atoms. A thermoplastic polymer is a polymer which has thermoplastic properties. A thermoplastic polymer allows plastic deformation when it is heated.
[0006] A silicone is typically a material based on a polymer chain containing repeating Si-O-Si bonds. A silicone may comprise mono-functional (M), di- functional (D), tri-functional (T) and/or tetra-functional siloxane (Q) unit(s). The Si atom of a M unit is bonded to 1 O atom. The Si atom of a D unit is bonded to 2 O atoms. The Si atom of a T unit is bonded to 3 O atoms. The Si atom of a Q unit is bonded to 4 O atoms.
A silicone resin contains at least one T unit and/or at least one Q unit. Preferably a silicone resin contains two or more T units and/or Q units.
A M unit typically has the formula R3S1O1/2. A D unit typically has the formula R2Si02 2. A T unit typically has the formula RS1O3/2. A Q unit typically has the formula S1O4/2. Each R is a substituent (also called a group) linked to the silicon atom. Where the unit contains more than one R, the Rs can be the same or can be different on one silicon atom. Furthermore the Rs can be different on different silicon atoms. R is often an organic substituent i.e. a substituent containing at least one C atom, preferably several C atoms forming C-C bonds.
[0007] The percentages by weight mentioned in the following description are, unless indicated differently, based on the weight of the total composition i.e. the composition containing the polymer and all other ingredients. The thermoplastic organic polymer can be formed of one or more polymers.
[0008] In one preferred embodiment of the invention, one of these polymers forming the thermoplastic organic polymer is polyamide. Preferably at least 50% by weight based on the total weight of all thermoplastic organic polymers present in the composition, is formed of polyamide. Preferably, the thermoplastic organic polymer is essentially formed of polyamide. We have found that amino- silicone resins are particularly suitable to provide flame retardant properties to polyamide.
[0009] In other preferred embodiments the thermoplastic organic polymer contains polyester. In such preferred embodiments, preferably at least 50% by weight based on the total weight of thermoplastic organic polymers present in the composition, is formed of polyester. More preferably, the thermoplastic organic polymer is essentially formed of polyester.
[0010] It is believed the aminosilicone resin is incorporated within the thermoplastic matrix without reaction between the amino functions of the additive and the matrix. Preferably the thermoplastic matrix is free of reactive unsaturations that could otherwise potentially react with the aminofunctions of the flame retardant agent. It is believed that the amino functions of the flame retardant agent are only susceptible to possibly react in case the composition is exposed to flame.
[0011] A reactive unsaturation is an unsaturation able to react in contrast with an unreactive unsaturation. For example unsaturations contained in aryl groups, for example phenyl, have very few reactivity because of their aromatic character. Those unsaturations are thus considered as non reactive unsaturations. The polymer(ic) matrix used in the present invention is preferably a polymer, a copolymer or a mixture of polymers which is /are free of reactive unsaturations. If present, the unsaturations of the polymer, copolymer or mixture of polymers are preferably only non reactive unsaturations.
[0012] Preferably the thermoplastic polymer is free from polymer containing reactive unsaturations. Preferably the thermoplastic polymer is free from ABS (acrylonitrile butadiene styrene), SBS (poly(styrene-butadiene-styrene)) and/or or diene elastomer. Preferably the thermoplastic polymer is free from polyphenylene ester. Preferably the thermoplastic polymer is free of EPDM (ethylene propoylene diene rubber).
[0013] The thermoplastic polymer can be a saturated polymer, substantially free of unsaturations. The thermoplastic polymer may be PE (polyester), PA (polyamide), polyolefin like PP (polypropylene) or PE (polyethylene), PC (polycarbonate), PS (polystyrene), PET (polyethylene terephtalate), PBT (polybutylene terephtalate),
PMMA (poly(methylmethacrylate)), POM (polyoxymethylene), PEEK (polyether ether ketone), PES (polyether sulfone), PPO (oly(phenylene oxide)).
The thermoplastic polymer may be a mixture of polymers or a copolymer.
[0014] Thermoplastic polyamides are widely used for many applications in which the polyamide is shaped, for example by injection moulding, blow moulding or extrusion. For example, thermoplastic polyamide compositions are frequently used for casings for electrical equipment or wiring. In such use the thermoplastic polyamide composition is required to have a certain level of fire resistance, but polyamides are not inherently flame retardant. Flame retardant polyamide compositions have been produced comprising halogen-containing flame retardant agents such as brominated polystyrene, polybromodiphenyl or polybromodiphenyl oxide. Such halogen- containing flame retardant agents may be hazardous to health and there is a need for flame retardant thermoplastic polyamide compositions which do not contain halogen- containing flame retardant agents.
[0015] CN- 102604377- A describes a flame retardant thermoplastic polyamide composition comprising 30-90% by weight thermoplastic polyamide resin, 5-40% bromine-containing flame retardant, 0.5-15% auxiliary flame retardant and 0-50% reinforcing material. The auxiliary flame retardant comprises zinc borate and organosilicone resin in weight ratio 9: 1 to 1 : 1.
[0016] JP-2004-115582-A describes preparing a flame retardant polyamide composition by kneading 80-99.9% by weight polyamide resin with 0.1-20% liquid silicone. JP-2004-115651-A describes a flame retardant polyamide composition comprising a polyamide resin containing aromatic units and a metal borate compound. JP-2003-192923-A describes a flame retardant thermoplastic resin composition comprising 20-94.9% by weight thermoplastic resin, 0.1-20% silicone compound containing a vinyl group and 5-60% reinforcement.
[0017] We have found according to the invention that certain silicone resins are particularly effective as flame retardant agents in halogen-free polyamide compositions and other thermoplastic organic polymer compositions. It is believed an
amino silicone compound containing only M and D units will not provide the flame retardancy effect. At least one T and/or at least one Q unit is needed. A linear aminosilicone compound is not appropriate for the present invention.
[0018] A halogen-free flame retardant thermoplastic organic polymer composition according to the invention comprises a thermoplastic organic polymer and is characterised in that the composition contains an amino-functional silicone resin as flame retardant agent
[0019] A flame retardant agent according to one aspect of the invention for a thermoplastic organic polymer composition is characterised in that the flame retardant agent comprises 5 to 90%, preferably 50 to 90%, by weight of an amino-functional silicone resin, from 5 to 30% by weight of an auxiliary flame retardant selected from borate salts, melamine compounds and phosphinate salts, and from 0 to 45% by weight of a mineral powder based on the weight of all flame retardant agents with the total being 100%.
[0020] The invention also includes the use of a flame retardant agent comprising an amino-functional silicone resin for improving the flame retardance of a thermoplastic organic polymer composition.
[0021] The amino group or the amino groups present in the silicone resin is or are usually present in at least one R substituent which R is linked to a silicon atom as explained above. R is preferably an amino-substituted alkyl, aryl or aralkyl substituent. For example R is an aminoalkyl substituent.
[0022] The amino-functional silicone resin may comprise siloxane units selected from M units of the formula R3S1O1/2, D units of the formula R2S1O2/2 or R2S1O1/2 OZ, T units of the formula RS1O3/2 , RS1O2/2 OZ or RSiOi/2(OZ)2, and Q units of the formula S1O4/2 , S1O3/2OZ, SiC>2/2(OZ)2, or SiOi 2(OZ)3, where each R represents an organic group bonded to silicon or an amino group bonded to silicon and Z represents hydrogen or an alkyl group. The amino groups of the silicone resin then are usually present in organic groups R which can be amino-substituted alkyl, aryl or aralkyl groups, for example aminoalkyl groups. At least some of the siloxane units of the
silicone resin are T units or Q units. The amino functional silicone resin thus has the formula Mx DyTzQw in which x, y, z and w can each be 0-100% in mole percent provided that z+w is different from 0, preferably at least 1%.
[0023] The amino-substituted organic group can for example be of the formula R'- (N(R")-A')q-N(R")-A- wherein A and A' are each independently a linear or branched alkylene, arylene or aralkylene group having 1 to 10 carbon atoms and optionally containing an ether linkage; q = 0-4; R' is hydrogen or an alkyl, hydroxyalkyl, aryl or aralkyl group having 1 to 10 carbon atoms; and each R" independently is hydrogen or an alkyl, hydroxyalkyl, aryl or aralkyl group having 1 to 10 carbon atoms. Where A and/or A' is an alkylene group, the alkylene group can for example have 1 to 6 carbon atoms. Where R' and /or R" is an alkyl group, the alkyl group can for example have 1 to 8 carbon atoms, usually 1 to 4 carbon atoms. For example, the amino-substituted organic group can contain a primary aminoalkyl group in which R' and R" are both hydrogen; q = 0 or 1; and A and A' (if present) each contain 2 to 4 carbon atoms. Examples of preferred aminoalkyl groups include:
-(CH2)3NH2, -(CH2)4NH2, -(CH2)3NH(CH2)2NH2, -CH2CH(CH3)CH2NH(CH2)2NH2, -(CH2)3NHCH2CH2NH(CH2)2NH2, -CH2CH(CH3)CH2NH(CH2)3NH2, -CH2NH2, -(CH2) NH(CH2)4NH2 and -(CH2) 0(CH2)2NH2. Many of these groups contain both primary and secondary amine groups. The amino-substituted organic group can alternatively contain only a secondary amine group, for example -(CH2)3-NH-(C6Hs) or -(CH2)3NH(CH3), or a tertiary amine group, for example -(CH2)3-N-(CH3)2
Examples of preferred aminoaryl groups include aminophenyl such as 4-aminophenyl. Examples of preferred aminoaralkyl groups include aminobenzyl groups such as - CH2C6H4-NH2 and -CH(C6H5)NH2. The amino-substituted organic group can be present in M, D and/or T siloxane units.
[0024] The amino-functional silicone resin preferably has an amine equivalent weight of 200 to 2000 g/amine nitrogen, more preferably 300 to 1000 g/ amine nitrogen.
[0025] Organic groups R in the amino-functional silicone resin other than amino- substituted organic groups can for example be alkyl and/or alkenyl groups having 1 to 6 carbon atoms and/or aryl or aralkyl groups having 6 to 10 carbon atoms. Alkyl groups R bonded to silicon are preferably methyl groups but can for example be ethyl groups. Alkenyl groups are not usually present in the amino-functional silicone resin but if present can be vinyl groups.
[0026] We have found that amino-functional silicone resins containing aryl groups, for example phenyl groups, can be more effective flame retardants for polyamide compositions than amino-functional silicone resins which do not contain aryl groups. The amino-functional silicone resin may for example comprise at least 50% by weight aryl groups based on the total weight of organic groups R in the amino-functional silicone resin, more preferably at least 60% aryl groups, and may for example contain 70 or 75 up to 80% or more aryl groups, preferably phenyl groups. One preferred type of silicone resin is thus an amino-functional phenyl methyl silicone resin.
[0027] The amino-functional resin used as flame retardant agent may contain other functionalities than the amino functionalities. Preferably, the resin also contains aryl functionalities, for example phenyl functionalities. It is meant that such additional functionalities are present in the resin at positions not directly linked to the aminofunctions. Those aryl functionalities can enhance compatibility with polymeric matrix, and/or the Tg and or thermal resistance.
[0028] The amino-functional silicone resin contains T and/or Q units. It preferably contains T units of the formula RS1O3/2 in combination with M units of the formula R3S1O1/2 and/or D units of the formula R2Si022- Amino-substituted organic groups are usually present in D units. Such D units can be (methyl)aminoalkylsiloxane units, for example (methyl)aminopropylsiloxane units NH2(CH2)3(CH3)Si022, (methyl)N- methylaminopropylsiloxane units, CH3NH(CH2)3(CH3)Si022, (methyl)N- phenylaminopropylsiloxane units, C6HsNH(CH2)3(CH3)Si02/2, or (methyl)-N- benzylaminopropylsiloxane units C6H5(CH2)NH(CH2)3(CH3)Si022 · The amino- substituted groups can alternatively be present in M units. Such M units can be
(dimethyl)aminoalkylsiloxy units, for example NH2(CH2)3(CH3)2SiOi 2 or aminoalkylsiloxane T units NH2(CH2)3SiC>3/2. Amino groups bonded to silicon can be present in D units such as (methyl)aminosiloxane units (H3C)(NH2)SiC>2/2- Aryl groups can be present in D units such as diphenylsiloxane units or methylphenylsiloxane units and/or in T units such as phenylsiloxane T units. Aralkyl groups can be present in D units such as for example methylbenzylsiloxane units and/or in T units such as benzylsiloxane T units. Alkyl groups can be present in D units such as (methyl)aminoalkylsiloxane units as described above or in (methyl)aminoarylsiloxane or (methyl)aminobenzylsiloxane units, and optionally in methylphenylsiloxane units and/or dimethylsiloxane units, and/or in M units such as trimethylsiloxy units and/or T units such as methylsiloxane units CH3S1O3/2.
[0029] The amino-functional silicone resin preferably contains less than 25% by weight hydroxy and/or alkoxy groups, for example 0 to 12% or 0 to 8% by weight combined hydroxy and/or alkoxy groups. Preferably the amino-functional silicone resin is free of residual alkoxy groups. Any hydroxy and/or alkoxy groups can be present in T units for example methylmethoxysilicone units CH3(OCH3)SiC>2/2 , methylhydroxysilicone units CH3(HO)SiC>2/2 or phenylhydroxysilicone units C6H5(HO)SiC>2/2, or D units for example dimethylmethoxysilicone units (CH3)2(CH30)SiOi 2 or in Q units for example ROS1O3/2 where R is alkyl or H .
[0030] The amino-functional silicone resin can be a liquid or solid resin. A liquid amino-functional silicone resin can for example have a kinetic viscosity of 200 to 50,000 centiStokes at 25°C. A solid resin can be preferred for ease of incorporation into the polymer matrix, which is usually in solid form too before forming the composition.
[0031] The thermoplastic organic polymer composition in which the amino-functional silicone resin flame retardant agent is incorporated comprises a thermoplastic organic polymer and optionally one or more fillers and/or reinforcing agents. The thermoplastic organic polymer is often the major component of the thermoplastic organic polymer composition i.e. it forms at least 50% by weight of the total
thermoplastic organic polymer composition. The thermoplastic organic polymer can for example be a polyamide or alternatively can be a polyester. A polyamide is often designated by the term nylon.
[0032] Suitable thermoplastic polyamides include for example polycaprolactam (nylon-6), polyhexamethyleneadipamide (nylon-6,6), polyhexamethylenesebacamide (nylon-6, 10), polytetramethyleneadipamide (nylon-4,6), poly(metaxylylyene adipamide), polyhexamethylenephthalamide, polyhexamethyleneisophthalamide, Polyricin Polyamide 11 derived from vegetable oils: polyundecanolactam (such as Rilsan (trade mark) by Arkema), polyamide 12 (polydodecanolactam such as Vestamid L (trade mark) by Evonik). Alternatively the thermoplastic polyamide can contain aromatic moieties, for example polyhexamethyleneisophtalamide (nylon 61) or polyhexamethyleneterephtalamide (nylon 6T), or can be a fully aromatic polyamide such as Kevlar (trade mark) or Nomex (trade mark) from Dupont, Teijinconex, Twaron or Technora (trade marks) from Teijin, Kermel (trade mark) from Kermel or Sepctra from Honeywell. The thermoplastic polyamide can be a copolymer such as nylon-6, 66 made from caprolactam, hexamethylenediamine and adipic acid or nylon-66,610 made from hexamethylenediamine, adipic acid and sebacic acid. The thermoplastic polyamide can be a blend of any of the above polymers to achieve more balanced set of performances.
[0033] Examples of suitable polyesters include polyethylene terephthalate and polybutylene terephthalate, and blends and copolymers thereof.
[0034] The amino-functional silicone resin flame retardant agent can for example be incorporated in the thermoplastic organic polymer composition at 10 to 50% by weight amino-functional silicone resin, preferably 15 to 50%, for example 20 to 40% by weight, based on the weight of the thermoplastic organic polymer.
[0035] Examples of reinforcing agents which can be used in the thermoplastic organic polymer composition include fibrous compounds such as glass fibres, carbon fibres, metal fibres, natural fibres or ceramic fibres. Glass fibres can for example be in the form of continuous glass fibres, glass fibres cut to staple fibre length, milled glass
fibre or a nonwoven or woven glass fire fabric. A fibrous reinforcing agent can for example be present at 0 to 150% by weight based on the weight of the thermoplastic organic polymer. For example glass fibres can be present in a polyamide composition at 10 to 150% by weight based on the weight of the thermoplastic organic polymer, preferably 15-100%, particularly from 15 up to 50 or 60% by weight. For example, the glass fibres can be present at 0 to 60% by weight of the composition based on the weight of the organic polymer and the glass fibres.
[0036] Examples of fillers which can be used in the thermoplastic organic polymer composition include talc, silica, calcium carbonate, mica, kaolin, titanium oxide, carbon black, metals, ceramic powder, borosilicate and/or clays such as wollastonite. Fillers can for example be present at 0 or 5 up to 50 or 95% by weight based on the weight of the thermoplastic organic polymer.
[0037] The amino-functional silicone resin can be used as the only flame retardant in the thermoplastic organic polymer composition but is most effectively used in combination with an auxiliary flame retardant which can for example be selected from borate salts, melamine compounds and phosphinate salts. The amino-functional silicone resin preferably comprises the major proportion by weight of the total flame retardants in the thermoplastic organic polymer composition. The amino-functional resin preferably forms at least 50% by weight of the weight of all flame retardant agents present in the composition.
[0038] An example of a suitable flame retardant borate salt is zinc borate such as that sold by U.S. Borax as 'Zinc Borate 500'. Zinc borate can for example be used at 1 to 20% by weight based on the thermoplastic organic polymer.
[0039] Melamine cyanurate, a hydrogen-bonded complex of melamine and cyanuric acid, is one example of a suitable melamine compound and is available for example from BASF as 'Melapur MC 25' . Melamine cyanurate can for example be used at 1 to 20% by weight based on the thermoplastic organic polymer. Other examples of melamine compounds are melamine phosphates such as melamine polyphosphate.
[0040] An example of a suitable phosphinate salt is the metal phosphinate sold by Clariant as 'Exolit PO-1230' . The metal phosphinate can for example be used at 1 to 50% by weight based on the thermoplastic organic polymer, for example 1 to 20%.
[0041] The invention thus includes a halogen-free flame retardant agent for a thermoplastic organic polymer composition, characterised in that the flame retardant agent comprises 50 to 90% by weight of an amino-functional silicone resin, from 5 to 30% by weight of an auxiliary flame retardant selected from borate salts, melamine compounds and phosphinate salts, and from 0 to 45% by weight of a mineral powder, all based on the weight of total of all flame retardant agents. The mineral powder can for example be talc. The flame retardant agent may contain an intumescent additive such as for example ammonium polyphosphate. No halogen containing compound is added.
[0042] The flame retardant agent is thus halogen- free, that is it contains less than 1 % by weight halogen and preferably has no measurable halogen content. Similarly the thermoplastic organic polymer composition is halogen-free in the sense that it contains less than 1% by weight halogen. In one preferred embodiment the composition is phosphorus free, although in other embodiments a phosphorus compound can be present for a particular purpose, for example a melamine phosphate or metal phosphinate as auxiliary flame retardant or ammonium polyphosphate as an intumescent additive.
[0043] The thermoplastic organic polymer composition can be shaped by moulding, for example by injection moulding, extrusion or blow moulding, to form a variety of products such as casings, containers, profiles or fibres. The amino-functional silicone resin, or a flame retardant agent comprising the amino-functional silicone resin, can conveniently be incorporated in the thermoplastic organic polymer composition by extrusion, for example in a twin screw extruder. If the amino-functional silicone resin is a liquid, the twin screw extruder may be equipped with a liquid injection line for the silicone compounds and also a side feeder for feeding the thermoplastic organic polymer and any powder form co-additives such as an auxiliary flame retardant or
mineral powder. The thermoplastic organic polymer and co-additives may be physically mixed before introduction to the side feeder. It may be convenient to premix the thermoplastic organic polymer with any fibrous reinforcing agent such as glass fibres before mixing with other ingredients. If the amino-functional silicone resin is a solid, all components of the thermoplastic organic polymer composition may be physically mixed before introduction to the extruder. The amino-functional silicone resin, or a flame retardant agent comprising the amino-functional silicone resin, can alternatively be incorporated in the thermoplastic organic polymer composition in an internal mixer such as a Brabender Plastograph (Trade Mark) mixer equipped with roller blades, or a Banbury mixer, or on a roll mill. When forming injection moulded articles from the thermoplastic organic polymer composition, the amino-functional silicone resin, or a flame retardant agent comprising the amino- functional silicone resin, can be incorporated in the thermoplastic organic polymer composition by extrusion as described above and the extrudate can be pelletized and then moulded in an injection moulding machine.
[0044] Polyamide compositions, particularly compositions based on nylon-6 or nylon- 6, 6, are widely used for casings for electrical and electronic products and wiring and are required to be flame retardant because of the risk of fire started by an electrical fault. The main benchmark test for compositions for such casings is the UL-94 test of Underwriters Laboratories Inc., particularly the Vertical Burning Test. In this test a total of 5 specimens each of length 125mm and width 13mm and of thickness 0.7mm or 1.5 mm or 3.0mm are tested per thickness. Each specimen is mounted with long axis vertical and supported such that its lower end is 10 mm above a Bunsen burner. A blue 20 mm high flame is applied to the center of the lower edge of the specimen for 10 seconds and removed. If burning ceases within 30 seconds, the flame is reapplied for an additional 10 seconds. If the specimen drips, particles are allowed to fall onto a layer of dry absorbent surgical cotton placed 300 mm below.
[0045] The requirements for a UL94 rating of V-0 are that the specimens must not burn with flaming combustion for more than 10 s after application of the test flame.
The total flaming combustion time must not exceed 50 s for the 5 flame applications. The burning and glowing time after the second flame application must not exceed 30 s. The specimens must not burn with flaming or glowing combustion up to the holding clamp and must not drip flaming particles that ignite the dry absorbent surgical cotton located 300 mm below. The requirements for a UL94 rating of V- 1 are that the specimens must not burn with flaming combustion for more than 30 s after application of the test flame. The total flaming combustion time must not exceed 250 s for the 5 flame applications. The burning and glowing time after the second flame application must not exceed 60 s. The specimens must not burn with flaming or glowing combustion up to the holding clamp and must not drip flaming particles that ignite the dry absorbent surgical cotton located 300 mm below. The halogen-free and phosphorus-free flame retardant polyamide compositions of the present invention are capable of achieving a UL94 rating of V-l for specimens of thickness 1.5mm.
[0046] The invention is illustrated by the following Examples, in which parts and percentages are by weight.
Examples 1 to 18
[0047] Polyamide compositions were prepared from the following materials in the proportions shown in Table 1 below
PA-6 nylon-6
GF glass fibre
ASR 1 amino-functional silicone resin comprising NH2(CH2)3(CH3)Si022 D units, diphenylsiloxane D units, phenylsiloxane T units and trimethylsiloxy M units, having an alkoxy content of less than 0.5%, an amine hydrogen equivalent weight of 500 g/mole amine nitrogen, a phenyl content of 64.6% and a viscosity of 3750 centiStokes at 25°C
ASR2 amino-functional silicone resin comprising NH2(CH2)3(CH3)SiC>2/2 D units, phenylsiloxane T units, diphenylsiloxane D units, trimethylsiloxy M units and dimethylsiloxy D units, having an alkoxy content of 4%, an
amine hydrogen equivalent weight of 890 g/ mole amine nitrogen , a phenyl content of 70.0% and a viscosity of 5000 centiStokes at 25°C ASR3 amino-functional silicone resin comprising NH2(CH2)3(CH3)SiC>2/2 D units, phenylsiloxane T units and trimethylsiloxy M units, having a viscosity of 2000 centiStokes at 25°C
Talc talc from Imifabi sold as HTP Ultra 5 talc
ZB US Borax Zinc Borate 500
MC MC 25 melamine cyanurate
Table 1
[0049] The flame retardant polyamide composition extruded was passed through a water bath for cooling and then pelletized. Pelletized material was injected moulded into rectangular bars of dimensions 135 mm x 12.5 mm x 1.5 mm for UL-94 testing. Prior to injection moulding, the polymer pellets were dried again to avoid any degradation due to moisture present in the pellets. The sample bars were tested according to the UL-94 Vertical Burning Test as described above. The results are shown in Table 2 below.
Table 2
Comparative Example CI
[0051] The 30 wt.% glass filled nylon-6 polyamide was extruded and injection moulded into sample bars as described above. The sample bars failed the UL-94 Vertical Burning Test, burning totally up to the holding clamp and ignite the dry absorbent surgical cotton located 300 mm below.
Comparative Example C2
[0052] The 30 wt.% glass filled nylon-6 polyamide was blended with talc and extruded with a methoxy-terminated dimethyl, methoxyphenyl siloxane phenyl silsesquioxane resin to form a composition comprising 56% nylon-6, 24% glass fibre, 16% silsesquioxane resin and 4% talc. The composition was pelletized and injection moulded into sample bars as described above. The sample bars failed the UL-94 Vertical Burning Test, burning totally up to the holding clamp and ignite the dry absorbent surgical cotton located 300 mm below.
[0053] Comparison of Comparative Example C2 with the Examples of the invention indicates that the presence of amino groups in the silicone resin is essential for effective flame retardancy of the polyamide.
Comparative Example C3
[0054] The 30 wt.% glass filled nylon-6 polyamide was blended with talc, melamine cyanurate and zinc borate and extruded with a mixture of aminopropyltriethoxysilane and a diphenyl methylphenyl silicone resin to form a composition comprising 47.25% nylon-6, 20.25% glass fibre, 15% aminopropyltriethoxysilane, 7.5% diphenyl methylphenyl silicone resin, 4% talc, 5% melamine cyanurate and 1% zinc borate. The composition was pelletized and injection moulded into sample bars as described above. The sample bars failed the UL-94 Vertical Burning Test, burning totally up to the holding clamp and ignite the dry absorbent surgical cotton located 300 mm below.
[0055] Comparison of Comparative Example C3 with the Examples of the invention such as Examples 9, 17 and 18 indicates that the presence of amino groups in the
silicone resin is essential for effective flame retardancy of the polyamide, and that a mixture of an aminosilicone and a phenyl silicone resin is not effective as a flame retardant for polyamide.
Claims
1. A halogen-free flame retardant thermoplastic polymer composition comprising a thermoplastic organic polymer, characterised in that the composition contains an amino-functional silicone resin as flame retardant agent.
2. A halogen-free flame retardant thermoplastic polymer composition according to Claim 1, characterised in that the composition contains from 10 to 50% by weight, based on the weight of thermoplastic organic polymer, of the amino- functional silicone resin.
3. A halogen- free flame retardant thermoplastic polymer composition according to Claim 1 or Claim 2 characterised in that the amino-functional silicone resin contains aryl groups.
4. A halogen-free flame retardant thermoplastic polymer composition according to Claim 3 characterised in that the silicone resin is an amino-functional phenyl methyl silicone resin.
5. A halogen- free flame retardant thermoplastic polymer composition according to Claim 3 or Claim 4 characterised in that at least 50% by weight of the organic groups bonded to the silicon atoms of the silicone resin are aryl groups.
6. A halogen-free flame retardant thermoplastic polymer composition according to any of Claims 1 to 5 characterised in that the amino-functional silicone resin contains T units.
7. A halogen-free flame retardant thermoplastic polymer composition according to any of Claims 1 to 6 characterised in that the amine equivalent weight of the amino-functional silicone resin is from 300 to 1000 grams per mole amine nitrogen.
8. A halogen-free flame retardant thermoplastic polymer composition according to any of Claims 1 to 7 characterised in that the amino-functional silicone resin is present at 20 to 40% by weight based on the weight of thermoplastic organic polymer.
9. A halogen-free flame retardant thermoplastic polymer composition according to any of Claims 1 to 8 characterised in that the composition contains 10 to 50% by weight glass fibres based on the weight of thermoplastic organic polymer.
10. A halogen- free flame retardant thermoplastic polymer composition according to any of Claims 1 to 9 characterised in that the amino-functional silicone resin forms 50 to 100% of the total flame retardant agent(s) present(s) in the thermoplastic polymer composition.
11. A halogen- free flame retardant thermoplastic polymer composition according to any of Claims 1 to 10 characterised in that the thermoplastic organic polymer is a polyamide.
12. A halogen- free flame retardant thermoplastic polymer composition according to any of Claims 1 to 10 characterised in that the thermoplastic organic polymer is a polyester.
13. A halogen-free flame retardant agent for a thermoplastic organic polymer composition, characterised in that the flame retardant agent comprises 5 to 90% by weight of an amino-functional silicone resin, from 5 to 30% by weight, of an auxiliary flame retardant selected from borate salts, melamine compounds and phosphinate salts, and from 0 to 45% by weight of a mineral powder all based on the weight of the total of flame retardant agents.
14. A halogen-free flame retardant agent according to Claim 13, characterised in that the auxiliary flame retardant comprises zinc borate.
15. A halogen- free flame retardant agent according to Claim 13 or Claim 14, characterised in that the auxiliary flame retardant comprises melamine cyanurate.
16. A halogen- free flame retardant agent according to any of Claims 13 to 15, characterised in that the auxiliary flame retardant comprises melamine polyphosphate.
17. A halogen-free flame retardant agent according to any of Claims 13 to 16, characterised in that the auxiliary flame retardant comprises a metal phosphinate.
18. Use of a flame retardant agent comprising an amino-functional silicone resin for improving the flame retardancy of a thermoplastic organic polymer composition.
A process for improving the flame retardancy of a thermoplastic organic polymer composition wherein an aminofunctional silicone resin is incorporated in the thermoplastic organic polymer composition as flame retardant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361896919P | 2013-10-29 | 2013-10-29 | |
| US61/896,919 | 2013-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015066138A1 true WO2015066138A1 (en) | 2015-05-07 |
Family
ID=53005055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2014/062838 WO2015066138A1 (en) | 2013-10-29 | 2014-10-29 | Flame retardant thermoplastic polymer compositions |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TW201527424A (en) |
| WO (1) | WO2015066138A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3176218A1 (en) * | 2015-12-04 | 2017-06-07 | Samsung Electronics Co., Ltd. | Polymer composition, electronic device and method of manufacturing the same |
| WO2020025350A1 (en) * | 2018-08-03 | 2020-02-06 | Dsm Ip Assets B.V. | Fiber reinforced polyamide composition and molded part made thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302961A (en) * | 1999-04-23 | 2000-10-31 | Sumitomo Dow Ltd | Flame-retardant polycarbonate resin composition |
| US20040242768A1 (en) * | 2003-06-02 | 2004-12-02 | Butts Matthew David | Silicone based flame retardant systems for textiles |
| US20060205868A1 (en) * | 2003-07-16 | 2006-09-14 | Glenn Gordon | Coating compositions containg aminofunctional silicone resins |
| CN101671568A (en) * | 2009-09-06 | 2010-03-17 | 青岛科技大学 | Phosphorus-contained organic silicon resin fire retardant and preparation method thereof |
| US20110275743A1 (en) * | 2009-07-17 | 2011-11-10 | Toray Industries, Inc. | Flame-retardant thermoplastic resin composition and molded article |
-
2014
- 2014-10-29 WO PCT/US2014/062838 patent/WO2015066138A1/en active Application Filing
- 2014-10-29 TW TW103137468A patent/TW201527424A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302961A (en) * | 1999-04-23 | 2000-10-31 | Sumitomo Dow Ltd | Flame-retardant polycarbonate resin composition |
| US20040242768A1 (en) * | 2003-06-02 | 2004-12-02 | Butts Matthew David | Silicone based flame retardant systems for textiles |
| US20060205868A1 (en) * | 2003-07-16 | 2006-09-14 | Glenn Gordon | Coating compositions containg aminofunctional silicone resins |
| US20110275743A1 (en) * | 2009-07-17 | 2011-11-10 | Toray Industries, Inc. | Flame-retardant thermoplastic resin composition and molded article |
| CN101671568A (en) * | 2009-09-06 | 2010-03-17 | 青岛科技大学 | Phosphorus-contained organic silicon resin fire retardant and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3176218A1 (en) * | 2015-12-04 | 2017-06-07 | Samsung Electronics Co., Ltd. | Polymer composition, electronic device and method of manufacturing the same |
| KR20170065850A (en) * | 2015-12-04 | 2017-06-14 | 삼성전자주식회사 | Polymer composition, electronic device and method for producing of the same |
| CN106883600A (en) * | 2015-12-04 | 2017-06-23 | 三星电子株式会社 | Polymer composition, electronic equipment and its manufacture method |
| US10450458B2 (en) | 2015-12-04 | 2019-10-22 | Samsung Electronics Co., Ltd. | Polymer composition, electronic device and method of manufacturing the same |
| KR102506408B1 (en) * | 2015-12-04 | 2023-03-07 | 삼성전자주식회사 | Polymer composition, electronic device and method for producing of the same |
| WO2020025350A1 (en) * | 2018-08-03 | 2020-02-06 | Dsm Ip Assets B.V. | Fiber reinforced polyamide composition and molded part made thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201527424A (en) | 2015-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8188172B2 (en) | Polyester compositions, method of manufacture, and uses thereof | |
| CN1997699B (en) | Halogen-free flame retardant polyamide composition with improved electrical properties | |
| CN107250267B (en) | Corrosion resistant flame retardant formulations for thermoplastic polymers | |
| CN1980988B (en) | Halogen-free flame retardant polyamide composition with improved electrical and flammability properties | |
| JP4267945B2 (en) | Flame retardant resin composition | |
| WO2002028953A1 (en) | Halogen-free flame retarder composition and flame retardant polyamide composition | |
| KR101928259B1 (en) | Flame retardant polymer composition | |
| WO2016157098A1 (en) | Flame retardant composition, methods of manufacture thereof and articles comprising the same | |
| CN102618023A (en) | Flame-proofed polyamide molding materials and the use thereof | |
| KR102711533B1 (en) | Flame retardant mixture | |
| EP3347418A1 (en) | Flame retardant resin composition | |
| CN1902275B (en) | Flame retardant composition based on thermoplastic matrix | |
| KR20130092411A (en) | Polymer compositions containing oxazine-based alkoxysilanes | |
| JP2015523444A (en) | Flame retardant polymer composition and molded article containing the same | |
| EP3480255A1 (en) | Thermoplastic resin composition and molded body obtained by molding same | |
| EP2593496A1 (en) | Polymer compositions containing alkoxysilanes | |
| WO2010023155A2 (en) | Flame retardant compositions with polymeric dispersing agents | |
| WO2015066138A1 (en) | Flame retardant thermoplastic polymer compositions | |
| EP3221401A1 (en) | Flame retardant, reinforced polyamide-poly(phenylene ether) composition | |
| JP4307882B2 (en) | Flame retardant polyamide resin composition | |
| KR20130132004A (en) | Halogen-free flame retardant polyester resin composition with good mechanical properties and molded article thereof | |
| JPH03100064A (en) | Flame retardant thermoplastic compound and its manufacturing method | |
| JP2010248351A (en) | Flame retardant thermoplastic polyester resin composition | |
| KR20130115981A (en) | Polymer compositions containing alkoxysilanes | |
| JP2024513441A (en) | Flame retardant-stabilizer combinations for thermoplastic polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14857695 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 14857695 Country of ref document: EP Kind code of ref document: A1 |