US20150322262A1 - Article comprising poly(phenylene ether)-polysiloxane copolymer composition - Google Patents
Article comprising poly(phenylene ether)-polysiloxane copolymer composition Download PDFInfo
- Publication number
- US20150322262A1 US20150322262A1 US14/270,478 US201414270478A US2015322262A1 US 20150322262 A1 US20150322262 A1 US 20150322262A1 US 201414270478 A US201414270478 A US 201414270478A US 2015322262 A1 US2015322262 A1 US 2015322262A1
- Authority
- US
- United States
- Prior art keywords
- poly
- phenylene ether
- weight percent
- block copolymer
- polysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 poly(phenylene ether) Polymers 0.000 title claims abstract description 372
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 197
- 239000000203 mixture Substances 0.000 title claims abstract description 149
- 229920001400 block copolymer Polymers 0.000 claims abstract description 147
- 239000003063 flame retardant Substances 0.000 claims abstract description 54
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 50
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 36
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims description 48
- 239000004793 Polystyrene Substances 0.000 claims description 27
- 229920002223 polystyrene Polymers 0.000 claims description 27
- 150000001993 dienes Chemical class 0.000 claims description 23
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 19
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 claims description 18
- 239000004609 Impact Modifier Substances 0.000 claims description 14
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 14
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 14
- 239000011324 bead Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- 229920006030 multiblock copolymer Polymers 0.000 claims description 9
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 claims description 9
- 229910052618 mica group Inorganic materials 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 29
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 25
- 125000001183 hydrocarbyl group Chemical group 0.000 description 24
- 239000013032 Hydrocarbon resin Substances 0.000 description 21
- 229920006270 hydrocarbon resin Polymers 0.000 description 21
- 229920000428 triblock copolymer Polymers 0.000 description 19
- 0 *OC1=C(C)C(C)=C(*)C(C)=C1C Chemical compound *OC1=C(C)C(C)=C(*)C(C)=C1C 0.000 description 18
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 229910052736 halogen Inorganic materials 0.000 description 16
- 150000002367 halogens Chemical class 0.000 description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 11
- 229920000578 graft copolymer Polymers 0.000 description 11
- 229920001519 homopolymer Polymers 0.000 description 11
- NNVKEOMPDSKFGZ-UHFFFAOYSA-N COC1=C(C)C=C(C)C=C1C Chemical compound COC1=C(C)C=C(C)C=C1C NNVKEOMPDSKFGZ-UHFFFAOYSA-N 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 description 9
- 150000004692 metal hydroxides Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 150000003505 terpenes Chemical class 0.000 description 9
- 235000007586 terpenes Nutrition 0.000 description 9
- OBKUVRMDPCXRMC-UHFFFAOYSA-N COC1=CC=C(CCC[Si](C)(C)O[Si](C)(C)CCCC2=CC(OC)=C(OC)C=C2)C=C1CO Chemical compound COC1=CC=C(CCC[Si](C)(C)O[Si](C)(C)CCCC2=CC(OC)=C(OC)C=C2)C=C1CO OBKUVRMDPCXRMC-UHFFFAOYSA-N 0.000 description 8
- 229920002633 Kraton (polymer) Polymers 0.000 description 8
- 229920000877 Melamine resin Polymers 0.000 description 8
- 125000006267 biphenyl group Chemical group 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 8
- 229920000388 Polyphosphate Polymers 0.000 description 7
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920005669 high impact polystyrene Polymers 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 239000001205 polyphosphate Substances 0.000 description 7
- 235000011176 polyphosphates Nutrition 0.000 description 7
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 229920000359 diblock copolymer Polymers 0.000 description 6
- 239000004797 high-impact polystyrene Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000005027 hydroxyaryl group Chemical group 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000010445 mica Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical group NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 3
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical group CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 3
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000007706 flame test Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical group OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 3
- 229920002627 poly(phosphazenes) Polymers 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 150000003097 polyterpenes Chemical class 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KPTMGJRRIXXKKW-UHFFFAOYSA-N 2,3,5-trimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical group O1C2=C(C)C(C)=C1C=C2C KPTMGJRRIXXKKW-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GFNZJAUVJCGWLW-UHFFFAOYSA-N [H]C1=C([H])C(C)=C(OC)C(C)=C1[H] Chemical compound [H]C1=C([H])C(C)=C(OC)C(C)=C1[H] GFNZJAUVJCGWLW-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 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 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- SMSKIVCCLIQXFD-UHFFFAOYSA-N 1-tert-butyl-3-ethenylbenzene Chemical compound CC(C)(C)C1=CC=CC(C=C)=C1 SMSKIVCCLIQXFD-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical class ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- 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
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- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- 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
- C08K3/40—Glass
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- 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
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- Poly(phenylene ether) is a type of plastic known for its excellent water resistance, dimensional stability, and inherent flame retardancy. Properties such as strength, stiffness, chemical resistance, and heat resistance can be tailored by blending it with various other plastics in order to meet the requirements of a wide variety of consumer and industrial products, for example, plumbing fixtures, electrical boxes, automotive parts, and insulation for wire and cable.
- poly(phenylene ether)-based compositions require high flame retardancy.
- Examples include fuser holders for electrophotographic copiers, fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes.
- Poly(phenylene ether) is inherently flame retardant, but it is often blended with other components, such as impact modifiers and flow promoters, that reduce the flame retardancy of the resulting composition even as they improve its processing and mechanical properties. So, flame retardant additives are often required for blends of poly(phenylene ether)s with these other components.
- V-0 flammability rating of plastic Materials, UL 94.
- This V-0 rating can be difficult to achieve in a poly(phenylene ether) composition, even when flame retardant concentration is increased, and concentrations of flammable components are decreased. And when the V-0 rating is achievable, it often comes at the expense of diminished heat resistance and diminished stiffness.
- One embodiment is an article comprising a composition, wherein the article is selected from the group consisting of fuser holders for electrophotographic copiers, fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes; wherein the composition comprises 0.5 to 85 weight percent of a poly(phenylene ether)-polysiloxane copolymer comprising a poly(phenylene ether)-polysiloxane block copolymer, a poly(phenylene ether)-polysiloxane graft copolymer, or a combination thereof; 5 to 25 weight percent of a flame retardant comprising an organophosphate ester, a phosphazene, or a combination thereof; and 10 to 35 weight percent of a reinforcing filler; wherein all weight percent values are based on the total weight of the composition; provided that when the article is a fuser holder, the composition comprises 2 to 10 weight percent of a poly(phenylene ether)-
- parts also referred to herein as “articles” fabricated from a composition containing specific amounts of a poly(phenylene ether)-polysiloxane copolymer, a flame retardant, and a reinforcing filler exhibit a UL 94 V-0 rating while maintaining high heat resistance and stiffness.
- the high heat resistance is manifested as a heat deflection temperature of 110 to 180° C., specifically 130 to 170° C., determined according to ASTM D 648-07 using 6.4 millimeter thick bars, an edgewise test direction, a support span of 100 millimeters (Method B), a stress of 1.82 megapascals, a deflection of 0.25 millimeters at reading, and a heating rate of 2° C./minute.
- the high stiffness is manifested as a flexural modulus of 3,500 to 7,000 megapascals, specifically 4,500 to 6,500 megapascals, determined at 23° C.
- the composition exhibits high melt flow, which facilitates injection molding of parts.
- the high melt flow can be objectively manifested as a melt volume flow rate of 10 to 30 cubic centimeters per 10 minutes, specifically 10 to 25 cubic centimeters per 10 minutes, determined according to ASTM D 1238-04 at 300° C. using a load of 5 kilograms, automatic timing (Procedure B), a capillary diameter of 2.0955 millimeters, and a capillary length of 8.00 millimeters.
- Examples of articles benefiting from the flame retardancy, heat resistance, and stiffness of the composition include fuser holders for electrophotographic copiers (including fuser gates, fuser covers, and fuser frames), fan blades (including blades in fans employed in computer and telecommunication equipment such as personal computers, servers, routers, and base stations; blades in fans employed in business equipment such as printers, copiers, faxes, and projectors; blades in fans employed in electrical appliances such as refrigerators, freezers, washing machines and driers, microwave ovens, dishwashers, air conditioners, and audiovisual equipment; and blades in fans used in industrial equipment, including robots), battery parts for hybrid and electric vehicles (including battery cases, battery module cases, battery terminal blocks, battery spacers, and battery trays), parts for automotive kinetic energy recovery systems (including battery module cases and capacitor cases), and electric vehicle junction boxes.
- electrophotographic copiers including fuser gates, fuser covers, and fuser frames
- fan blades including blades in fans employed in computer and telecommunication equipment such as personal computers, servers,
- the composition comprises a poly(phenylene ether)-polysiloxane copolymer that comprises a poly(phenylene ether)-polysiloxane block copolymer, a poly(phenylene ether)-polysiloxane graft copolymer, or a combination thereof.
- the composition comprises a poly(phenylene ether)-polysiloxane copolymer.
- the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block and a polysiloxane block.
- poly(phenylene ether)-polysiloxane block copolymers include diblock copolymers comprising one poly(phenylene ether) block and one polysiloxane block; triblock copolymers comprising two poly(phenylene ether) blocks and one polysiloxane block, or one poly(phenylene ether) block and two polysiloxane blocks; and multiblock copolymers comprising at least two poly(phenylene ether) blocks and at least two polysiloxane blocks.
- Poly(phenylene ether)-polysiloxane diblock and triblock copolymers can be synthesized by oxidative polymerization of a mixture of monohydric phenol and hydroxyaryl-terminated polysiloxane. This oxidative polymerization produces a poly(phenylene ether)-polysiloxane block copolymer reaction product that comprises poly(phenylene ether)-polysiloxane block copolymer as the desired product and poly(phenylene ether) as a by-product.
- This poly(phenylene ether) present in the reaction product is sometimes referred to herein as the “first poly(phenylene ether)” to distinguish it from a “second poly(phenylene ether)” that is optionally present in the composition and not derived from the poly(phenylene ether)-polysiloxane block copolymer reaction product. It is unnecessary to separate the first poly(phenylene ether) from the poly(phenylene ether)-polysiloxane block copolymer.
- the poly(phenylene ether)-polysiloxane block copolymer can therefore be incorporated into the present composition as the poly(phenylene ether)-polysiloxane block copolymer reaction product that comprises the first poly(phenylene ether) in addition to the poly(phenylene ether)-polysiloxane block copolymer.
- the poly(phenylene ether)-polysiloxane block copolymer is synthesized by oxidative polymerization of a mixture of monohydric phenol and hydroxyaryl-terminated polysiloxane
- the poly(phenylene ether) block is a polymerization product of the monohydric phenol.
- the monohydric phenol has the structure
- poly(phenylene ether) block comprises phenylene ether repeat units having the structure
- each Z 1 is independently unsubstituted or substituted C 1 -C 12 hydrocarbylthio, unsubstituted or substituted C 1 -C 12 hydrocarbyloxy, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; and each Z 2 is independently hydrogen, unsubstituted or substituted C 1 -C 12 hydrocarbylthio, unsubstituted or substituted C 1 -C 12 hydrocarbyloxy, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl.
- hydrocarbyl refers to a residue that contains only carbon and hydrogen.
- the residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
- the hydrocarbyl residue when described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue.
- the hydrocarbyl residue when described as substituted, can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or it can contain heteroatoms within the backbone of the hydrocarbyl residue.
- Z 1 of the phenylene ether repeat unit can be a di-n-butylaminomethyl group formed by reaction of a terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.
- the monohydric phenol comprises 2,6-dimethylphenol, 2,3,6-trimethylphenol, or a combination thereof
- the poly(phenylene ether) block comprises, respectfully, 2,6-dimethyl-1,4-phenylene ether repeat units, that is, repeat units having the structure
- the polysiloxane block is a residue of the hydroxyaryl-terminated polysiloxane.
- the polysiloxane block comprises repeat units having the structure
- each occurrence of R 1 and R 2 is independently hydrogen or C 1 -C 12 hydrocarbyl; and the polysiloxane block further comprises a terminal unit having the structure
- the polysiloxane repeat units comprise dimethylsiloxane (—Si(CH 3 ) 2 O—) units.
- the polysiloxane block has the structure
- n 20 to 60.
- the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- n 30 to 60.
- the hydroxyaryl-terminated polysiloxane comprises at least one hydroxyaryl terminal group.
- the hydroxyaryl-terminated polysiloxane has a single hydroxyaryl terminal group, in which case a poly(phenylene ether)-polysiloxane diblock copolymer is formed.
- the hydroxyaryl-terminated polysiloxane has two hydroxyaryl terminal groups, in which case in which case poly(phenylene ether)-polysiloxane diblock copolymer and/or poly(phenylene ether)-polysiloxane-poly(phenylene ether) triblock copolymer are formed. It is also possible for the hydroxyaryl-terminated polysiloxane to have a branched structure that allows three or more hydroxyaryl terminal groups and the formation of corresponding branched block copolymers.
- the monohydric phenol is 2,6-dimethylphenol
- the hydroxyaryl-terminated polysiloxane is a eugenol-capped polydimethylsiloxane comprising 35 to 60 dimethylsiloxane units
- the oxidative copolymerization is conducted with a reaction time of 170 to 220 minutes
- the hydroxyaryl-terminated polysiloxane constitutes 2 to 7 weight percent of the combined weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane.
- the hydroxyaryl-terminated polysiloxane comprises 20 to 80 siloxane repeat units, specifically 25 to 70 siloxane repeat units, more specifically 30 to 60 siloxane repeat units, still more specifically 35 to 50 siloxane repeat units, yet more specifically 40 to 50 siloxane repeat units.
- the number of siloxane repeat units in the polysiloxane block is essentially unaffected by the copolymerization and isolation conditions, and it is therefore equivalent to the number of siloxane repeat units in the hydroxyaryl-terminated polysiloxane starting material.
- the average number of siloxane repeat units per hydroxyaryl-terminated polysiloxane molecule can be determined by nuclear magnetic resonance (NMR) methods that compare the intensities of signals associated with the siloxane repeat units to those associated with the hydroxyaryl terminal groups.
- NMR nuclear magnetic resonance
- the hydroxyaryl-terminated polysiloxane is a eugenol-capped polydimethylsiloxane
- the poly(phenylene ether)-polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units.
- the reaction product can have a weight average molecular weight of 30,000 to 150,000 atomic mass units, specifically 35,000 to 120,000 atomic mass units, more specifically 40,000 to 90,000 atomic mass units, even more specifically 45,000 to 70,000 atomic mass units.
- the poly(phenylene ether)-polysiloxane block copolymer reaction product has a number average molecular weight of 10,000 to 50,000 atomic mass units, specifically 10,000 to 30,000 atomic mass units, more specifically 14,000 to 24,000 atomic mass units.
- the poly(phenylene ether)-polysiloxane block copolymer reaction product has an intrinsic viscosity of at least 0.3 deciliter per gram, as measured by Ubbelohde viscometer at 25° C. in chloroform. In some embodiments, the intrinsic viscosity is 0.3 to 0.5 deciliter per gram, specifically 0.31 to 0.5 deciliter per gram, more specifically 0.35 to 0.47 deciliter per gram.
- the term “2,6-dimethylphenoxy” refers to a monovalent group and does not encompass divalent 2,6-dimethyl-1,4-phenylene ether groups.
- incorporation of the hydroxyaryl-terminated polysiloxane into block copolymer will reduce the concentration of phenylene ether “tail” groups.
- the monohydric phenol consists of 2,6-dimethylphenol, and the reaction product of comprises less than or equal to 0.4 weight percent, specifically 0.1 to 0.4 weight percent, of 2,6-dimethylphenoxy groups, based on the weight of the reaction product.
- the low concentration of 2,6-dimethylphenoxy tail end groups is an indication that the reaction product comprises a reduced concentration of the 2,6-dimethylphenol homopolymer and an increased concentration of the desired poly(phenylene ether)-polysiloxane block copolymer.
- the poly(phenylene ether)-polysiloxane block copolymer reaction product can further include groups derived from a diphenoquinone, which is itself an oxidation product of the monohydric phenol.
- a diphenoquinone which is itself an oxidation product of the monohydric phenol.
- the diphenoquinone is 3,3′,5,5′-tetramethyl-4,4′-diphenoquinone.
- the diphenoquinone is typically incorporated into the “tail” end of a head-to-tail poly(phenylene ether) as the corresponding biphenyl group.
- the terminal biphenyl group can become an internal biphenyl group in the first poly(phenylene ether) chain.
- the monohydric phenol consists of 2,6-dimethylphenol
- the reaction product comprises 0.1 to 2.0 weight percent, and specifically 1.1 to 2.0 weight percent, of 2,6-dimethyl-4-(3,5-dimethyl-4-hydroxyphenyl)-phenoxy (“biphenyl”) groups.
- the biphenyl groups are present only in bifunctional (head-to-head or hydroxyl-diterminated) structure.
- the low concentration of biphenyl group is an indication that the reaction product comprises a reduced concentration of such bifunctional 2,6-dimethylphenol homopolymer and an increased concentration of the desired poly(phenylene ether)-polysiloxane block copolymer.
- the poly(phenylene ether)-polysiloxane block copolymer content of a poly(phenylene ether)-polysiloxane block copolymer reaction product can be estimated by nuclear magnetic resonance spectroscopy (NMR).
- the reaction product can be approximated as a mixture of head-to-tail poly(phenylene ether) homopolymer, head-to-head poly(phenylene ether) homopolymer (incorporating a biphenyl group), and poly(phenylene ether)-polysiloxane-poly(phenylene ether) triblock copolymer.
- Nuclear magnetic resonance analysis of the mixture can be used to determine the relative concentrations of “head groups” having the structure
- the concentration of poly(phenylene ether)-polysiloxane-poly(phenylene ether) triblock copolymer (PSP) can then be calculated as
- the poly(phenylene ether)-polysiloxane block copolymer reaction product incorporates greater than 75 weight percent, of the hydroxyaryl-terminated polysiloxane starting material into the poly(phenylene ether)-polysiloxane block copolymer.
- the amount of the hydroxyaryl-terminated polysiloxane incorporated into the poly(phenylene ether)-polysiloxane block copolymer can be at least 80 weight percent, more specifically at least 85 weight percent, still more specifically at least 90 weight percent, yet more specifically at least 95 weight percent.
- a polyesterification method can be used to form the poly(phenylene ether)-polysiloxane block copolymer.
- the product is a multiblock copolymer comprising at least two poly(phenylene ether) blocks and at least two polysiloxane blocks.
- the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether)-polysiloxane multiblock copolymer that is the product of copolymerizing a hydroxy-diterminated poly(phenylene ether), a hydroxyaryl-diterminated polysiloxane, and an aromatic diacid chloride.
- the hydroxy-diterminated poly(phenylene ether) can have the structure
- each occurrence of Q 1 is independent selected from the group consisting of halogen, unsubstituted or substituted C 1 -C 12 hydrocarbylthio, unsubstituted or substituted C 1 -C 12 hydrocarbyloxy, unsubstituted or substituted C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q 2 is independently selected from the group consisting of hydrogen, halogen, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen
- each occurrence of R 5 and R 6 is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbylthio, unsubstituted or substituted C 1 -C 12 hydrocarbyloxy, unsubstituted or substituted C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; z is 0 or 1; and Y has a structure selected from the group consisting of
- each occurrence of R 7 -R 10 is independently hydrogen or C 1 -C 12 hydrocarbyl.
- the hydroxy-diterminated poly(phenylene ether) has the structure
- each occurrence of Q 3 is independently methyl or di-n-butylaminomethyl; and each occurrence of a and b is independently 0 to about 100, provided that the sum of a and b is 3 to 100. In some embodiments, the sum of a and b is 4 to 30.
- the aromatic diacid chloride used in the polyesterification method can be, for example, terephthaloyl chloride, isophthaloyl chloride, 4,4′-biphenyldicarbonyl chloride, 3,3′-biphenyldicarbonyl chloride, 3,4′-biphenyldicarbonyl chloride, 4,4′-oxybis(benzoyl chloride), 3,3′-oxybis(benzoyl chloride), 3,4′-oxybis(benzoyl chloride), 4,4′-sulfonylbis(benzoyl chloride), 3,3′-sulfonylbis(benzoyl chloride), 3,4′-sulfonylbis(benzoyl chloride), naphthalene-2,6-dicarbonyl chloride, or a mixture thereof.
- the aromatic diacid chloride comprises terephthaloyl chloride.
- the poly(phenylene ether)-polysiloxane multiblock copolymer when the poly(phenylene ether)-polysiloxane multiblock copolymer is prepared by the polyesterification method, it comprises at least two poly(phenylene ether) blocks and at least two polysiloxane blocks. However, it can contain many more of each type of block. For example, in some embodiments, the poly(phenylene ether)-polysiloxane multiblock copolymer comprises about 5 to about 25 poly(phenylene ether) blocks and about 10 to about 30 polysiloxane blocks.
- the poly(phenylene ether)-polysiloxane copolymer can include a poly(phenylene ether)-polysiloxane graft copolymer.
- a poly(phenylene ether)-polysiloxane graft copolymer comprises a poly(phenylene ether) backbone and at least one polysiloxane graft at an internal (not terminal) phenylene ether unit of the poly(phenylene ether) backbone.
- Poly(phenylene ether)-polysiloxane graft copolymers can be prepared by oxidative copolymerization of a monohydric phenol, as defined above, and a phenol-polysiloxane macromer having the structure
- R 11 is halogen, unsubstituted or substituted C 1 -C 12 hydrocarbylthio, unsubstituted or substituted C 1 -C 12 hydrocarbyloxy, unsubstituted or substituted C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl;
- R 12 is hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbylthio, unsubstituted or substituted C 1 -C 12 hydrocarbyloxy, unsubstituted or substituted C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that
- the monohydric phenol is 2,6-dimethylphenol
- R 11 is methyl
- R 12 is hydrogen
- R 13 is trimethylene (—CH 2 —CH 2 —CH 2 —)
- each occurrence of R 14 is methyl
- R 15 is methyl
- m is 20 to 60.
- the molar ratio of monohydric phenol to phenol-polysiloxane macromere is 10:1 to 1000:1, specifically 20:1 to 100:1 during the oxidative copolymerization.
- the weight percent siloxane in the poly(phenylene ether)-polysiloxane graft copolymer is 0.5 to 10 weight percent, specifically 1 to 8 weight percent. Additional details relating to poly(phenylene ether)-polysiloxane graft copolymers prepared by oxidative copolymerization can be found in U.S. Pat. No. 5,281,686 to Blohm et al. Poly(phenylene ether)-polysiloxane graft copolymers can also be prepared by redistribution of a poly(phenylene ether) in the presence of a hydroxyaryl-terminated polysiloxane. This procedure is described in U.S. Pat. No. 5,596,048 to Blohm et al.
- the composition can comprise a mixture of a poly(phenylene ether)-polysiloxane block copolymer and a poly(phenylene ether)-polysiloxane graft copolymer.
- the composition comprises 0.025 to 5 weight percent of polysiloxane covalently bound in the poly(phenylene ether)-polysiloxane copolymer.
- the poly(phenylene ether)-polysiloxane copolymer contributes 0.025 to 5 weight percent of polysiloxane to the composition as a whole.
- the covalently bound polysiloxane amount is 0.025 to 2 weight percent, specifically 0.05 to 1 weight percent, based on the total weight of the composition. In other embodiments, the covalently bound polysiloxane amount is 1 to 6 weight percent, specifically 2 to 4 weight percent, based on the total weight of the composition.
- the polysiloxane content of the composition consists essentially of polysiloxane that has been incorporated into the poly(phenylene ether)-polysiloxane copolymer.
- the poly(phenylene ether)-polysiloxane copolymer comprises 1 to 8 weight percent siloxane repeat units and 12 to 99 weight percent phenylene ether repeat units, based on the total weight of the poly(phenylene ether)-polysiloxane copolymer.
- the amount of siloxane repeat units can be 2 to 7 weight percent, specifically 3 to 6 weight percent, more specifically 4 to 5 weight percent; and the amount of phenylene ether repeat units can be 93 to 98 weight percent, specifically 94 to 97 weight percent, more specifically 95 to 96 weight percent.
- the poly(phenylene ether)-polysiloxane copolymer can include relatively small amounts of very low molecular weight species.
- the poly(phenylene ether)-polysiloxane copolymer comprises less than 25 weight percent of molecules having a molecular weight less than 10,000 atomic mass units, specifically 5 to 25 weight percent of molecules having a molecular weight less than 10,000 atomic mass units, more specifically 7 to 21 weight percent of molecules having a molecular weight less than 10,000 atomic mass units.
- the molecules having a molecular weight less than 10,000 atomic mass units comprise 5 to 10 weight percent siloxane repeat units, specifically 6 to 9 weight percent siloxane repeat units.
- the poly(phenylene ether)-polysiloxane copolymer can also include relatively small amounts of very high molecular weight species.
- the poly(phenylene ether)-polysiloxane copolymer comprises less than 25 weight percent of molecules having a molecular weight greater than 100,000 atomic mass units, specifically 5 to 25 weight percent of molecules having a molecular weight greater than 100,000 atomic mass units, more specifically 7 to 23 weight percent of molecules having a molecular weight greater than 100,000 atomic mass units.
- the molecules having a molecular weight greater than 100,000 atomic mass units comprise 3 to 6 weight percent siloxane repeat units, specifically 4 to 5 weight percent siloxane repeat units.
- the composition comprises 0.5 to 85 weight percent of the poly(phenylene ether)-polysiloxane copolymer, based on the total weight of the composition.
- the poly(phenylene ether)-polysiloxane copolymer amount is 1 to 20 weight percent, specifically 2 to 10 weight percent.
- the poly(phenylene ether)-polysiloxane copolymer amount is 30 to 85 weight percent, specifically 40 to 75 weight percent, more specifically 53 to 63 weight percent.
- second poly(phenylene ether) refers to a poly(phenylene ether) that is not derived from the poly(phenylene ether)-polysiloxane block copolymer reaction.
- the second poly(phenylene ether) can be chemically the same as or different from the first poly(phenylene ether).
- Suitable first and second poly(phenylene ether)s include those comprising repeating structural units having the formula
- each occurrence of Z 1 is independently halogen, unsubstituted or substituted C 1 -C 12 hydrocarbylthio, unsubstituted or substituted C 1 -C 12 hydrocarbyloxy, unsubstituted or substituted C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; and each occurrence of Z 2 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbylthio, unsubstituted or substituted C 1 -C 12 hydrocarbyloxy, unsubstituted or substituted C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C 1
- the second poly(phenylene ether) has an intrinsic viscosity of 0.2 to 1 deciliter per gram measured by Ubbelohde viscometer at 25° C. in chloroform. Within this range, the second poly(phenylene ether) intrinsic viscosity can be 0.2 to 0.5 deciliter per gram, specifically 0.2 to 0.4 deciliter per gram, still more specifically 0.25 to 0.35 deciliter per gram.
- the second poly(phenylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or a combination thereof. In some embodiments, the second poly(phenylene ether) comprises a poly(2,6-dimethyl-1,4-phenylene ether). In some embodiments, the second poly(phenylene ether) comprises a poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.2 to 0.4 deciliter per gram, specifically 0.25 to 0.35 deciliter per gram, measured by Ubbelohde viscometer at 25° C. in chloroform.
- the second poly(phenylene ether) can be used in an amount of 5 to 84.5 weight percent, specifically 20 to 80 weight percent, more specifically 55 to 75 weight percent, based on the total weight of the composition.
- the composition comprises a flame retardant.
- the flame retardant comprises an organophosphate ester, a phosphazene, or a combination thereof.
- the flame retardant comprises an organophosphate ester.
- organophosphate ester flame retardants include phosphate esters comprising phenyl groups, substituted phenyl groups, or a combination of phenyl groups and substituted phenyl groups, bis(aryl phosphate) esters based upon resorcinol such as, for example, resorcinol bis(diphenyl phosphate), as well as those based upon bisphenols such as, for example, bisphenol A bis(diphenyl phosphate).
- the organophosphate ester is selected from tris(alkylphenyl) phosphates (for example, CAS Reg. No. 89492-23-9 or CAS Reg. No.
- the organophosphate ester comprises a bis(aryl phosphate) having the formula
- R is independently at each occurrence a C 1 -C 12 alkylene group;
- R 20 and R 21 are independently at each occurrence a C 1 -C 5 alkyl group;
- R 16 , R 17 , and R 19 are independently a C 1 -C 12 hydrocarbyl group;
- R 18 is independently at each occurrence a C 1 -C 12 hydrocarbyl group;
- n is 1 to 25; and
- s1 and s2 are independently an integer equal to 0, 1, or 2.
- OR 16 , OR 17 , OR 18 and OR 19 are independently derived from phenol, a monoalkylphenol, a dialkylphenol, or a trialkylphenol.
- the bis(aryl phosphate) is derived from a bisphenol.
- exemplary bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane and 1,1-bis(4-hydroxypheny)ethane.
- the bisphenol comprises bisphenol A.
- the flame retardant comprises a phosphazene.
- a phosphazene is a compound comprising repeat units having the structure
- each occurrence of R 22 is independently C 1 -C 6 alkoxy, unsubstituted or substituted phenoxy, or unsubstituted or substituted naphthyloxy.
- the substituents on the phenoxy or naphthyloxy groups can be, for example, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or phenyl.
- the phosphazene comprises a cyclic oligophosphazene having the structure
- R 22 is defined above and a is 3 to 12, specifically 3 to 6. In some embodiments, a is 3 and each occurrence of R 22 is unsubstituted phenoxy.
- the phosphazene comprises a linear oligophosphazene or polyphosphazene having the structure
- R 22 is defined above; b is 3 to 1,000; A is —N ⁇ P(O)(R 22 ) or —N ⁇ P(R 22 ) 3 ; and B is —P(R 22 ) 4 or —P(O)(R 22 ) 2 .
- the phosphazene can be a crosslinked polyphosphazene comprising a phenylene group, a biphenylene group, or a group having the structure
- X is C 1 -C 6 alkylidene, O, S, or SO 2 .
- This crosslinking group is typically directly bonded at each end to a phosphazene phosphorus atom.
- a mixture of at least two of cyclic oligophosphazenes, linear oligophosphazenes, linear polyphosphazenes, and crosslinked phosphazenes can be used.
- the phosphazene comprises at last 80 weight percent cyclic phosphazenes, based on the weight of the phosphazene.
- phosphazenes are known, and phosphazenes are commercially available as, for example, RABITLETM FP-100 and RABITLETM FP-110 from Fushimi Pharmaceutical Co., Ltd.; and IDB-Poretar-201 from ID-Biochem, and SPB-100 from Otsuka Chemical Company.
- the flame retardant can, optionally, further comprise a metal dialkylphosphinate, a nitrogen-containing flame retardant, a metal hydroxide, or a combination thereof.
- metal dialkylphosphinate refers to a salt comprising at least one metal cation and at least one dialkylphosphinate anion.
- the metal dialkylphosphinate has the formula
- R a and R b are each independently C 1 -C 6 alkyl; M is calcium, magnesium, aluminum, or zinc; and d is 2 or 3.
- R a and R b include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl.
- R a and R b are ethyl, M is aluminum, and d is 3 (that is, the metal dialkylphosphinate is aluminum tris(diethylphosphinate)).
- the metal dialkylphosphinate is in particulate form.
- the metal dialkylphosphinate particles may have a median particle diameter (D50) less than or equal to 40 micrometers, or, more specifically, a D50 less than or equal to 30 micrometers, or, even more specifically, a D50 less than or equal to 25 micrometers.
- the metal dialkylphosphinate may be combined with a polymer, such as the poly(phenylene ether)-polysiloxane block copolymer reaction product, the optional second poly(phenylene ether), or the optional impact modifier, to form a masterbatch.
- the metal dialkylphosphinate masterbatch comprises the metal dialkylphosphinate in an amount greater than is present in the thermoplastic composition.
- Employing a masterbatch for the addition of the metal dialkylphosphinate to the other components of the composition can facilitate addition and improve distribution of the metal dialkylphosphinate.
- Nitrogen-containing flame retardants include those comprising a nitrogen-containing heterocyclic base and a phosphate or pyrophosphate or polyphosphate acid.
- the nitrogen-containing flame retardant has the formula
- g is 1 to 10,000, and the ratio of f to g is 0.5:1 to 1.7:1, specifically 0.7:1 to 1.3:1, more specifically 0.9:1 to 1.1:1. It will be understood that this formula includes species in which one or more protons are transferred from the phosphate group(s) to the melamine group(s).
- the nitrogen-containing flame retardant is melamine phosphate (CAS Reg. No. 20208-95-1).
- the nitrogen-containing flame retardant is melamine pyrophosphate (CAS Reg. No. 15541 60-3).
- g is, on average, greater than 2
- the nitrogen-containing flame retardant is a melamine polyphosphate (CAS Reg. No. 56386-64-2).
- the nitrogen-containing flame retardant is melamine pyrophosphate, melamine polyphosphate, or a mixture thereof.
- g has an average value of greater than 2 to 10,000, specifically 5 to 1,000, more specifically 10 to 500.
- g has an average value of greater than 2 to 500.
- Methods for preparing melamine phosphate, melamine pyrophosphate, and melamine polyphosphate are known in the art, and all are commercially available.
- melamine polyphosphates may be prepared by reacting polyphosphoric acid and melamine, as described, for example, in U.S.
- the nitrogen-containing flame retardant comprises melamine cyanurate.
- the nitrogen-containing flame retardant can have a low volatility.
- the nitrogen-containing flame retardant exhibits less than 1 percent weight loss by thermogravimetric analysis when heated at a rate of 20° C. per minute from 25 to 280° C., specifically 25 to 300° C., more specifically 25 to 320° C.
- Suitable metal hydroxides include all those capable of providing fire retardancy, as well as combinations of such metal hydroxides.
- the metal hydroxide can be chosen to have substantially no decomposition during processing of the fire additive composition and/or flame retardant thermoplastic composition. Substantially no decomposition is defined herein as amounts of decomposition that do not prevent the flame retardant additive composition from providing the desired level of fire retardancy.
- Exemplary metal hydroxides include, but are not limited to, magnesium hydroxide (for example, CAS Reg. No. 1309-42-8), aluminum hydroxide (for example, CAS Reg. No. 21645-51-2), cobalt hydroxide (for example, CAS Reg. No. 21041-93-0), and combinations thereof.
- the metal hydroxide comprises magnesium hydroxide.
- the metal hydroxide has an average particle size less than or equal to 10 micrometers and/or a purity greater than or equal to 90 weight percent. In some embodiments it is desirable for the metal hydroxide to contain substantially no water, for example as evidenced by a weight loss of less than 1 weight percent upon drying at 120° C. for 1 hour.
- the metal hydroxide can be coated, for example, with stearic acid or other fatty acid.
- the amount of the flame retardant can be 5 to 25 weight percent, based on the total weight of the composition. In some embodiments, the amount of the flame retardant is 5 to 20 weight percent, specifically 5 to 15 weight percent. In other embodiments, the amount of the flame retardant is 10 to 25 weight percent, specifically 15 to 25 weight percent.
- the composition comprises a reinforcing filler.
- Reinforcing fillers include, for example, glass fibers, carbon fibers, wollastonite, halloysite, clays, talcs, micas, glass flakes, solid glass beads, hollow glass beads, solid ceramic beads, hollow ceramic beads, and combinations thereof.
- the reinforcing filler comprises or consists of glass fibers.
- Suitable glass fibers include those based on E, A, C, ECR, R, S, D, and NE glasses, as well as quartz.
- the glass fiber has a diameter of 2 to 30 micrometers, specifically 5 to 25 micrometers, more specifically 10 to 15 micrometers.
- the length of the glass fibers before compounding is 2 to 7 millimeters, specifically 3 to 5 millimeters.
- Suitable glass fiber is commercially available from suppliers including, for example, Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.
- the reinforcing filler can, optionally, include an adhesion promoter to improve its compatibility with the poly(phenylene ether)-polysiloxane block copolymer reaction product.
- Adhesion promoters include chromium complexes, silanes, titanates, zircoaluminates, propylene maleic anhydride copolymers, reactive cellulose esters, and the like.
- the reinforcing filler can be used in an amount of 10 to 35 weight percent, based on the total weight of the composition. In some embodiments, the reinforcing filler amount is 10 to 25 weight percent, specifically 10 to 20 weight percent. In other embodiments, the reinforcing filler amount is 15 to 30 weight percent, specifically 15 to 25 weight percent.
- the composition can, optionally, further include an impact modifier
- Impact modifiers include, for example, rubber-modified polystyrenes, unhydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, hydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, acrylate core-shell impact modifiers (e.g., those having a crosslinked poly(butyl acrylate) core and a grafted poly(methyl methacrylate) shell), and combinations thereof.
- the impact modifier can include a rubber-modified polystyrene.
- Rubber-modified polystyrene comprises polystyrene and polybutadiene. Rubber-modified polystyrenes are sometimes referred to as “high-impact polystyrenes” or “HIPS”.
- the rubber-modified polystyrene comprises 80 to 96 weight percent polystyrene, specifically 88 to 94 weight percent polystyrene; and 4 to 20 weight percent polybutadiene, specifically 6 to 12 weight percent polybutadiene, based on the weight of the rubber-modified polystyrene.
- Suitable rubber-modified polystyrenes are commercially available as, for example, HIPS3190 from SABIC Innovative Plastics.
- the impact modifier can include an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- this component is referred to as an “unhydrogenated block copolymer”.
- the unhydrogenated block copolymer can comprise 10 to 90 weight percent of poly(alkenyl aromatic) content and 90 to 10 weight percent of poly(conjugated diene) content, based on the weight of the unhydrogenated block copolymer.
- the unhydrogenated block copolymer is a low poly(alkenyl aromatic content) unhydrogenated block copolymer in which the poly(alkenyl aromatic) content is 10 to less than 40 weight percent, specifically 20 to 35 weight percent, more specifically 25 to 35 weight percent, yet more specifically 30 to 35 weight percent, all based on the weight of the low poly(alkenyl aromatic) content unhydrogenated block copolymer.
- the unhydrogenated block copolymer is a high poly(alkenyl aromatic) content unhydrogenated block copolymer in which the poly(alkenyl aromatic) content is 40 to 90 weight percent, specifically 50 to 80 weight percent, more specifically 60 to 70 weight percent, all based on the weight of the high poly(alkenyl aromatic) content unhydrogenated block copolymer.
- the unhydrogenated block copolymer has a weight average molecular weight of 40,000 to 400,000 atomic mass units.
- the number average molecular weight and the weight average molecular weight can be determined by gel permeation chromatography and based on comparison to polystyrene standards.
- the unhydrogenated block copolymer has a weight average molecular weight of 200,000 to 400,000 atomic mass units, specifically 220,000 to 350,000 atomic mass units.
- the unhydrogenated block copolymer has a weight average molecular weight of 40,000 to 200,000 atomic mass units, specifically 40,000 to 180,000 atomic mass units, more specifically 40,000 to 150,000 atomic mass units.
- the alkenyl aromatic monomer used to prepare the unhydrogenated block copolymer can have the structure
- R 23 and R 24 each independently represent a hydrogen atom, a C 1 -C 8 alkyl group, or a C 2 -C 8 alkenyl group
- R 25 and R 29 each independently represent a hydrogen atom, a C 1 -C 8 alkyl group, a chlorine atom, or a bromine atom
- R 26 , R 27 , and R 28 each independently represent a hydrogen atom, a C 1 -C 8 alkyl group, or a C 2 -C 8 alkenyl group, or R 26 and R 27 are taken together with the central aromatic ring to form a naphthyl group, or R 27 and R 28 are taken together with the central aromatic ring to form a naphthyl group.
- alkenyl aromatic monomers include, for example, styrene, chlorostyrenes such as p-chlorostyrene, methylstyrenes such as alpha-methylstyrene and p-methylstyrene, and t-butylstyrenes such as 3-t-butylstyrene and 4-t-butylstyrene.
- the alkenyl aromatic monomer is styrene.
- the conjugated diene used to prepare the unhydrogenated block copolymer can be a C 4 -C 20 conjugated diene.
- Suitable conjugated dienes include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and combinations thereof.
- the conjugated diene is 1,3-butadiene, 2-methyl-1,3-butadiene, or a combination thereof.
- the conjugated diene consists of 1,3-butadiene.
- the unhydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene.
- the arrangement of blocks (A) and (B) includes a linear structure, a grafted structure, and a radial teleblock structure with or without a branched chain.
- Linear block copolymers include tapered linear structures and non-tapered linear structures.
- the unhydrogenated block copolymer has a tapered linear structure.
- the unhydrogenated block copolymer has a non-tapered linear structure.
- the unhydrogenated block copolymer comprises a (B) block that comprises random incorporation of alkenyl aromatic monomer.
- Linear block copolymer structures include diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block), and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures as well as linear structures containing 6 or more blocks in total of (A) and (B), wherein the molecular weight of each (A) block can be the same as or different from that of other (A) blocks, and the molecular weight of each (B) block can be the same as or different from that of other (B) blocks.
- the unhydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.
- the unhydrogenated block copolymer excludes the residue of monomers other than the alkenyl aromatic compound and the conjugated diene. In some embodiments, the unhydrogenated block copolymer consists of blocks derived from the alkenyl aromatic compound and the conjugated diene. It does not comprise grafts formed from these or any other monomers. It also consists of carbon and hydrogen atoms and therefore excludes heteroatoms.
- the unhydrogenated block copolymer includes the residue of one or more acid functionalizing agents, such as maleic anhydride.
- the unhydrogenated block copolymer comprises a polystyrene-polybutadiene-polystyrene triblock copolymer. In some embodiments, the unhydrogenated block copolymer comprises a polystyrene-polyisoprene-polystyrene triblock copolymer.
- unhydrogenated block copolymers Methods for preparing unhydrogenated block copolymers are known in the art and unhydrogenated block copolymers are commercially available.
- Illustrative commercially available unhydrogenated block copolymers include the polystyrene-polybutadiene-polystyrene triblock copolymers from Kraton Performance Polymers Inc. under the trade names KratonTM D1101 and D1102; and the styrene-butadiene radial teleblock copolymers from Chevron Phillips Chemical Company under the trade names K-RESINTM KK38, KR01, KR03, and KR05.
- the impact modifier can be a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- this component is referred to as a “hydrogenated block copolymer”.
- the hydrogenated block copolymer is the same as the unhydrogenated block copolymer, except that in the hydrogenated block copolymer the aliphatic unsaturated group content in the block (B) derived from a conjugated diene has been at least partially reduced by hydrogenation. In some embodiments, the aliphatic unsaturation in the (B) block is reduced by at least 50 percent, specifically at least 70 percent, more specifically at least 90 percent.
- Illustrative commercially available hydrogenated block copolymers include the polystyrene-poly(ethylene-propylene) diblock copolymers available from Kraton Performance Polymers Inc. as KRATONTM G1701 and G1702; the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers available from Kraton Performance Polymers Inc.
- KRATONTM G1901, G1924, and MD-6684 the maleic anhydride-grafted polystyrene-poly(ethylene-butylene-styrene)-polystyrene triblock copolymer available from Kraton Performance Polymers Inc.
- polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer comprising 67 weight percent polystyrene available from Asahi Kasei Elastomer as TUFTECTM H1043; the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer comprising 42 weight percent polystyrene available from Asahi Kasei Elastomer as TUFTECTM H1051; the polystyrene-poly(butadiene-butylene)-polystyrene triblock copolymers available from Asahi Kasei Elastomer as TUFTECTM P1000 and P2000; the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer comprising 60 weight polystyrene available from Kuraray as SEPTONTM S8104; the polystyrene-poly(ethylene-
- the impact modifier is a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a polystyrene content of 25 to 35 weight percent and a weight average molecular weight of 200,000 to 400,000 atomic mass units.
- the impact modifier can be used in an amount of 1 to 10 weight percent, specifically 1 to 5 weight percent, based on the total weight of the composition.
- the composition can, optionally, further comprise a hydrocarbon resin.
- hydrocarbon resins are aliphatic hydrocarbon resins, hydrogenated aliphatic hydrocarbon resins, aliphatic/aromatic hydrocarbon resins, hydrogenated aliphatic/aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, hydrogenated cycloaliphatic resins, cycloaliphatic/aromatic hydrocarbon resins, hydrogenated cycloaliphatic/aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, terpene resins, hydrogenated terpene resins, terpene-phenol resins, rosins, and rosin esters, hydrogenated rosins and rosin esters, and mixtures thereof.
- hydrocarbon resin when referring to the hydrocarbon resin, includes fully, substantially, and partially hydrogenated resins.
- Suitable aromatic resins include aromatic modified aliphatic resins, aromatic modified cycloaliphatic resins, and hydrogenated aromatic hydrocarbon resins having an aromatic content of 1 to 30 weight percent. Any of the above resins can be grafted with an unsaturated ester or anhydride using methods known in the art. Such grafting can provide enhanced properties to the resin.
- the hydrocarbon resin is a hydrogenated aromatic hydrocarbon resin.
- Suitable hydrocarbon resins are commercially available and include, for example, EMPRTM 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 116, 117, and 118 resins, and OPPERATM resins, available from ExxonMobil Chemical Company; ARKONTM P140, P125, P115, M115, and M135, and SUPER ESTERTM rosin esters available from Arakawa Chemical Company of Japan; SYLVARESTM polyterpene resins, styrenated terpene resins and terpene phenolic resins available from Arizona Chemical Company; SYLVATACTM and SYLVALITETM rosin esters available from Arizona Chemical Company; NORSOLENETM aliphatic aromatic resins available from Cray Valley; DERTOPHENETM terpene phenolic resins and DERCOLYTETM polyterpene resins available from DRT Chemical Company; EASTOTACTM resins, PICCOTACTM resins
- the hydrocarbon resin can have a softening point of at least 120° C. measured according to ASTM E28. Specifically, the softening point can be 120 to 180° C., specifically 130 to 170° C., more specifically 140 to 160° C.
- the hydrocarbon resin comprises a hydrogenated alicyclic hydrocarbon resin, a hydrogenated terpene resin, or a combination thereof.
- the hydrocarbon resin comprises a hydrogenated alicyclic hydrocarbon resin having a softening point of 120 to 135° C.
- the hydrocarbon resin comprises a hydrogenated alicyclic hydrocarbon resin having a softening point of 135 to 145° C.
- An example of such a resin is ARKONTM P140 having a softening point of about 140° C., available from Arakawa Chemical Company
- the hydrocarbon resin comprises a hydrogenated terpene resin having a softening point of 145 to 160° C.
- An example of such a resin is CLEARONTM P150 available from Yasuhara.
- the hydrocarbon resin can be used in an amount of 1 to 8 weight percent, specifically 2 to 6 weight percent, based on the total weight of the composition.
- the composition can, optionally, further comprise a trihydrocarbyl phosphite.
- Trihydrocarbyl phosphites have the general structure P(OR 30 ) 3 , wherein each occurrence of R 30 is independently C 1 -C 18 hydrocarbyl. In some embodiments, each R 30 is independently C 6 -C 18 alkyl. In other embodiments, at least one R 30 is C 6 -C 18 aryl. In some embodiments, each occurrence of R 19 is independently an unsubstituted or substituted C 6 -C 18 aryl.
- Suitable trihydrocarbyl phosphites include, for example, trioctyl phosphite, tridecyl phosphite, tridodecyl phosphite, phenyl didecyl phosphite, decyl diphenyl phosphite, triphenyl phosphite, tritolyl phosphites, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and the like, and combinations thereof.
- Suitable trihydrocarbyl phosphites further include spiro diphosphites such as, for example, 3,9-bis[2,4-bis(1,1-dimethylethyl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (CAS Reg. No. 26741-53-7; commercially available from Ciba under the trade name IRGAFOSTM 126).
- the aryl phosphite comprises tris(2,4-di-tert-butylphenyl)phosphite (CAS Reg. No. 31570-04-4).
- the aryl phosphite comprises bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (CAS Reg. No. 26741-53-7).
- the trihydrocarbyl phosphite can be used in an amount of 0.05 to 1 weight percent, specifically 0.1 to 0.5 weight percent, based on the total weight of the composition.
- the composition can, optionally, further comprise linear low density polyethylene (LLDPE).
- Linear low density polyethylene is a copolymer of ethylene and a longer chain olefin such as 1-butene, 1-hexene, or 1-octene.
- the linear low density polyethylene is a copolymer of ethylene and 1-butene.
- Linear low density polyethylene typically has a density of about 0.92 grams/centimeter 3 .
- the linear low density polyethylene can be used in an amount of 0.5 to 5 weight percent, specifically 0.5 to 3 weight percent, based on the total weight of the composition.
- the composition can, optionally, further comprise one or more additives known in the thermoplastics art.
- the composition can, optionally, further comprise an additive chosen from stabilizers, mold release agents, lubricants, processing aids, drip retardants, nucleating agents, UV blockers, dyes, pigments, antioxidants, anti-static agents, blowing agents, mineral oil, metal deactivators, antiblocking agents, and the like, and combinations thereof.
- additives are typically used in a total amount of less than or equal to 5 weight percent, specifically less than or equal to 4 weight percent, more specifically less than or equal to 3 weight percent, based on the total weight of the composition.
- the composition can, optionally, exclude polymers other than those required.
- the composition can comprise less than or equal to 1 weight percent of each of polyamides and polyesters.
- the composition comprises less than or equal to 4 weight percent, specifically less than or equal to 3 weight percent, more specifically less than or equal to 2 weight percent, of polyolefins.
- the composition comprises less than or equal to 1 weight percent of polyolefins other than linear low density polyethylene. In other embodiments, the composition comprises less than or equal to 1 weight percent of any polyolefins.
- composition can achieve a UL 94 V-0 rating without using the halogenated flame retardants that are typically employed in glass-filled polyester compositions utilized for similar product applications.
- the composition can comprise less than or equal to 0.1 weight percent halogens, specifically less than or equal to 0.01 weight percent halogens, based on the total weight of the composition.
- composition is halogen-free.
- the article is a fuser holder, and the composition comprises 2 to 10 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product, and further comprises 55 to 75 weight percent of a second poly(phenylene ether).
- the reinforcing filler amount is, optionally, 10 to 20 weight percent, and the reinforcing filler optionally comprises glass fibers.
- the composition optionally further comprises 1 to 5 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- the article is a fuser holder
- the poly(phenylene ether)-polysiloxane copolymer comprises a poly(phenylene ether)-polysiloxane block copolymer provided in the form of a poly(phenylene ether)-polysiloxane block copolymer reaction product
- the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- n 30 to 60; the reinforcing filler comprises glass fibers; the flame retardant comprises bisphenol A bis(diphenyl phosphate); the composition comprises 2 to 10 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 5 to 15 weight percent of the flame retardant, and 10 to 20 weight percent of the reinforcing filler; and the composition further comprises 55 to 75 weight percent of a second poly(phenylene ether) comprising poly(2,6-dimethyl-1,4-phenylene ether), and 1 to 5 weight percent of a polystyrene-poly(ethylene-butylene)-polystyrene block copolymer.
- the flame retardant comprises bisphenol A bis(diphenyl phosphate)
- the composition comprises 2 to 10 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 5 to 15 weight percent of the flame retardant, and 10 to 20 weight percent of the reinfor
- the article is selected from the group consisting of fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes, and the composition comprises 53 to 63 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product.
- the reinforcing filler amount is, optionally, 15 to 25 weight percent, and the reinforcing filler optionally comprises glass fibers.
- the composition optionally comprises 0 to 4 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- the composition optionally comprises 0.5 to 3 weight percent of a linear low density polyethylene.
- the article is selected from the group consisting of fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes;
- the poly(phenylene ether)-polysiloxane copolymer comprises a poly(phenylene ether)-polysiloxane block copolymer provided in the form of a poly(phenylene ether)-polysiloxane block copolymer reaction product;
- the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- n 30 to 60; the reinforcing filler comprises glass fibers; the flame retardant comprises bisphenol A bis(diphenyl phosphate); the composition comprises 53 to 63 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 15 to 25 weight percent of the flame retardant, and 15 to 25 weight percent of the reinforcing filler; and the composition further comprises 0.5 to 3 weight percent of a linear low density polyethylene.
- the article can be a fuser holder for an electrophotographic copier, a fan blade, a battery part for hybrid and electric vehicles, a part for an automotive kinetic energy recovery system, or an electric vehicle junction box.
- a fuser holder for an electrophotographic copier is known, as are methods for their fabrication.
- U.S. Pat. No. 5,499,087 of Hiraoka et al. describes a fuser holder for an electrophotographic copier. Suitable methods of forming such articles include single layer and multilayer sheet extrusion, injection molding, blow molding, film extrusion, profile extrusion, pultrusion, compression molding, thermoforming, pressure forming, hydroforming, vacuum forming, and the like.
- the article is formed by injection molding.
- the injection molding uses a barrel temperature of 285 to 330° C., specifically 295 to 325° C., and a mold temperature of 60 to 120° C., specifically 80 to 110° C.
- the invention includes at least the following embodiments.
- An article comprising a composition, wherein the article is selected from the group consisting of fuser holders for electrophotographic copiers, fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes; wherein the composition comprises 0.5 to 85 weight percent of a poly(phenylene ether)-polysiloxane copolymer comprising a poly(phenylene ether)-polysiloxane block copolymer, a poly(phenylene ether)-polysiloxane graft copolymer, or a combination thereof; 5 to 25 weight percent of a flame retardant comprising an organophosphate ester, a phosphazene, or a combination thereof; and 10 to 35 weight percent of a reinforcing filler; wherein all weight percent values are based on the total weight of the composition; provided that when the article is a fuser holder, the composition comprises 2 to 10 weight percent of a poly(phenylene ether)-polys
- poly(phenylene ether)-polysiloxane copolymer comprises the poly(phenylene ether)-polysiloxane block copolymer.
- composition comprises a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether), and wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- n 30 to 60.
- poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether)-polysiloxane multiblock copolymer.
- poly(phenylene ether)-polysiloxane copolymer comprises the poly(phenylene ether)-polysiloxane graft copolymer.
- the reinforcing filler is selected from the group consisting of glass fibers, carbon fibers, wollastonite, halloysite, clays, talcs, micas, glass flakes, solid glass beads, hollow glass beads, solid ceramic beads, hollow ceramic beads, and combinations thereof.
- organophosphate ester comprises bisphenol A bis(diphenyl phosphate).
- the flame retardant comprises a cyclic oligo(bis(phenoxy)phosphazene), a linear oligo(bis(phenoxy)phosphazene), a linear poly(bis(phenoxy)phosphazene), a crosslinked poly(bis(phenoxy)phosphazene), or a combination thereof.
- composition further comprises 1 to 10 weight percent of an impact modifier selected from the group consisting of rubber-modified polystyrenes, unhydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, hydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, acrylate core-shell impact modifiers, and combinations thereof.
- an impact modifier selected from the group consisting of rubber-modified polystyrenes, unhydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, hydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, acrylate core-shell impact modifiers, and combinations thereof.
- composition comprises 2 to 10 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether); and wherein the composition further comprises 55 to 75 weight percent of a second poly(phenylene ether).
- composition comprises 10 to 20 weight percent of the reinforcing filler, and the reinforcing filler comprises glass fibers.
- composition further comprises 1 to 5 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- the article is a fuser holder; wherein the composition comprises a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether); wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- n is 30 to 60; wherein the first poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether); wherein the reinforcing filler comprises glass fibers; wherein the flame retardant comprises bisphenol A bis(diphenyl phosphate); wherein the composition comprises 2 to 10 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 5 to 15 weight percent of the flame retardant, and 10 to 20 weight percent of the reinforcing filler; and wherein the composition further comprises 55 to 75 weight percent of a second poly(phenylene ether) comprising poly(2,6-dimethyl-1,4-phenylene ether), and 1 to 5 weight percent of a polystyrene-poly(ethylene-butylene)-polystyrene block copolymer.
- composition comprises 15 to 25 weight percent of the reinforcing filler, and the reinforcing filler comprises glass fibers.
- composition comprises 0 to 4 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- composition further comprises 0.5 to 3 weight percent of a linear low density polyethylene.
- the article is selected from the group consisting of fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes; wherein the composition comprises a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether); wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- n is 30 to 60; wherein the reinforcing filler comprises glass fibers; wherein the flame retardant comprises bisphenol A bis(diphenyl phosphate); wherein the composition comprises 53 to 63 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 15 to 25 weight percent of the flame retardant, and 15 to 25 weight percent of the reinforcing filler; and wherein the composition further comprises 0.5 to 3 weight percent of a linear low density polyethylene.
- 25134-01-4 having an intrinsic viscosity of about 0.33 deciliter per gram measured in chloroform at 25° C.; available as PPO TM 630 from SABIC Innovative Plastics.
- PPE-Si A mixture of poly(2,6-dimethyl-1,4-phenylene ether) (CAS Reg. No.
- poly(2,6-dimethyl-1,4-phenylene ether)-polydimethylsiloxane block copolymer (CAS Reg. No. 1202019-56-4), the mixture having a polysiloxane content of about 5 weight percent and an intrinsic viscosity of about 0.4 deciliter per gram as measured in chloroform at 25° C.; prepared according to the procedure of U.S. Pat. No. 8,017,697 to Carrillo et al., Example 16.
- SEBS Polystyrene-poly(ethylene/butylene)-polystyrene triblock copolymer CAS Reg. No.
- 66070-58-4 having a polystyrene content of 30-33 weight percent and a weight average molecular weight of 240,000-301,000 atomic mass units; obtained as KRATON TM G1651 from Kraton Performance Polymers Inc.
- AO 168 Tris(2,4-di-tert-butylphenyl) phosphite, CAS Reg. No. 31570-04-4, available from BASF Corp. as IRGAFOS TM 168, or from Chemtura as ALKANOX TM 240.
- AO 626 Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, CAS Reg. No.
- Glass Fiber Chopped glass fiber having a diameter of about 14 micrometers and a pre- compounded length of about 4 millimeters; available from Owens Corning as 122Y-14C.
- Carbon Black Carbon black pigment CAS Reg. No. 1333-86-4, available from Cabot as BLACK PEARLS TM 800 or MONARCH TM 800.
- Resin compositions were compounded on a 30 millimeter Werner & Pfleiderer ZSK twin-screw extruder operating at 350 rotations per minute and a throughput of 18 kilograms per hour (40 pounds per hour) and using barrel set temperatures of 240° C./260° C./290° C./290° C./290° C./290° C. from the feed port to die. Glass fibers were added downstream to the extruder, while all other solid components were added at the feed throat and the liquid flame retardant (But-TPP or BPADP) was injected at a port between the feed throat and the glass fiber feed location. The compounded resins were pelletized by strand-cutting.
- Test articles for ASTM determinations of heat deflection temperature and flexural properties were injection molded on a 120 Ton VanDorn injection molding machine using a barrel temperature of 288-310° C. (550-590° F.) and a mold temperature of about 88° C. (about 190° F.).
- Flame bars with 1.0 or 1.5 millimeter thickness were injection molded on an 80 Ton VanDorn injection molding machine using a barrel temperature of 299-321° C. (570-610° F.) and a mold temperature of 88-99° C. (190-210° F.).
- Flame retardancy of injection molded flame bars was determined according to Underwriter's Laboratory Bulletin 94 “Tests for Flammability of Plastic Materials, UL 94”, 20 mm Vertical Burning Flame Test. Before testing, flame bars with a thickness of 1.0 or 1.5 millimeters were conditioned at 23° C. and 50% relative humidity for at least 24 hours. In the UL 94 20 mm Vertical Burning Flame Test, a set of ten flame bars was tested. For each bar, a flame was applied to the bar then removed, and the time required for the bar to self-extinguish (first afterflame time, t1) was noted.
- the flame was then reapplied and removed, and the time required for the bar to self-extinguish (second afterflame time, t2) and the post-flame glowing time (afterglow time, t3) were noted.
- the afterflame times t1 and t2 for each individual specimen must have been less than or equal to 10 seconds; and the total afterflame time for all ten specimens (t1 plus t2 for all ten specimens) must have been less than or equal to 100 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2+t3) must have been less than or equal to 30 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops.
- the afterflame times t1 and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all ten specimens (t1 plus t2 for all ten specimens) must have been less than or equal to 500 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2+t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops.
- the afterflame times t1 and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all ten specimens (t1 plus t2 for all ten specimens) must have been less than or equal to 250 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2+t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; but the cotton indicator can have been ignited by flaming particles or drops. Compositions not achieving a rating of V-2 were considered to have failed.
- Heat deflection temperature (HDT) values expressed in units of degrees centigrade, were determined according to ASTM D 648-07 using 6.4 millimeter thick bars (except where specified as 3.2 millimeter thickness), an edgewise test direction, a support span of 100 millimeters (Method B), a stress of 1.82 megapascals, a deflection of 0.25 millimeters at reading, a heating rate of 2° C./minute, and three specimens per composition.
- Flexural modulus and flexural strength values were determined at 23° C. according to ASTM D 790-07e1 using 6.4 millimeter thick bars, a support span of 101.6 millimeters, a test speed of 2.54 millimeters/minute (0.1 inch/minute; Procedure A), and three specimens per composition.
- compositions and results are summarized in Table 2, where component amounts are expressed in weight percent based on the total weight of the composition.
- inventive and comparative examples illustrate the use of a poly(phenylene ether)-polysiloxane block copolymer in combination with the hydrogenated block copolymer SEBS.
- inventive Examples 1-6 all have heat deflection temperature values of at least 155° C., as well as UL 94 ratings of V-0 at 1.5 millimeter thickness, and flexural modulus values greater than 3,500 megapascals.
- Comparative Examples 24 and 25 are unfilled and exhibit substantially lower heat deflection temperature values, flexural modulus values, and flexural strength values.
- Melt volume flow rate (MVR) values expressed in units of cubic centimeters per 10 minutes, were determined according to ASTM D 1238-04 at 300° C. using a load of 5 kilograms, automatic timing (Procedure B), a capillary diameter of 2.0955 millimeters, a capillary length of 8.00 millimeters, a test specimen form of pellets, specimen conditioning for one hour at 70° C. prior to testing, and one sample with five readings per composition.
- Comparative Example 26 shows again that with poly(phenylene ether) homopolymer rather than poly(phenylene ether)-polysiloxane block copolymer reaction product, even a higher concentration of flame retardant does not result in V-0 flammability rating at 1.5 millimeters.
- compositions comprising as little as 0.5 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product. They further illustrate compositions comprising a first poly(phenylene ether) (derived from the poly(phenylene ether)-polysiloxane block copolymer reaction product) and a second poly(phenylene ether) (separately added; see Examples 28-43).
- Notched Izod values and unnotched Izod values were determined according to ASTM D256-08 at 25° C. using a hammer energy of 2 foot-pounds (2.71 joules), and bar cross-sectional dimensions of 3.2 by 12.7 millimeters.
- Flexural modulus, flexural stress at yield, and flexural stress at break values were determined at 23° C. according to ASTM D 790-07e1 using 6.4 millimeter thick bars, a support span of 101.6 millimeters, a test speed of 2.54 millimeters/minute (0.1 inch/minute; Procedure A), and three specimens per composition.
- Tensile modulus and tensile stress at break values were determined according to ASTM D 638-08 at 23° C. using a Type I bar having a thickness of 3.2 millimeters, a gage length of 50 millimeters, and a testing speed of 5 millimeters per minute.
- compositions with 0.5 to 40 weight percent poly(phenylene ether)-polysiloxane block copolymer reaction product exhibit a UL 94 V-0 rating at a thickness of 1.5 millimeters.
- physical properties were not measured for all samples, the available results show that compositions with 2 to 40 weight percent poly(phenylene ether)-polysiloxane block copolymer reaction product further exhibit a heat deflection temperature of at least 150° C. determined according to ASTM D 648-07 using a stress of 1.82 megapascals (MPa) and a sample thickness of 6.4 millimeters, and a flexural modulus of at least 5,000 megapascals measured at 23° C.
- MPa modulus
- MPa Flex. stress at yield
- MPa Flex. stress at break
- MPa Flex. stress at break
- MPa Tens. modulus
- MPa Tensile stress at break
- MPa — — — — — — — Tens. elong. at break (%) — — — — — — — — —
- This example illustrates a composition exhibiting high flame retardancy, heat resistance, and melt flow.
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Abstract
Description
- Poly(phenylene ether) is a type of plastic known for its excellent water resistance, dimensional stability, and inherent flame retardancy. Properties such as strength, stiffness, chemical resistance, and heat resistance can be tailored by blending it with various other plastics in order to meet the requirements of a wide variety of consumer and industrial products, for example, plumbing fixtures, electrical boxes, automotive parts, and insulation for wire and cable.
- Some parts made from poly(phenylene ether)-based compositions require high flame retardancy. Examples include fuser holders for electrophotographic copiers, fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes. Poly(phenylene ether) is inherently flame retardant, but it is often blended with other components, such as impact modifiers and flow promoters, that reduce the flame retardancy of the resulting composition even as they improve its processing and mechanical properties. So, flame retardant additives are often required for blends of poly(phenylene ether)s with these other components.
- Some molded parts require a flammability rating of V-0 in the 20 millimeter Vertical Burning Flame Test of Underwriter's Laboratory Bulletin 94 “Tests for Flammability of Plastic Materials, UL 94”. This V-0 rating can be difficult to achieve in a poly(phenylene ether) composition, even when flame retardant concentration is increased, and concentrations of flammable components are decreased. And when the V-0 rating is achievable, it often comes at the expense of diminished heat resistance and diminished stiffness.
- There remains a need for poly(phenylene ether)-containing parts that exhibit a UL 94 V-0 rating while maintaining high heat resistance and stiffness.
- One embodiment is an article comprising a composition, wherein the article is selected from the group consisting of fuser holders for electrophotographic copiers, fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes; wherein the composition comprises 0.5 to 85 weight percent of a poly(phenylene ether)-polysiloxane copolymer comprising a poly(phenylene ether)-polysiloxane block copolymer, a poly(phenylene ether)-polysiloxane graft copolymer, or a combination thereof; 5 to 25 weight percent of a flame retardant comprising an organophosphate ester, a phosphazene, or a combination thereof; and 10 to 35 weight percent of a reinforcing filler; wherein all weight percent values are based on the total weight of the composition; provided that when the article is a fuser holder, the composition comprises 2 to 10 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the a poly(phenylene ether)-polysiloxane block copolymer and a first a poly(phenylene ether), and further comprises 55 to 75 weight percent of a second poly(phenylene ether).
- This and other embodiments are described in detail below.
- The present inventors have determined that parts (also referred to herein as “articles”) fabricated from a composition containing specific amounts of a poly(phenylene ether)-polysiloxane copolymer, a flame retardant, and a reinforcing filler exhibit a UL 94 V-0 rating while maintaining high heat resistance and stiffness. In some embodiments, the high heat resistance is manifested as a heat deflection temperature of 110 to 180° C., specifically 130 to 170° C., determined according to ASTM D 648-07 using 6.4 millimeter thick bars, an edgewise test direction, a support span of 100 millimeters (Method B), a stress of 1.82 megapascals, a deflection of 0.25 millimeters at reading, and a heating rate of 2° C./minute. In some embodiments, the high stiffness is manifested as a flexural modulus of 3,500 to 7,000 megapascals, specifically 4,500 to 6,500 megapascals, determined at 23° C. according to ASTM D 790-07e1 using 6.4 millimeter thick bars, a support span of 101.6 millimeters, and a test speed of 2.54 millimeters/minute. In some embodiments, the composition exhibits high melt flow, which facilitates injection molding of parts. The high melt flow can be objectively manifested as a melt volume flow rate of 10 to 30 cubic centimeters per 10 minutes, specifically 10 to 25 cubic centimeters per 10 minutes, determined according to ASTM D 1238-04 at 300° C. using a load of 5 kilograms, automatic timing (Procedure B), a capillary diameter of 2.0955 millimeters, and a capillary length of 8.00 millimeters.
- Examples of articles benefiting from the flame retardancy, heat resistance, and stiffness of the composition include fuser holders for electrophotographic copiers (including fuser gates, fuser covers, and fuser frames), fan blades (including blades in fans employed in computer and telecommunication equipment such as personal computers, servers, routers, and base stations; blades in fans employed in business equipment such as printers, copiers, faxes, and projectors; blades in fans employed in electrical appliances such as refrigerators, freezers, washing machines and driers, microwave ovens, dishwashers, air conditioners, and audiovisual equipment; and blades in fans used in industrial equipment, including robots), battery parts for hybrid and electric vehicles (including battery cases, battery module cases, battery terminal blocks, battery spacers, and battery trays), parts for automotive kinetic energy recovery systems (including battery module cases and capacitor cases), and electric vehicle junction boxes.
- The composition comprises a poly(phenylene ether)-polysiloxane copolymer that comprises a poly(phenylene ether)-polysiloxane block copolymer, a poly(phenylene ether)-polysiloxane graft copolymer, or a combination thereof.
- In some embodiments, the composition comprises a poly(phenylene ether)-polysiloxane copolymer. The poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block and a polysiloxane block. Included in poly(phenylene ether)-polysiloxane block copolymers are diblock copolymers comprising one poly(phenylene ether) block and one polysiloxane block; triblock copolymers comprising two poly(phenylene ether) blocks and one polysiloxane block, or one poly(phenylene ether) block and two polysiloxane blocks; and multiblock copolymers comprising at least two poly(phenylene ether) blocks and at least two polysiloxane blocks.
- Poly(phenylene ether)-polysiloxane diblock and triblock copolymers can be synthesized by oxidative polymerization of a mixture of monohydric phenol and hydroxyaryl-terminated polysiloxane. This oxidative polymerization produces a poly(phenylene ether)-polysiloxane block copolymer reaction product that comprises poly(phenylene ether)-polysiloxane block copolymer as the desired product and poly(phenylene ether) as a by-product. This poly(phenylene ether) present in the reaction product is sometimes referred to herein as the “first poly(phenylene ether)” to distinguish it from a “second poly(phenylene ether)” that is optionally present in the composition and not derived from the poly(phenylene ether)-polysiloxane block copolymer reaction product. It is unnecessary to separate the first poly(phenylene ether) from the poly(phenylene ether)-polysiloxane block copolymer. The poly(phenylene ether)-polysiloxane block copolymer can therefore be incorporated into the present composition as the poly(phenylene ether)-polysiloxane block copolymer reaction product that comprises the first poly(phenylene ether) in addition to the poly(phenylene ether)-polysiloxane block copolymer.
- When the poly(phenylene ether)-polysiloxane block copolymer is synthesized by oxidative polymerization of a mixture of monohydric phenol and hydroxyaryl-terminated polysiloxane, the poly(phenylene ether) block is a polymerization product of the monohydric phenol.
- In some embodiments, the monohydric phenol has the structure
- and the poly(phenylene ether) block comprises phenylene ether repeat units having the structure
- wherein for each repeating unit, each Z1 is independently unsubstituted or substituted C1-C12 hydrocarbylthio, unsubstituted or substituted C1-C12 hydrocarbyloxy, or unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; and each Z2 is independently hydrogen, unsubstituted or substituted C1-C12 hydrocarbylthio, unsubstituted or substituted C1-C12 hydrocarbyloxy, or unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl. As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. For example, when described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. As one example, Z1 of the phenylene ether repeat unit can be a di-n-butylaminomethyl group formed by reaction of a terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst. In some embodiments, the monohydric phenol comprises 2,6-dimethylphenol, 2,3,6-trimethylphenol, or a combination thereof, and the poly(phenylene ether) block comprises, respectfully, 2,6-dimethyl-1,4-phenylene ether repeat units, that is, repeat units having the structure
- 2,3,6-trimethyl-1,4-phenylene ether repeat units, or a combination thereof
- When the poly(phenylene ether)-polysiloxane block copolymer is synthesized by oxidative polymerization of a mixture of monohydric phenol and hydroxyaryl-terminated polysiloxane, the polysiloxane block is a residue of the hydroxyaryl-terminated polysiloxane. In some embodiments, the polysiloxane block comprises repeat units having the structure
- wherein each occurrence of R1 and R2 is independently hydrogen or C1-C12 hydrocarbyl; and the polysiloxane block further comprises a terminal unit having the structure
- wherein Y is hydrogen, C1-C12 hydrocarbyl, or C1-C12 hydrocarbyloxy, and wherein each occurrence of R3 and R4 is independently hydrogen or C1-C12 hydrocarbyl. In some embodiments, the polysiloxane repeat units comprise dimethylsiloxane (—Si(CH3)2O—) units. In some embodiments, the polysiloxane block has the structure
- wherein n is 20 to 60.
- In a very specific embodiment, the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- and
a polysiloxane block having the structure - wherein n is 30 to 60.
- The hydroxyaryl-terminated polysiloxane comprises at least one hydroxyaryl terminal group. In some embodiments, the hydroxyaryl-terminated polysiloxane has a single hydroxyaryl terminal group, in which case a poly(phenylene ether)-polysiloxane diblock copolymer is formed. In other embodiments, the hydroxyaryl-terminated polysiloxane has two hydroxyaryl terminal groups, in which case in which case poly(phenylene ether)-polysiloxane diblock copolymer and/or poly(phenylene ether)-polysiloxane-poly(phenylene ether) triblock copolymer are formed. It is also possible for the hydroxyaryl-terminated polysiloxane to have a branched structure that allows three or more hydroxyaryl terminal groups and the formation of corresponding branched block copolymers.
- In a very specific procedure for preparing the poly(phenylene ether)-polysiloxane block copolymer reaction product, the monohydric phenol is 2,6-dimethylphenol; the hydroxyaryl-terminated polysiloxane is a eugenol-capped polydimethylsiloxane comprising 35 to 60 dimethylsiloxane units; the oxidative copolymerization is conducted with a reaction time of 170 to 220 minutes; and the hydroxyaryl-terminated polysiloxane constitutes 2 to 7 weight percent of the combined weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane.
- In some embodiments, the hydroxyaryl-terminated polysiloxane comprises 20 to 80 siloxane repeat units, specifically 25 to 70 siloxane repeat units, more specifically 30 to 60 siloxane repeat units, still more specifically 35 to 50 siloxane repeat units, yet more specifically 40 to 50 siloxane repeat units. The number of siloxane repeat units in the polysiloxane block is essentially unaffected by the copolymerization and isolation conditions, and it is therefore equivalent to the number of siloxane repeat units in the hydroxyaryl-terminated polysiloxane starting material. When not otherwise known, the average number of siloxane repeat units per hydroxyaryl-terminated polysiloxane molecule can be determined by nuclear magnetic resonance (NMR) methods that compare the intensities of signals associated with the siloxane repeat units to those associated with the hydroxyaryl terminal groups. For example, when the hydroxyaryl-terminated polysiloxane is a eugenol-capped polydimethylsiloxane, it is possible to determine the average number of siloxane repeat units by a proton nuclear magnetic resonance (1H NMR) method in which integrals for the protons of the dimethylsiloxane resonance and the protons of the eugenol methoxy group are compared.
- In some embodiments, the poly(phenylene ether)-polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units. For example, the reaction product can have a weight average molecular weight of 30,000 to 150,000 atomic mass units, specifically 35,000 to 120,000 atomic mass units, more specifically 40,000 to 90,000 atomic mass units, even more specifically 45,000 to 70,000 atomic mass units. In some embodiments, the poly(phenylene ether)-polysiloxane block copolymer reaction product has a number average molecular weight of 10,000 to 50,000 atomic mass units, specifically 10,000 to 30,000 atomic mass units, more specifically 14,000 to 24,000 atomic mass units.
- In some embodiments, the poly(phenylene ether)-polysiloxane block copolymer reaction product has an intrinsic viscosity of at least 0.3 deciliter per gram, as measured by Ubbelohde viscometer at 25° C. in chloroform. In some embodiments, the intrinsic viscosity is 0.3 to 0.5 deciliter per gram, specifically 0.31 to 0.5 deciliter per gram, more specifically 0.35 to 0.47 deciliter per gram.
- One indication of the efficiency with which the hydroxyaryl-terminated polysiloxane is incorporated into block copolymer is the low concentration of so-called poly(phenylene ether) “tail” groups in the reaction product. In a homopolymerization of 2,6-dimethylphenol, a large fraction of product molecules have a so-called head-to-tail structure in which the linear product molecule is terminated on one end by a 3,5-dimethyl-4-hydroxyphenyl “head” and on the other end by a 2,6-dimethylphenoxy “tail”. Thus, when the monohydric phenol consists of 2,6-dimethylphenol, the poly(phenylene ether) tail group has the structure
- Note that the term “2,6-dimethylphenoxy” refers to a monovalent group and does not encompass divalent 2,6-dimethyl-1,4-phenylene ether groups. In a copolymerization of monohydric phenol with hydroxyaryl-terminated polysiloxane, incorporation of the hydroxyaryl-terminated polysiloxane into block copolymer will reduce the concentration of phenylene ether “tail” groups. Thus, in some embodiments, the monohydric phenol consists of 2,6-dimethylphenol, and the reaction product of comprises less than or equal to 0.4 weight percent, specifically 0.1 to 0.4 weight percent, of 2,6-dimethylphenoxy groups, based on the weight of the reaction product. The low concentration of 2,6-dimethylphenoxy tail end groups is an indication that the reaction product comprises a reduced concentration of the 2,6-dimethylphenol homopolymer and an increased concentration of the desired poly(phenylene ether)-polysiloxane block copolymer.
- The poly(phenylene ether)-polysiloxane block copolymer reaction product can further include groups derived from a diphenoquinone, which is itself an oxidation product of the monohydric phenol. For example, when the monohydric phenol is 2,6-dimethylphenol, the diphenoquinone is 3,3′,5,5′-tetramethyl-4,4′-diphenoquinone. During the build phase of the copolymerization, the diphenoquinone is typically incorporated into the “tail” end of a head-to-tail poly(phenylene ether) as the corresponding biphenyl group. Through further reactions, the terminal biphenyl group can become an internal biphenyl group in the first poly(phenylene ether) chain. In some embodiments, the monohydric phenol consists of 2,6-dimethylphenol, and the reaction product comprises 0.1 to 2.0 weight percent, and specifically 1.1 to 2.0 weight percent, of 2,6-dimethyl-4-(3,5-dimethyl-4-hydroxyphenyl)-phenoxy (“biphenyl”) groups. The biphenyl groups are present only in bifunctional (head-to-head or hydroxyl-diterminated) structure. So, the low concentration of biphenyl group is an indication that the reaction product comprises a reduced concentration of such bifunctional 2,6-dimethylphenol homopolymer and an increased concentration of the desired poly(phenylene ether)-polysiloxane block copolymer.
- The poly(phenylene ether)-polysiloxane block copolymer content of a poly(phenylene ether)-polysiloxane block copolymer reaction product can be estimated by nuclear magnetic resonance spectroscopy (NMR). For example, when the monohydric phenol is 2,6-dimethylphenol, and the hydroxylaryl-terminated polysiloxane is a eugenol-diterminated polydimethylsiloxane, the reaction product can be approximated as a mixture of head-to-tail poly(phenylene ether) homopolymer, head-to-head poly(phenylene ether) homopolymer (incorporating a biphenyl group), and poly(phenylene ether)-polysiloxane-poly(phenylene ether) triblock copolymer. Nuclear magnetic resonance analysis of the mixture can be used to determine the relative concentrations of “head groups” having the structure
- “tail groups” having the structure
- and
“biphenyl groups” having the structure - The concentration of poly(phenylene ether)-polysiloxane-poly(phenylene ether) triblock copolymer (PSP) can then be calculated as
-
PSP=½([head groups]−[tail groups]−2[biphenyl groups]). - In some embodiments, the poly(phenylene ether)-polysiloxane block copolymer reaction product incorporates greater than 75 weight percent, of the hydroxyaryl-terminated polysiloxane starting material into the poly(phenylene ether)-polysiloxane block copolymer. Specifically, the amount of the hydroxyaryl-terminated polysiloxane incorporated into the poly(phenylene ether)-polysiloxane block copolymer can be at least 80 weight percent, more specifically at least 85 weight percent, still more specifically at least 90 weight percent, yet more specifically at least 95 weight percent.
- Details relating to the preparation, characterization, and properties of the poly(phenylene ether)-polysiloxane block copolymer reaction product can be found in U.S. Pat. Nos. 8,017,697, 8,669,332, and 8,722,837 to Carrillo et al.
- In addition to the oxidative copolymerization method described above, a polyesterification method can be used to form the poly(phenylene ether)-polysiloxane block copolymer. When the polyesterification method is used, the product is a multiblock copolymer comprising at least two poly(phenylene ether) blocks and at least two polysiloxane blocks. Thus, in some embodiments, the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether)-polysiloxane multiblock copolymer that is the product of copolymerizing a hydroxy-diterminated poly(phenylene ether), a hydroxyaryl-diterminated polysiloxane, and an aromatic diacid chloride.
- The hydroxy-diterminated poly(phenylene ether) can have the structure
- wherein x and y are each independently 0 to about 100, provided that the sum of x and y is at least 2; each occurrence of Q1 is independent selected from the group consisting of halogen, unsubstituted or substituted C1-C12 hydrocarbylthio, unsubstituted or substituted C1-C12 hydrocarbyloxy, unsubstituted or substituted C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; each occurrence of Q2 is independently selected from the group consisting of hydrogen, halogen, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; and L has the structure
- wherein each occurrence of R5 and R6 is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbylthio, unsubstituted or substituted C1-C12 hydrocarbyloxy, unsubstituted or substituted C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; z is 0 or 1; and Y has a structure selected from the group consisting of
- wherein each occurrence of R7-R10 is independently hydrogen or C1-C12 hydrocarbyl.
- In some embodiments, the hydroxy-diterminated poly(phenylene ether) has the structure
- wherein each occurrence of Q3 is independently methyl or di-n-butylaminomethyl; and each occurrence of a and b is independently 0 to about 100, provided that the sum of a and b is 3 to 100. In some embodiments, the sum of a and b is 4 to 30.
- The aromatic diacid chloride used in the polyesterification method can be, for example, terephthaloyl chloride, isophthaloyl chloride, 4,4′-biphenyldicarbonyl chloride, 3,3′-biphenyldicarbonyl chloride, 3,4′-biphenyldicarbonyl chloride, 4,4′-oxybis(benzoyl chloride), 3,3′-oxybis(benzoyl chloride), 3,4′-oxybis(benzoyl chloride), 4,4′-sulfonylbis(benzoyl chloride), 3,3′-sulfonylbis(benzoyl chloride), 3,4′-sulfonylbis(benzoyl chloride), naphthalene-2,6-dicarbonyl chloride, or a mixture thereof. In some embodiments, the aromatic diacid chloride comprises terephthaloyl chloride.
- As noted above, when the poly(phenylene ether)-polysiloxane multiblock copolymer is prepared by the polyesterification method, it comprises at least two poly(phenylene ether) blocks and at least two polysiloxane blocks. However, it can contain many more of each type of block. For example, in some embodiments, the poly(phenylene ether)-polysiloxane multiblock copolymer comprises about 5 to about 25 poly(phenylene ether) blocks and about 10 to about 30 polysiloxane blocks.
- Additional details relating to the polyesterification method and the poly(phenylene ether)-polysiloxane multiblock copolymer prepared thereby can be found in U.S. Pat. No. 8,309,665 B2 to Kamalakaran et al. An alternative method of forming poly(phenylene ether)-polysiloxane multiblock copolymers is described in Cella et al.,
- The poly(phenylene ether)-polysiloxane copolymer can include a poly(phenylene ether)-polysiloxane graft copolymer. A poly(phenylene ether)-polysiloxane graft copolymer comprises a poly(phenylene ether) backbone and at least one polysiloxane graft at an internal (not terminal) phenylene ether unit of the poly(phenylene ether) backbone. Poly(phenylene ether)-polysiloxane graft copolymers can be prepared by oxidative copolymerization of a monohydric phenol, as defined above, and a phenol-polysiloxane macromer having the structure
- wherein R11 is halogen, unsubstituted or substituted C1-C12 hydrocarbylthio, unsubstituted or substituted C1-C12 hydrocarbyloxy, unsubstituted or substituted C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; R12 is hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbylthio, unsubstituted or substituted C1-C12 hydrocarbyloxy, unsubstituted or substituted C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; R13 is C2-C20 hydrocarbylene; each occurrence of R14 is independently hydrogen or C1-C12 hydrocarbyl; R15 is C1-C12 hydrocarbyl; and m is 3 to 100. In a specific embodiment, the monohydric phenol is 2,6-dimethylphenol, and in the phenol-polysiloxane macromer, R11 is methyl, R12 is hydrogen, R13 is trimethylene (—CH2—CH2—CH2—), each occurrence of R14 is methyl, R15 is methyl, and m is 20 to 60. In some embodiments, the molar ratio of monohydric phenol to phenol-polysiloxane macromere is 10:1 to 1000:1, specifically 20:1 to 100:1 during the oxidative copolymerization. In some embodiments, the weight percent siloxane in the poly(phenylene ether)-polysiloxane graft copolymer is 0.5 to 10 weight percent, specifically 1 to 8 weight percent. Additional details relating to poly(phenylene ether)-polysiloxane graft copolymers prepared by oxidative copolymerization can be found in U.S. Pat. No. 5,281,686 to Blohm et al. Poly(phenylene ether)-polysiloxane graft copolymers can also be prepared by redistribution of a poly(phenylene ether) in the presence of a hydroxyaryl-terminated polysiloxane. This procedure is described in U.S. Pat. No. 5,596,048 to Blohm et al.
- The composition can comprise a mixture of a poly(phenylene ether)-polysiloxane block copolymer and a poly(phenylene ether)-polysiloxane graft copolymer.
- In some embodiments, the composition comprises 0.025 to 5 weight percent of polysiloxane covalently bound in the poly(phenylene ether)-polysiloxane copolymer. In other words, the poly(phenylene ether)-polysiloxane copolymer contributes 0.025 to 5 weight percent of polysiloxane to the composition as a whole. In some embodiments, the covalently bound polysiloxane amount is 0.025 to 2 weight percent, specifically 0.05 to 1 weight percent, based on the total weight of the composition. In other embodiments, the covalently bound polysiloxane amount is 1 to 6 weight percent, specifically 2 to 4 weight percent, based on the total weight of the composition. In some embodiments, the polysiloxane content of the composition consists essentially of polysiloxane that has been incorporated into the poly(phenylene ether)-polysiloxane copolymer. In some embodiments, the poly(phenylene ether)-polysiloxane copolymer comprises 1 to 8 weight percent siloxane repeat units and 12 to 99 weight percent phenylene ether repeat units, based on the total weight of the poly(phenylene ether)-polysiloxane copolymer. Within these ranges, the amount of siloxane repeat units can be 2 to 7 weight percent, specifically 3 to 6 weight percent, more specifically 4 to 5 weight percent; and the amount of phenylene ether repeat units can be 93 to 98 weight percent, specifically 94 to 97 weight percent, more specifically 95 to 96 weight percent.
- The poly(phenylene ether)-polysiloxane copolymer can include relatively small amounts of very low molecular weight species. Thus, in some embodiments, the poly(phenylene ether)-polysiloxane copolymer comprises less than 25 weight percent of molecules having a molecular weight less than 10,000 atomic mass units, specifically 5 to 25 weight percent of molecules having a molecular weight less than 10,000 atomic mass units, more specifically 7 to 21 weight percent of molecules having a molecular weight less than 10,000 atomic mass units. In some embodiments, the molecules having a molecular weight less than 10,000 atomic mass units comprise 5 to 10 weight percent siloxane repeat units, specifically 6 to 9 weight percent siloxane repeat units.
- Similarly, the poly(phenylene ether)-polysiloxane copolymer can also include relatively small amounts of very high molecular weight species. Thus, in some embodiments, the poly(phenylene ether)-polysiloxane copolymer comprises less than 25 weight percent of molecules having a molecular weight greater than 100,000 atomic mass units, specifically 5 to 25 weight percent of molecules having a molecular weight greater than 100,000 atomic mass units, more specifically 7 to 23 weight percent of molecules having a molecular weight greater than 100,000 atomic mass units. In some embodiments, the molecules having a molecular weight greater than 100,000 atomic mass units comprise 3 to 6 weight percent siloxane repeat units, specifically 4 to 5 weight percent siloxane repeat units.
- The composition comprises 0.5 to 85 weight percent of the poly(phenylene ether)-polysiloxane copolymer, based on the total weight of the composition. In some embodiments, the poly(phenylene ether)-polysiloxane copolymer amount is 1 to 20 weight percent, specifically 2 to 10 weight percent. In other embodiments, the poly(phenylene ether)-polysiloxane copolymer amount is 30 to 85 weight percent, specifically 40 to 75 weight percent, more specifically 53 to 63 weight percent.
- In some embodiments, particularly those in which the amount of the poly(phenylene ether)-polysiloxane copolymer is less than 50 weight percent, it can be beneficial to include a second poly(phenylene ether) in the composition. As used herein, the term “second poly(phenylene ether)” refers to a poly(phenylene ether) that is not derived from the poly(phenylene ether)-polysiloxane block copolymer reaction. The second poly(phenylene ether) can be chemically the same as or different from the first poly(phenylene ether). Suitable first and second poly(phenylene ether)s include those comprising repeating structural units having the formula
- wherein each occurrence of Z1 is independently halogen, unsubstituted or substituted C1-C12 hydrocarbylthio, unsubstituted or substituted C1-C12 hydrocarbyloxy, unsubstituted or substituted C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl; and each occurrence of Z2 is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbylthio, unsubstituted or substituted C1-C12 hydrocarbyloxy, unsubstituted or substituted C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl.
- In some embodiments, the second poly(phenylene ether) has an intrinsic viscosity of 0.2 to 1 deciliter per gram measured by Ubbelohde viscometer at 25° C. in chloroform. Within this range, the second poly(phenylene ether) intrinsic viscosity can be 0.2 to 0.5 deciliter per gram, specifically 0.2 to 0.4 deciliter per gram, still more specifically 0.25 to 0.35 deciliter per gram.
- In some embodiments, the second poly(phenylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or a combination thereof. In some embodiments, the second poly(phenylene ether) comprises a poly(2,6-dimethyl-1,4-phenylene ether). In some embodiments, the second poly(phenylene ether) comprises a poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.2 to 0.4 deciliter per gram, specifically 0.25 to 0.35 deciliter per gram, measured by Ubbelohde viscometer at 25° C. in chloroform.
- When present, the second poly(phenylene ether) can be used in an amount of 5 to 84.5 weight percent, specifically 20 to 80 weight percent, more specifically 55 to 75 weight percent, based on the total weight of the composition.
- In addition to the poly(phenylene ether)-polysiloxane copolymer and the optional second poly(phenylene ether), the composition comprises a flame retardant. The flame retardant comprises an organophosphate ester, a phosphazene, or a combination thereof.
- In some embodiments, the flame retardant comprises an organophosphate ester. Exemplary organophosphate ester flame retardants include phosphate esters comprising phenyl groups, substituted phenyl groups, or a combination of phenyl groups and substituted phenyl groups, bis(aryl phosphate) esters based upon resorcinol such as, for example, resorcinol bis(diphenyl phosphate), as well as those based upon bisphenols such as, for example, bisphenol A bis(diphenyl phosphate). In some embodiments, the organophosphate ester is selected from tris(alkylphenyl) phosphates (for example, CAS Reg. No. 89492-23-9 or CAS Reg. No. 78-33-1), resorcinol bis(diphenyl phosphate) (CAS Reg. No. 57583-54-7), bisphenol A bis(diphenyl phosphate) (CAS Reg. No. 181028-79-5), triphenyl phosphate (CAS Reg. No. 115-86-6), tris(isopropylphenyl) phosphates (for example, CAS Reg. No. 68937-41-7), and combinations thereof.
- In some embodiments the organophosphate ester comprises a bis(aryl phosphate) having the formula
- wherein R is independently at each occurrence a C1-C12 alkylene group; R20 and R21 are independently at each occurrence a C1-C5 alkyl group; R16, R17, and R19 are independently a C1-C12 hydrocarbyl group; R18 is independently at each occurrence a C1-C12 hydrocarbyl group; n is 1 to 25; and s1 and s2 are independently an integer equal to 0, 1, or 2. In some embodiments OR16, OR17, OR18 and OR19 are independently derived from phenol, a monoalkylphenol, a dialkylphenol, or a trialkylphenol.
- As readily appreciated by one of ordinary skill in the art, the bis(aryl phosphate) is derived from a bisphenol. Exemplary bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane and 1,1-bis(4-hydroxypheny)ethane. In some embodiments, the bisphenol comprises bisphenol A.
- In some embodiments, the flame retardant comprises a phosphazene. A phosphazene is a compound comprising repeat units having the structure
- wherein each occurrence of R22 is independently C1-C6 alkoxy, unsubstituted or substituted phenoxy, or unsubstituted or substituted naphthyloxy. When present, the substituents on the phenoxy or naphthyloxy groups can be, for example, C1-C6 alkyl, C1-C6 alkoxy, or phenyl.
- In some embodiments, the phosphazene comprises a cyclic oligophosphazene having the structure
- wherein R22 is defined above and a is 3 to 12, specifically 3 to 6. In some embodiments, a is 3 and each occurrence of R22 is unsubstituted phenoxy.
- In some embodiments, the phosphazene comprises a linear oligophosphazene or polyphosphazene having the structure
- wherein R22 is defined above; b is 3 to 1,000; A is —N═P(O)(R22) or —N═P(R22)3; and B is —P(R22)4 or —P(O)(R22)2.
- The phosphazene can be a crosslinked polyphosphazene comprising a phenylene group, a biphenylene group, or a group having the structure
- wherein X is C1-C6 alkylidene, O, S, or SO2. This crosslinking group is typically directly bonded at each end to a phosphazene phosphorus atom.
- A mixture of at least two of cyclic oligophosphazenes, linear oligophosphazenes, linear polyphosphazenes, and crosslinked phosphazenes can be used. In some embodiments, the phosphazene comprises at last 80 weight percent cyclic phosphazenes, based on the weight of the phosphazene.
- Methods for making phosphazenes are known, and phosphazenes are commercially available as, for example, RABITLE™ FP-100 and RABITLE™ FP-110 from Fushimi Pharmaceutical Co., Ltd.; and IDB-Poretar-201 from ID-Biochem, and SPB-100 from Otsuka Chemical Company.
- In addition to the organophosphate ester, the phosphazene, or the combination thereof, the flame retardant can, optionally, further comprise a metal dialkylphosphinate, a nitrogen-containing flame retardant, a metal hydroxide, or a combination thereof.
- As used herein, the term “metal dialkylphosphinate” refers to a salt comprising at least one metal cation and at least one dialkylphosphinate anion. In some embodiments, the metal dialkylphosphinate has the formula
- wherein Ra and Rb are each independently C1-C6 alkyl; M is calcium, magnesium, aluminum, or zinc; and d is 2 or 3. Examples of Ra and Rb include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl. In some embodiments, Ra and Rb are ethyl, M is aluminum, and d is 3 (that is, the metal dialkylphosphinate is aluminum tris(diethylphosphinate)).
- In some embodiments, the metal dialkylphosphinate is in particulate form. The metal dialkylphosphinate particles may have a median particle diameter (D50) less than or equal to 40 micrometers, or, more specifically, a D50 less than or equal to 30 micrometers, or, even more specifically, a D50 less than or equal to 25 micrometers. Additionally, the metal dialkylphosphinate may be combined with a polymer, such as the poly(phenylene ether)-polysiloxane block copolymer reaction product, the optional second poly(phenylene ether), or the optional impact modifier, to form a masterbatch. The metal dialkylphosphinate masterbatch comprises the metal dialkylphosphinate in an amount greater than is present in the thermoplastic composition. Employing a masterbatch for the addition of the metal dialkylphosphinate to the other components of the composition can facilitate addition and improve distribution of the metal dialkylphosphinate.
- Nitrogen-containing flame retardants include those comprising a nitrogen-containing heterocyclic base and a phosphate or pyrophosphate or polyphosphate acid. In some embodiments, the nitrogen-containing flame retardant has the formula
- wherein g is 1 to 10,000, and the ratio of f to g is 0.5:1 to 1.7:1, specifically 0.7:1 to 1.3:1, more specifically 0.9:1 to 1.1:1. It will be understood that this formula includes species in which one or more protons are transferred from the phosphate group(s) to the melamine group(s). When g is 1, the nitrogen-containing flame retardant is melamine phosphate (CAS Reg. No. 20208-95-1). When g is 2, the nitrogen-containing flame retardant is melamine pyrophosphate (CAS Reg. No. 15541 60-3). When g is, on average, greater than 2, the nitrogen-containing flame retardant is a melamine polyphosphate (CAS Reg. No. 56386-64-2). In some embodiments, the nitrogen-containing flame retardant is melamine pyrophosphate, melamine polyphosphate, or a mixture thereof. In some embodiments in which the nitrogen-containing flame retardant is melamine polyphosphate, g has an average value of greater than 2 to 10,000, specifically 5 to 1,000, more specifically 10 to 500. In some embodiments in which the nitrogen-containing flame retardant is melamine polyphosphate, g has an average value of greater than 2 to 500. Methods for preparing melamine phosphate, melamine pyrophosphate, and melamine polyphosphate are known in the art, and all are commercially available. For example, melamine polyphosphates may be prepared by reacting polyphosphoric acid and melamine, as described, for example, in U.S. Pat. No. 6,025,419 to Kasowski et al., or by heating melamine pyrophosphate under nitrogen at 290° C. to constant weight, as described in U.S. Pat. No. 6,015,510 to Jacobson et al. In some embodiments, the nitrogen-containing flame retardant comprises melamine cyanurate.
- The nitrogen-containing flame retardant can have a low volatility. For example, in some embodiments, the nitrogen-containing flame retardant exhibits less than 1 percent weight loss by thermogravimetric analysis when heated at a rate of 20° C. per minute from 25 to 280° C., specifically 25 to 300° C., more specifically 25 to 320° C.
- Suitable metal hydroxides include all those capable of providing fire retardancy, as well as combinations of such metal hydroxides. The metal hydroxide can be chosen to have substantially no decomposition during processing of the fire additive composition and/or flame retardant thermoplastic composition. Substantially no decomposition is defined herein as amounts of decomposition that do not prevent the flame retardant additive composition from providing the desired level of fire retardancy. Exemplary metal hydroxides include, but are not limited to, magnesium hydroxide (for example, CAS Reg. No. 1309-42-8), aluminum hydroxide (for example, CAS Reg. No. 21645-51-2), cobalt hydroxide (for example, CAS Reg. No. 21041-93-0), and combinations thereof. In some embodiments, the metal hydroxide comprises magnesium hydroxide. In some embodiments the metal hydroxide has an average particle size less than or equal to 10 micrometers and/or a purity greater than or equal to 90 weight percent. In some embodiments it is desirable for the metal hydroxide to contain substantially no water, for example as evidenced by a weight loss of less than 1 weight percent upon drying at 120° C. for 1 hour. In some embodiments the metal hydroxide can be coated, for example, with stearic acid or other fatty acid.
- The amount of the flame retardant can be 5 to 25 weight percent, based on the total weight of the composition. In some embodiments, the amount of the flame retardant is 5 to 20 weight percent, specifically 5 to 15 weight percent. In other embodiments, the amount of the flame retardant is 10 to 25 weight percent, specifically 15 to 25 weight percent.
- In addition to the poly(phenylene ether)-polysiloxane block copolymer reaction product, the optional second poly(phenylene ether), and the flame retardant, the composition comprises a reinforcing filler. Reinforcing fillers include, for example, glass fibers, carbon fibers, wollastonite, halloysite, clays, talcs, micas, glass flakes, solid glass beads, hollow glass beads, solid ceramic beads, hollow ceramic beads, and combinations thereof. In some embodiments, the reinforcing filler comprises or consists of glass fibers.
- Suitable glass fibers include those based on E, A, C, ECR, R, S, D, and NE glasses, as well as quartz. In some embodiments, the glass fiber has a diameter of 2 to 30 micrometers, specifically 5 to 25 micrometers, more specifically 10 to 15 micrometers. In some embodiments, the length of the glass fibers before compounding is 2 to 7 millimeters, specifically 3 to 5 millimeters. Suitable glass fiber is commercially available from suppliers including, for example, Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.
- The reinforcing filler can, optionally, include an adhesion promoter to improve its compatibility with the poly(phenylene ether)-polysiloxane block copolymer reaction product. Adhesion promoters include chromium complexes, silanes, titanates, zircoaluminates, propylene maleic anhydride copolymers, reactive cellulose esters, and the like.
- The reinforcing filler can be used in an amount of 10 to 35 weight percent, based on the total weight of the composition. In some embodiments, the reinforcing filler amount is 10 to 25 weight percent, specifically 10 to 20 weight percent. In other embodiments, the reinforcing filler amount is 15 to 30 weight percent, specifically 15 to 25 weight percent.
- The composition can, optionally, further include an impact modifier Impact modifiers include, for example, rubber-modified polystyrenes, unhydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, hydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, acrylate core-shell impact modifiers (e.g., those having a crosslinked poly(butyl acrylate) core and a grafted poly(methyl methacrylate) shell), and combinations thereof.
- The impact modifier can include a rubber-modified polystyrene. Rubber-modified polystyrene comprises polystyrene and polybutadiene. Rubber-modified polystyrenes are sometimes referred to as “high-impact polystyrenes” or “HIPS”. In some embodiments, the rubber-modified polystyrene comprises 80 to 96 weight percent polystyrene, specifically 88 to 94 weight percent polystyrene; and 4 to 20 weight percent polybutadiene, specifically 6 to 12 weight percent polybutadiene, based on the weight of the rubber-modified polystyrene. Suitable rubber-modified polystyrenes are commercially available as, for example, HIPS3190 from SABIC Innovative Plastics.
- The impact modifier can include an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene. For brevity, this component is referred to as an “unhydrogenated block copolymer”. The unhydrogenated block copolymer can comprise 10 to 90 weight percent of poly(alkenyl aromatic) content and 90 to 10 weight percent of poly(conjugated diene) content, based on the weight of the unhydrogenated block copolymer. In some embodiments, the unhydrogenated block copolymer is a low poly(alkenyl aromatic content) unhydrogenated block copolymer in which the poly(alkenyl aromatic) content is 10 to less than 40 weight percent, specifically 20 to 35 weight percent, more specifically 25 to 35 weight percent, yet more specifically 30 to 35 weight percent, all based on the weight of the low poly(alkenyl aromatic) content unhydrogenated block copolymer. In other embodiments, the unhydrogenated block copolymer is a high poly(alkenyl aromatic) content unhydrogenated block copolymer in which the poly(alkenyl aromatic) content is 40 to 90 weight percent, specifically 50 to 80 weight percent, more specifically 60 to 70 weight percent, all based on the weight of the high poly(alkenyl aromatic) content unhydrogenated block copolymer.
- In some embodiments, the unhydrogenated block copolymer has a weight average molecular weight of 40,000 to 400,000 atomic mass units. The number average molecular weight and the weight average molecular weight can be determined by gel permeation chromatography and based on comparison to polystyrene standards. In some embodiments, the unhydrogenated block copolymer has a weight average molecular weight of 200,000 to 400,000 atomic mass units, specifically 220,000 to 350,000 atomic mass units. In other embodiments, the unhydrogenated block copolymer has a weight average molecular weight of 40,000 to 200,000 atomic mass units, specifically 40,000 to 180,000 atomic mass units, more specifically 40,000 to 150,000 atomic mass units.
- The alkenyl aromatic monomer used to prepare the unhydrogenated block copolymer can have the structure
- wherein R23 and R24 each independently represent a hydrogen atom, a C1-C8 alkyl group, or a C2-C8 alkenyl group; R25 and R29 each independently represent a hydrogen atom, a C1-C8 alkyl group, a chlorine atom, or a bromine atom; and R26, R27, and R28 each independently represent a hydrogen atom, a C1-C8 alkyl group, or a C2-C8 alkenyl group, or R26 and R27 are taken together with the central aromatic ring to form a naphthyl group, or R27 and R28 are taken together with the central aromatic ring to form a naphthyl group. Specific alkenyl aromatic monomers include, for example, styrene, chlorostyrenes such as p-chlorostyrene, methylstyrenes such as alpha-methylstyrene and p-methylstyrene, and t-butylstyrenes such as 3-t-butylstyrene and 4-t-butylstyrene. In some embodiments, the alkenyl aromatic monomer is styrene.
- The conjugated diene used to prepare the unhydrogenated block copolymer can be a C4-C20 conjugated diene. Suitable conjugated dienes include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and combinations thereof. In some embodiments, the conjugated diene is 1,3-butadiene, 2-methyl-1,3-butadiene, or a combination thereof. In some embodiments, the conjugated diene consists of 1,3-butadiene.
- The unhydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene. The arrangement of blocks (A) and (B) includes a linear structure, a grafted structure, and a radial teleblock structure with or without a branched chain. Linear block copolymers include tapered linear structures and non-tapered linear structures. In some embodiments, the unhydrogenated block copolymer has a tapered linear structure. In some embodiments, the unhydrogenated block copolymer has a non-tapered linear structure. In some embodiments, the unhydrogenated block copolymer comprises a (B) block that comprises random incorporation of alkenyl aromatic monomer. Linear block copolymer structures include diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block), and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures as well as linear structures containing 6 or more blocks in total of (A) and (B), wherein the molecular weight of each (A) block can be the same as or different from that of other (A) blocks, and the molecular weight of each (B) block can be the same as or different from that of other (B) blocks. In some embodiments, the unhydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.
- In some embodiments, the unhydrogenated block copolymer excludes the residue of monomers other than the alkenyl aromatic compound and the conjugated diene. In some embodiments, the unhydrogenated block copolymer consists of blocks derived from the alkenyl aromatic compound and the conjugated diene. It does not comprise grafts formed from these or any other monomers. It also consists of carbon and hydrogen atoms and therefore excludes heteroatoms.
- In some embodiments, the unhydrogenated block copolymer includes the residue of one or more acid functionalizing agents, such as maleic anhydride.
- In some embodiments, the unhydrogenated block copolymer comprises a polystyrene-polybutadiene-polystyrene triblock copolymer. In some embodiments, the unhydrogenated block copolymer comprises a polystyrene-polyisoprene-polystyrene triblock copolymer.
- Methods for preparing unhydrogenated block copolymers are known in the art and unhydrogenated block copolymers are commercially available. Illustrative commercially available unhydrogenated block copolymers include the polystyrene-polybutadiene-polystyrene triblock copolymers from Kraton Performance Polymers Inc. under the trade names Kraton™ D1101 and D1102; and the styrene-butadiene radial teleblock copolymers from Chevron Phillips Chemical Company under the trade names K-RESIN™ KK38, KR01, KR03, and KR05.
- The impact modifier can be a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene. For brevity, this component is referred to as a “hydrogenated block copolymer”. The hydrogenated block copolymer is the same as the unhydrogenated block copolymer, except that in the hydrogenated block copolymer the aliphatic unsaturated group content in the block (B) derived from a conjugated diene has been at least partially reduced by hydrogenation. In some embodiments, the aliphatic unsaturation in the (B) block is reduced by at least 50 percent, specifically at least 70 percent, more specifically at least 90 percent.
- Illustrative commercially available hydrogenated block copolymers include the polystyrene-poly(ethylene-propylene) diblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1701 and G1702; the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1641, G1650, G1651, G1654, G1657, G1726, G4609, G4610, GRP-6598, MD-6932M, MD-6933, and MD-6939; the polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1730; the maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1901, G1924, and MD-6684; the maleic anhydride-grafted polystyrene-poly(ethylene-butylene-styrene)-polystyrene triblock copolymer available from Kraton Performance Polymers Inc. as KRATON™ MD-6670; the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer comprising 67 weight percent polystyrene available from Asahi Kasei Elastomer as TUFTEC™ H1043; the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer comprising 42 weight percent polystyrene available from Asahi Kasei Elastomer as TUFTEC™ H1051; the polystyrene-poly(butadiene-butylene)-polystyrene triblock copolymers available from Asahi Kasei Elastomer as TUFTEC™ P1000 and P2000; the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer comprising 60 weight polystyrene available from Kuraray as SEPTON™ S8104; the polystyrene-poly(ethylene-ethylene/propylene)-polystyrene triblock copolymers available from Kuraray as SEPTON™ S4044, S4055, S4077, and S4099; and the polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymer comprising 65 weight percent polystyrene available from Kuraray as SEPTON™ S2104.
- In some embodiments, the impact modifier is a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a polystyrene content of 25 to 35 weight percent and a weight average molecular weight of 200,000 to 400,000 atomic mass units.
- When present, the impact modifier can be used in an amount of 1 to 10 weight percent, specifically 1 to 5 weight percent, based on the total weight of the composition.
- The composition can, optionally, further comprise a hydrocarbon resin. Examples of hydrocarbon resins are aliphatic hydrocarbon resins, hydrogenated aliphatic hydrocarbon resins, aliphatic/aromatic hydrocarbon resins, hydrogenated aliphatic/aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, hydrogenated cycloaliphatic resins, cycloaliphatic/aromatic hydrocarbon resins, hydrogenated cycloaliphatic/aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, terpene resins, hydrogenated terpene resins, terpene-phenol resins, rosins, and rosin esters, hydrogenated rosins and rosin esters, and mixtures thereof. As used herein, “hydrogenated”, when referring to the hydrocarbon resin, includes fully, substantially, and partially hydrogenated resins. Suitable aromatic resins include aromatic modified aliphatic resins, aromatic modified cycloaliphatic resins, and hydrogenated aromatic hydrocarbon resins having an aromatic content of 1 to 30 weight percent. Any of the above resins can be grafted with an unsaturated ester or anhydride using methods known in the art. Such grafting can provide enhanced properties to the resin. In some embodiments, the hydrocarbon resin is a hydrogenated aromatic hydrocarbon resin.
- Suitable hydrocarbon resins are commercially available and include, for example, EMPR™ 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 116, 117, and 118 resins, and OPPERA™ resins, available from ExxonMobil Chemical Company; ARKON™ P140, P125, P115, M115, and M135, and SUPER ESTER™ rosin esters available from Arakawa Chemical Company of Japan; SYLVARES™ polyterpene resins, styrenated terpene resins and terpene phenolic resins available from Arizona Chemical Company; SYLVATAC™ and SYLVALITE™ rosin esters available from Arizona Chemical Company; NORSOLENE™ aliphatic aromatic resins available from Cray Valley; DERTOPHENE™ terpene phenolic resins and DERCOLYTE™ polyterpene resins available from DRT Chemical Company; EASTOTAC™ resins, PICCOTAC™ resins, REGALITE™ and REGALREZ™ hydrogenated cycloaliphatic/aromatic resins, and PICCOLYTE™ and PERMALYN™ polyterpene resins, rosins, and rosin esters available from Eastman Chemical Company; WINGTACK™ resins available from Goodyear Chemical Company; coumarone/indene resins available from Neville Chemical Company; QUINTONE™ acid modified C5 resins, C5/C9 resins, and acid-modified C5/C9 resins available from Nippon Zeon; and CLEARON™ hydrogenated terpene resins available from Yasuhara. In some embodiments, the hydrocarbon resin is a hydrogenated terpene resin. In some embodiments, the hydrocarbon resin is a saturated polyalicyclic hydrocarbon resin.
- The hydrocarbon resin can have a softening point of at least 120° C. measured according to ASTM E28. Specifically, the softening point can be 120 to 180° C., specifically 130 to 170° C., more specifically 140 to 160° C. In some embodiments, the hydrocarbon resin comprises a hydrogenated alicyclic hydrocarbon resin, a hydrogenated terpene resin, or a combination thereof. In some embodiments, the hydrocarbon resin comprises a hydrogenated alicyclic hydrocarbon resin having a softening point of 120 to 135° C. An example of such a resin is ARKON™ P125 having a softening point of about 125° C., available from Arakawa Chemical Company, In some embodiments, the hydrocarbon resin comprises a hydrogenated alicyclic hydrocarbon resin having a softening point of 135 to 145° C. An example of such a resin is ARKON™ P140 having a softening point of about 140° C., available from Arakawa Chemical Company, In some embodiments, the hydrocarbon resin comprises a hydrogenated terpene resin having a softening point of 145 to 160° C. An example of such a resin is CLEARON™ P150 available from Yasuhara.
- When present, the hydrocarbon resin can be used in an amount of 1 to 8 weight percent, specifically 2 to 6 weight percent, based on the total weight of the composition.
- The composition can, optionally, further comprise a trihydrocarbyl phosphite. Trihydrocarbyl phosphites have the general structure P(OR30)3, wherein each occurrence of R30 is independently C1-C18 hydrocarbyl. In some embodiments, each R30 is independently C6-C18 alkyl. In other embodiments, at least one R30 is C6-C18 aryl. In some embodiments, each occurrence of R19 is independently an unsubstituted or substituted C6-C18 aryl. Suitable trihydrocarbyl phosphites include, for example, trioctyl phosphite, tridecyl phosphite, tridodecyl phosphite, phenyl didecyl phosphite, decyl diphenyl phosphite, triphenyl phosphite, tritolyl phosphites, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and the like, and combinations thereof. Suitable trihydrocarbyl phosphites further include spiro diphosphites such as, for example, 3,9-bis[2,4-bis(1,1-dimethylethyl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (CAS Reg. No. 26741-53-7; commercially available from Ciba under the trade name IRGAFOS™ 126). In some embodiments, the aryl phosphite comprises tris(2,4-di-tert-butylphenyl)phosphite (CAS Reg. No. 31570-04-4). In some embodiments, the aryl phosphite comprises bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (CAS Reg. No. 26741-53-7).
- When present, the trihydrocarbyl phosphite can be used in an amount of 0.05 to 1 weight percent, specifically 0.1 to 0.5 weight percent, based on the total weight of the composition.
- The composition can, optionally, further comprise linear low density polyethylene (LLDPE). Linear low density polyethylene is a copolymer of ethylene and a longer chain olefin such as 1-butene, 1-hexene, or 1-octene. In some embodiments, the linear low density polyethylene is a copolymer of ethylene and 1-butene. Linear low density polyethylene typically has a density of about 0.92 grams/centimeter3. When present, the linear low density polyethylene can be used in an amount of 0.5 to 5 weight percent, specifically 0.5 to 3 weight percent, based on the total weight of the composition.
- The composition can, optionally, further comprise one or more additives known in the thermoplastics art. For example, the composition can, optionally, further comprise an additive chosen from stabilizers, mold release agents, lubricants, processing aids, drip retardants, nucleating agents, UV blockers, dyes, pigments, antioxidants, anti-static agents, blowing agents, mineral oil, metal deactivators, antiblocking agents, and the like, and combinations thereof. When present, such additives are typically used in a total amount of less than or equal to 5 weight percent, specifically less than or equal to 4 weight percent, more specifically less than or equal to 3 weight percent, based on the total weight of the composition.
- The composition can, optionally, exclude polymers other than those required. For example, the composition can comprise less than or equal to 1 weight percent of each of polyamides and polyesters. In some embodiments, the composition comprises less than or equal to 4 weight percent, specifically less than or equal to 3 weight percent, more specifically less than or equal to 2 weight percent, of polyolefins. In some embodiments, the composition comprises less than or equal to 1 weight percent of polyolefins other than linear low density polyethylene. In other embodiments, the composition comprises less than or equal to 1 weight percent of any polyolefins.
- One advantage of the composition is that it can achieve a UL 94 V-0 rating without using the halogenated flame retardants that are typically employed in glass-filled polyester compositions utilized for similar product applications. Thus, the composition can comprise less than or equal to 0.1 weight percent halogens, specifically less than or equal to 0.01 weight percent halogens, based on the total weight of the composition. In some embodiments, composition is halogen-free.
- In some embodiments, the article is a fuser holder, and the composition comprises 2 to 10 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product, and further comprises 55 to 75 weight percent of a second poly(phenylene ether). In these embodiments, the reinforcing filler amount is, optionally, 10 to 20 weight percent, and the reinforcing filler optionally comprises glass fibers. Also in these embodiments, the composition optionally further comprises 1 to 5 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- In a very specific embodiment, the article is a fuser holder, the poly(phenylene ether)-polysiloxane copolymer comprises a poly(phenylene ether)-polysiloxane block copolymer provided in the form of a poly(phenylene ether)-polysiloxane block copolymer reaction product, the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- and
a polysiloxane block having the structure - wherein n is 30 to 60; the reinforcing filler comprises glass fibers; the flame retardant comprises bisphenol A bis(diphenyl phosphate); the composition comprises 2 to 10 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 5 to 15 weight percent of the flame retardant, and 10 to 20 weight percent of the reinforcing filler; and the composition further comprises 55 to 75 weight percent of a second poly(phenylene ether) comprising poly(2,6-dimethyl-1,4-phenylene ether), and 1 to 5 weight percent of a polystyrene-poly(ethylene-butylene)-polystyrene block copolymer.
- In some embodiments, the article is selected from the group consisting of fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes, and the composition comprises 53 to 63 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product. In these embodiments, the reinforcing filler amount is, optionally, 15 to 25 weight percent, and the reinforcing filler optionally comprises glass fibers. Also in these embodiments, the composition optionally comprises 0 to 4 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene. Also in these embodiments, the composition optionally comprises 0.5 to 3 weight percent of a linear low density polyethylene.
- In a very specific embodiment, the article is selected from the group consisting of fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes; the poly(phenylene ether)-polysiloxane copolymer comprises a poly(phenylene ether)-polysiloxane block copolymer provided in the form of a poly(phenylene ether)-polysiloxane block copolymer reaction product; the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- and
a polysiloxane block having the structure - wherein n is 30 to 60; the reinforcing filler comprises glass fibers; the flame retardant comprises bisphenol A bis(diphenyl phosphate); the composition comprises 53 to 63 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 15 to 25 weight percent of the flame retardant, and 15 to 25 weight percent of the reinforcing filler; and the composition further comprises 0.5 to 3 weight percent of a linear low density polyethylene.
- As described above, the article can be a fuser holder for an electrophotographic copier, a fan blade, a battery part for hybrid and electric vehicles, a part for an automotive kinetic energy recovery system, or an electric vehicle junction box. Other than their being fabricated with the composition described herein, such articles are known, as are methods for their fabrication. For example, U.S. Pat. No. 5,499,087 of Hiraoka et al. describes a fuser holder for an electrophotographic copier. Suitable methods of forming such articles include single layer and multilayer sheet extrusion, injection molding, blow molding, film extrusion, profile extrusion, pultrusion, compression molding, thermoforming, pressure forming, hydroforming, vacuum forming, and the like. Combinations of the foregoing article fabrication methods can be used. In some embodiments, the article is formed by injection molding. In some of these embodiments, the injection molding uses a barrel temperature of 285 to 330° C., specifically 295 to 325° C., and a mold temperature of 60 to 120° C., specifically 80 to 110° C.
- All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Each range disclosed herein constitutes a disclosure of any point or sub-range lying within the disclosed range.
- The invention includes at least the following embodiments.
- An article comprising a composition, wherein the article is selected from the group consisting of fuser holders for electrophotographic copiers, fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes; wherein the composition comprises 0.5 to 85 weight percent of a poly(phenylene ether)-polysiloxane copolymer comprising a poly(phenylene ether)-polysiloxane block copolymer, a poly(phenylene ether)-polysiloxane graft copolymer, or a combination thereof; 5 to 25 weight percent of a flame retardant comprising an organophosphate ester, a phosphazene, or a combination thereof; and 10 to 35 weight percent of a reinforcing filler; wherein all weight percent values are based on the total weight of the composition; provided that when the article is a fuser holder, the composition comprises 2 to 10 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the a poly(phenylene ether)-polysiloxane block copolymer and a first a poly(phenylene ether), and further comprises 55 to 75 weight percent of a second poly(phenylene ether).
- The article of embodiment 1, wherein the poly(phenylene ether)-polysiloxane copolymer comprises the poly(phenylene ether)-polysiloxane block copolymer.
- The article of embodiment 2, wherein composition comprises a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether), and wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- and
a polysiloxane block having the structure - wherein n is 30 to 60.
- The article of embodiment 2, wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether)-polysiloxane multiblock copolymer.
- The article of embodiment 1, wherein the poly(phenylene ether)-polysiloxane copolymer comprises the poly(phenylene ether)-polysiloxane graft copolymer.
- The article of any of embodiments 1-5, wherein the reinforcing filler is selected from the group consisting of glass fibers, carbon fibers, wollastonite, halloysite, clays, talcs, micas, glass flakes, solid glass beads, hollow glass beads, solid ceramic beads, hollow ceramic beads, and combinations thereof.
- The article of any of embodiments 1-5, wherein the reinforcing filler comprises glass fibers.
- The article of any of embodiments 1-7, wherein the flame retardant comprises the organophosphate ester.
- The article of embodiment 8, wherein the organophosphate ester comprises bisphenol A bis(diphenyl phosphate).
- The article of any of embodiments 1-9, wherein the flame retardant comprises the phosphazene.
- The article of embodiment 10, wherein the flame retardant comprises a cyclic oligo(bis(phenoxy)phosphazene), a linear oligo(bis(phenoxy)phosphazene), a linear poly(bis(phenoxy)phosphazene), a crosslinked poly(bis(phenoxy)phosphazene), or a combination thereof.
- The article of any of embodiments 1-11, wherein the composition further comprises 1 to 10 weight percent of an impact modifier selected from the group consisting of rubber-modified polystyrenes, unhydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, hydrogenated block copolymers of an alkenyl aromatic monomer and a conjugated diene, acrylate core-shell impact modifiers, and combinations thereof.
- The article of embodiment 1, wherein the article is a fuser holder; and wherein the composition comprises 2 to 10 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether); and wherein the composition further comprises 55 to 75 weight percent of a second poly(phenylene ether).
- The article of embodiment 13, wherein the composition comprises 10 to 20 weight percent of the reinforcing filler, and the reinforcing filler comprises glass fibers.
- The article of embodiment 13 or 14, wherein the composition further comprises 1 to 5 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- The article of embodiment 1, wherein the article is a fuser holder; wherein the composition comprises a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether); wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- and
a polysiloxane block having the structure - wherein n is 30 to 60; wherein the first poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether); wherein the reinforcing filler comprises glass fibers; wherein the flame retardant comprises bisphenol A bis(diphenyl phosphate); wherein the composition comprises 2 to 10 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 5 to 15 weight percent of the flame retardant, and 10 to 20 weight percent of the reinforcing filler; and wherein the composition further comprises 55 to 75 weight percent of a second poly(phenylene ether) comprising poly(2,6-dimethyl-1,4-phenylene ether), and 1 to 5 weight percent of a polystyrene-poly(ethylene-butylene)-polystyrene block copolymer.
- The article of embodiment 1, wherein the article is selected from the group consisting of fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes; and wherein the composition comprises 53 to 63 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether).
- The article of embodiment 17, wherein the composition comprises 15 to 25 weight percent of the reinforcing filler, and the reinforcing filler comprises glass fibers.
- The article of embodiment 17 or 18, wherein the composition comprises 0 to 4 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene.
- The article of any of embodiments 17-19, wherein the composition further comprises 0.5 to 3 weight percent of a linear low density polyethylene.
- The article of embodiment 1, wherein the article is selected from the group consisting of fan blades, battery parts for hybrid and electric vehicles, parts for automotive kinetic energy recovery systems, and electric vehicle junction boxes; wherein the composition comprises a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising the poly(phenylene ether)-polysiloxane block copolymer and a first poly(phenylene ether); wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block comprising phenylene ether repeat units having the structure
- and
a polysiloxane block having the structure - wherein n is 30 to 60; wherein the reinforcing filler comprises glass fibers; wherein the flame retardant comprises bisphenol A bis(diphenyl phosphate); wherein the composition comprises 53 to 63 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 15 to 25 weight percent of the flame retardant, and 15 to 25 weight percent of the reinforcing filler; and wherein the composition further comprises 0.5 to 3 weight percent of a linear low density polyethylene.
- The invention is further illustrated by the following non-limiting examples.
- These comparative examples utilize poly(phenylene ether) homopolymer, rather than poly(phenylene ether)-polysiloxane block copolymer reaction product. Components used to prepare the compositions are summarized in Table 1.
-
TABLE 1 Component Description PPE 0.46 Poly(2,6-dimethyl-1,4-phenylene ether), CAS Reg. No. 25134-01-4, having an intrinsic viscosity of about 0.46 deciliter per gram measured in chloroform at 25° C.; available as PPO ™ from SABIC Innovative Plastics. PPE 0.40 Poly(2,6-dimethyl-1,4-phenylene ether), CAS Reg. No. 25134-01-4, having an intrinsic viscosity of about 0.40 deciliter per gram measured in chloroform at 25° C.; available as PPO ™ 640 from SABIC Innovative Plastics. PPE 0.33 Poly(2,6-dimethyl-1,4-phenylene ether), CAS Reg. No. 25134-01-4, having an intrinsic viscosity of about 0.33 deciliter per gram measured in chloroform at 25° C.; available as PPO ™ 630 from SABIC Innovative Plastics. PPE 0.30 Poly(2,6-dimethyl-1,4-phenylene ether), CAS Reg. No. 25134-01-4, having an intrinsic viscosity of about 0.30 deciliter per gram measured in chloroform at 25° C.; available as PPO ™ 808 from SABIC Innovative Plastics. PPE-Si A mixture of poly(2,6-dimethyl-1,4-phenylene ether) (CAS Reg. No. 24938-67-8) and poly(2,6-dimethyl-1,4-phenylene ether)-polydimethylsiloxane block copolymer (CAS Reg. No. 1202019-56-4), the mixture having a polysiloxane content of about 5 weight percent and an intrinsic viscosity of about 0.4 deciliter per gram as measured in chloroform at 25° C.; prepared according to the procedure of U.S. Pat. No. 8,017,697 to Carrillo et al., Example 16. SEBS Polystyrene-poly(ethylene/butylene)-polystyrene triblock copolymer, CAS Reg. No. 66070-58-4, having a polystyrene content of 30-33 weight percent and a weight average molecular weight of 240,000-301,000 atomic mass units; obtained as KRATON ™ G1651 from Kraton Performance Polymers Inc. AO 168 Tris(2,4-di-tert-butylphenyl) phosphite, CAS Reg. No. 31570-04-4, available from BASF Corp. as IRGAFOS ™ 168, or from Chemtura as ALKANOX ™ 240. AO 626 Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, CAS Reg. No. 26741- 53-7, available from Chemtura as ULTRANOX ™ 626 HCR Saturated polyalicyclic hydrocarbon resin, CAS Reg. No. 4742-16-1, available from Arakawa Chemical as ARKON ™ P-125. HIPS Rubber-modified polystyrene, CAS Reg. No. 9003-55-8, available from SABIC Innovative Plastics as HIPS3190. Clay Water-washed kaolin clay, CAS Reg. No. 1332-58-7, available as KaMin POLYFIL ™ HG90 from KaMin Performance Minerals. Mica Phlogopite mica, CAS Reg. No. 12001-26-2, available from Imerys Performance Minerals as SUZORITE ™ HK-200. Glass Fiber Chopped glass fiber having a diameter of about 14 micrometers and a pre- compounded length of about 4 millimeters; available from Owens Corning as 122Y-14C. Carbon Black Carbon black pigment, CAS Reg. No. 1333-86-4, available from Cabot as BLACK PEARLS ™ 800 or MONARCH ™ 800. LLDPE Linear low density polyethylene (copolymer of ethylene and 1-butene), CAS Reg. No. 25087-34-7, having a density of 0.925 grams per cubic centimeter and a melt volume flow rate of 20 cubic centimeters per 10 minutes at 190° C. and 2.16 kilogram load, available from ExxonMobil as ESCORENE ™ LL5100.09. MgO Magnesium oxide, CAS Reg. No. 1309-48-4, available from Kyowa Chemical Co. Ltd. as KYOWAMAG ™ 150. ZnS Zinc sulfide, CAS Reg. No. 1314-98-3, available from Sachtleben Chemie GmbH as SACHTOLITH ™ HD-S. But-TPP t-Butylated triphenyl phosphate, CAS Reg. No. 220352-35-2, available as PHOSFLEX ™ 71B from Supresta LLC. BPADP Bisphenol A bis(diphenyl phosphate), CAS Reg. No. 181028-79-5; obtained as FYROFLEX ™ BDP from Supresta LLC, or REOFOS ™ BAPP from Great Lakes Chemical Co. Ltd. - Resin compositions were compounded on a 30 millimeter Werner & Pfleiderer ZSK twin-screw extruder operating at 350 rotations per minute and a throughput of 18 kilograms per hour (40 pounds per hour) and using barrel set temperatures of 240° C./260° C./290° C./290° C./290° C. from the feed port to die. Glass fibers were added downstream to the extruder, while all other solid components were added at the feed throat and the liquid flame retardant (But-TPP or BPADP) was injected at a port between the feed throat and the glass fiber feed location. The compounded resins were pelletized by strand-cutting.
- Test articles for ASTM determinations of heat deflection temperature and flexural properties were injection molded on a 120 Ton VanDorn injection molding machine using a barrel temperature of 288-310° C. (550-590° F.) and a mold temperature of about 88° C. (about 190° F.). Flame bars with 1.0 or 1.5 millimeter thickness were injection molded on an 80 Ton VanDorn injection molding machine using a barrel temperature of 299-321° C. (570-610° F.) and a mold temperature of 88-99° C. (190-210° F.).
- Flame retardancy of injection molded flame bars was determined according to Underwriter's Laboratory Bulletin 94 “Tests for Flammability of Plastic Materials, UL 94”, 20 mm Vertical Burning Flame Test. Before testing, flame bars with a thickness of 1.0 or 1.5 millimeters were conditioned at 23° C. and 50% relative humidity for at least 24 hours. In the UL 94 20 mm Vertical Burning Flame Test, a set of ten flame bars was tested. For each bar, a flame was applied to the bar then removed, and the time required for the bar to self-extinguish (first afterflame time, t1) was noted. The flame was then reapplied and removed, and the time required for the bar to self-extinguish (second afterflame time, t2) and the post-flame glowing time (afterglow time, t3) were noted. To achieve a rating of V-0, the afterflame times t1 and t2 for each individual specimen must have been less than or equal to 10 seconds; and the total afterflame time for all ten specimens (t1 plus t2 for all ten specimens) must have been less than or equal to 100 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2+t3) must have been less than or equal to 30 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops. To achieve a rating of V-1, the afterflame times t1 and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all ten specimens (t1 plus t2 for all ten specimens) must have been less than or equal to 500 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2+t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops. To achieve a rating of V-2, the afterflame times t1 and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all ten specimens (t1 plus t2 for all ten specimens) must have been less than or equal to 250 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2+t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; but the cotton indicator can have been ignited by flaming particles or drops. Compositions not achieving a rating of V-2 were considered to have failed.
- Heat deflection temperature (HDT) values, expressed in units of degrees centigrade, were determined according to ASTM D 648-07 using 6.4 millimeter thick bars (except where specified as 3.2 millimeter thickness), an edgewise test direction, a support span of 100 millimeters (Method B), a stress of 1.82 megapascals, a deflection of 0.25 millimeters at reading, a heating rate of 2° C./minute, and three specimens per composition.
- Flexural modulus and flexural strength values, each in units of megapascals, were determined at 23° C. according to ASTM D 790-07e1 using 6.4 millimeter thick bars, a support span of 101.6 millimeters, a test speed of 2.54 millimeters/minute (0.1 inch/minute; Procedure A), and three specimens per composition.
- Compositions and results are summarized in Table 2, where component amounts are expressed in weight percent based on the total weight of the composition.
- The Table 2 results show that the achievement of a flame retardancy rating of V-0 at a bar thickness of 1.5 millimeters is limited to Comparative Examples 1-3 with very high flame retardant concentrations (≧21.00 weight percent) and correspondingly low heat deflection temperatures (≦112° C.). A flame retardancy rating of V-0 at 1.0 millimeter thickness was only observed for Comparative Example 1 with a low heat deflection temperature of 106° C.
-
TABLE 2 C. Ex. 1 C. Ex. 2 C. Ex. 3 C. Ex. 4 C. Ex. 5 COMPOSITIONS PPE 0.40 63 56 49 67.5 60 BPADP 27 24 21 22.5 20 Glass fiber 10 20 30 10 20 PROPERTIES UL 94 rating at 1.5 mm V-0 V-0 V-0 Fail Fail UL 94 rating at 1.0 mm V-0 V-1 V-1 V-1 V-1 HDT (° C.) 106 111 112 120 124 Flex. modulus (MPa) 4670 7120 9610 4670 6850 Flex. strength (MPa) 144 153 159 145 149 C. Ex. 6 C. Ex. 7 C. Ex. 8 C. Ex. 9 C. Ex. 10 COMPOSITIONS PPE 0.40 52.5 72 64 56 76.5 BPADP 17.5 18 16 14 13.5 Glass fiber 30 10 20 30 10 PROPERTIES UL 94 rating at 1.5 mm V-1 V-1 V-1 V-1 V-1 UL 94 rating at 1.0 mm V-1 V-1 V-1 V-1 V-1 HDT (° C.) 124 133 137 138 149 Flex. modulus (MPa) 9090 4370 6490 8380 4250 Flex. strength (MPa) 158 147 149 151 145 C. Ex. 11 C. Ex. 12 C. Ex. 13 C. Ex. 14 C. Ex. 15 COMPOSITIONS PPE 0.40 68 59.5 81 72 63 BPADP 12 10.5 9 8 7 Glass fiber 20 30 10 20 30 PROPERTIES UL 94 rating at 1.5 mm Fail V-1 V-1 V-1 V-1 UL 94 rating at 1.0 mm V-1 Fail V-1 V-1 V-1 HDT (° C.) 152 154 164 168 170 Flex. modulus (MPa) 6000 8050 4100 5830 7890 Flex. strength (MPa) 142 152 142 145 155 - Eight comparative examples were prepared using poly(phenylene ether) homopolymer and the hydrogenated block copolymer SEBS. These examples illustrate that it is not feasible to achieve a V-0 rating at 1.5 millimeter thickness in a composition with a heat deflection temperature of at least 150° C. and at least 10% glass fiber reinforcement, even though the corresponding unfilled compositions (Comparative Examples 16 and 20) have a V-0 flame retardancy. Relative to the property balance exhibited by the inventive composition, unfilled Comparative Examples 16 and 20 are deficient, at least, in flexural modulus, and filled Comparative Examples 17-19 and 21-23 are deficient, at least, in UL 94 rating.
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TABLE 3 C. Ex. 16 C. Ex. 17 C. Ex. 18 C. Ex. 19 C. Ex. 20 COMPOSITIONS PPE 0.46 84.70 76.23 67.76 72.00 82.70 BPADP 10.00 9.00 8.00 8.50 12.00 SEBS 5.00 4.5 4.00 4.25 5.00 AO 168 0.30 0.27 0.24 0.25 0.30 Glass fiber 0.00 10 20 10.00 0.00 Clay 0.00 0.00 0.00 5.00 0.00 PROPERTIES UL 94 rating at 1.5 mm V-0 V-1 V-1 V-1 V-0 HDT (° C.) 146 159 163 159 139 Flex. modulus (MPa) 2520 3721 5234 4235 2570 Flex. strength (MPa) 106 122 132 136 108 C. Ex. 21 C. Ex. 22 C. Ex. 23 COMPOSITIONS PPE 0.46 74.43 66.16 70.30 BPADP 10.80 9.60 10.20 SEBS 4.50 4.00 4.25 AO 168 0.27 0.24 0.25 Glass fiber 10.00 20.00 10.00 Clay 0.00 0.00 5.00 PROPERTIES UL 94 rating at 1.5 mm V-1 V-1 V-1 HDT (° C.) 152 156 153 Flex. modulus (MPa) 3937 5363 4297 Flex. strength (MPa) 128 131 135 - These inventive and comparative examples illustrate the use of a poly(phenylene ether)-polysiloxane block copolymer in combination with the hydrogenated block copolymer SEBS. Inventive Examples 1-6 all have heat deflection temperature values of at least 155° C., as well as UL 94 ratings of V-0 at 1.5 millimeter thickness, and flexural modulus values greater than 3,500 megapascals. Comparative Examples 24 and 25 are unfilled and exhibit substantially lower heat deflection temperature values, flexural modulus values, and flexural strength values.
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TABLE 4 C. Ex. 24 Ex. 1 Ex. 2 Ex. 3 C. Ex. 25 COMPOSITIONS PPE-Si 87.70 78.93 70.16 74.55 85.70 BPADP 7.00 6.30 5.60 5.95 9.00 SEBS 5.00 4.50 4.00 4.25 5.00 AO 168 0.30 0.27 0.24 0.25 0.30 Glass fiber 0.00 10.00 20.00 10.00 0.00 Clay 0.00 0.00 0.00 5.00 0.00 PROPERTIES UL 94 rating at V-0 V-0 V-0 V-0 V-0 1.5 mm HDT (° C.) 149 163 168 163 140 Flex. modulus 2310 3506 4942 3891 2350 (MPa) Flex. strength (MPa) 94 119 133 125 96 Ex. 4 Ex. 5 Ex. 6 COMPOSITIONS PPE-Si 77.13 68.56 72.85 BPADP 8.10 7.20 7.65 SEBS 4.50 4.00 4.25 AO 168 0.27 0.24 0.25 Glass fiber 10.00 20.00 10.00 Clay 0.00 0.00 5.00 PROPERTIES UL 94 rating at 1.5 mm V-0 V-0 V-0 HDT (° C.) 155 160 158 Flex. modulus (MPa) 3739 5027 4039 Flex. strength (MPa) 123 130 129 - These inventive and comparative examples illustrate means of achieving improved melt flow.
- Melt volume flow rate (MVR) values, expressed in units of cubic centimeters per 10 minutes, were determined according to ASTM D 1238-04 at 300° C. using a load of 5 kilograms, automatic timing (Procedure B), a capillary diameter of 2.0955 millimeters, a capillary length of 8.00 millimeters, a test specimen form of pellets, specimen conditioning for one hour at 70° C. prior to testing, and one sample with five readings per composition.
- The results in Table 5 show that the inventive compositions can be modified to increase melt flow while still maintaining a high heat deflection temperature and a UL 94 rating of V-0 at 1.5 millimeters. Inventive Example 13 shows that a reduced concentration of poly(phenylene ether)-polysiloxane block copolymer also still results in V-0 at 1.5 mm. Inventive Example 15 illustrates the use of a mixed filler reinforcement. The examples also show that melt flow increases can be accomplished through use of a hydrocarbon resin flow promoter (Examples 10-15) and/or a phosphite antioxidant like AO 626. Inventive Example 7, without either hydrocarbon resin or phosphite antioxidant, exhibits relatively lower melt flow. Comparative Example 26 shows again that with poly(phenylene ether) homopolymer rather than poly(phenylene ether)-polysiloxane block copolymer reaction product, even a higher concentration of flame retardant does not result in V-0 flammability rating at 1.5 millimeters.
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TABLE 5 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 COMPOSITIONS PPE-Si 68.66 68.26 67.86 68.26 68.26 PPE 0.40 0.00 0.00 0.00 0.00 0.00 BPADP 6.97 6.97 6.97 6.97 6.97 SEBS 3.98 3.98 3.98 1.99 0.00 HCR 0.00 0.00 0.00 1.99 3.98 AO 626 0.00 0.40 0.80 0.40 0.40 Carbon black 0.50 0.50 0.50 0.50 0.50 Glass fiber 19.90 19.90 19.90 19.90 19.90 Mica 0.00 0.00 0.00 0.00 0.00 PROPERTIES UL 94 rating at V-0 V-0 V-0 V-0 V-0 1.5 mm HDT (° C.) 161 158 157 156 153 MVR (cc/10 min) 2.8 8.8 12.6 11.6 14.1 Flex. modulus (MPa) 5150 5180 5310 5320 5500 Flex. strength (MPa) 137 136 131 131 138 Ex. 12 Ex. 13 Ex. 14 Ex. 15 C. Ex. 26 COMPOSITIONS PPE-Si 67.86 33.43 77.21 72.74 0.00 PPE 0.40 0.00 33.43 0.00 0.00 65.27 BPADP 6.97 8.36 7.96 7.46 9.95 SEBS 0.00 1.99 1.99 1.99 3.98 HCR 3.98 1.99 1.99 1.99 0.00 AO 626 0.80 0.40 0.40 0.40 0.40 Carbon black 0.50 0.50 0.50 0.50 0.50 Glass fiber 19.90 19.90 9.95 9.95 19.90 Mica 0.00 0.00 0.00 4.98 0.00 PROPERTIES UL 94 rating at V-0 V-0 V-0 V-0 V-1 1.5 mm HDT (° C.) 151 153 152 153 155 MVR (cc/10 min) 21.8 13.1 16.3 13.4 8.28 Flex. modulus (MPa) 5660 5480 3910 4367 5640 Flex. strength (MPa) 134 133 122 124 136 - These inventive examples illustrate that omission of hydrogenated block copolymer is associated with even higher heat deflection temperature values.
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TABLE 6 Ex. 16 Ex. 17 Ex. 18 Ex. 19 COMPOSITIONS PPE-Si 76.32 71.84 67.86 73.83 BPADP 7.46 6.97 6.97 4.98 HCR 0.00 0.00 3.98 0.00 AO 626 0.80 0.80 0.80 0.80 Carbon black 0.50 0.50 0.50 0.50 Glass fiber 9.95 19.90 19.90 19.90 Mica 4.98 0.00 0.00 0.00 PROPERTIES UL 94 rating at 1.5 mm V-0 V-0 V-0 V-0 HDT (° C.) 157 159 153 168 MVR (cc/10 min) 18 14 23 9 Flex. modulus (MPa) 4700 5680 5650 5520 Flex. strength (MPa) 118 136 128 135 - These inventive and comparative examples, all with 20% glass fiber reinforcement, illustrate that the improved flame retardancy associated with the use of poly(phenylene ether)-polysiloxane block copolymer reaction product rather than poly(phenylene ether) homopolymer can be obtained without sacrificing heat resistance. Comparative Example 28 also illustrates that a reduction of HIPS concentration and increases in flame retardant and poly(phenylene ether) homopolymer, all relative to Comparative Example 27, are not sufficient to result in V-0 flame performance at 1.5 millimeters.
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TABLE 7 C. Ex. 27 Ex. 20 C. Ex. 28 Ex. 21 COMPOSITIONS TPPE 0.46 48.00 0.00 55.00 0.00 PPE-Si 0.00 52.00 0.00 59.00 HIPS 24.50 20.50 16.50 12.50 But-TPP 6.00 6.00 7.00 7.00 LLDPE 1.00 1.00 1.00 1.00 AO 626 0.30 0.30 0.30 0.30 ZnS 0.10 0.10 0.10 0.10 MgO 0.10 0.10 0.10 0.10 Glass fiber 20.00 20.00 20.00 20.00 PROPERTIES UL 94 rating at 1.5 mm V-1 V-0 V-1 V-0 HDT at 3.2 mm (° C.) 132 132 135 137 - These inventive and comparative examples, all with 30% glass fiber reinforcement, further illustrate that the improved flame retardancy associated with the use of poly(phenylene ether)-polysiloxane block copolymer reaction product rather than poly(phenylene ether) homopolymer can be obtained without substantially sacrificing heat resistance. Comparative Example 30 also illustrates that a reduction of HIPS concentration and increases in flame retardant and poly(phenylene ether) homopolymer, all relative to Comparative Example 29, are not sufficient to result in V-0 flame performance at 1.5 millimeters.
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TABLE 8 C. Ex. 29 Ex. 22 C. Ex. 30 Ex. 23 COMPOSITIONS PPE 0.46 49.00 0.00 51.50 0.00 PPE-Si 0.00 53.00 0.00 56.00 HIPS 12.00 8.00 8.50 4.00 But-TPP 7.50 7.50 8.50 8.50 LLDPE 1.00 1.00 1.00 1.00 AO 168 0.30 0.30 0.30 0.30 ZnS 0.10 0.10 0.10 0.10 MgO 0.10 0.10 0.10 0.10 Glass fiber 30.00 30.00 30.00 30.00 PROPERTIES UL 94 rating at 1.5 mm V-1 V-0 V-1 V-0 HDT at 3.2 mm (° C.) 136 135 135 136 - These inventive and comparative examples demonstrate that it is also possible to achieve a UL 94 rating of V-0 at a thickness of 0.75 millimeters in a 20% glass fiber reinforced composition containing poly(phenylene ether)-polysiloxane block copolymer, while maintaining a heat deflection temperature greater than 110° C. Comparative Example 36 achieved a V-0 rating but was deficient in heat deflection temperature.
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TABLE 9 Ex. 24 Ex. 25 Ex. 26 C. Ex. 31 C. Ex. 32 COMPOSITIONS PPE-Si 57.81 59.80 61.79 0.00 0.00 PPE 0.40 0.00 0.00 0.00 57.81 54.83 PPE 0.46 0.00 0.00 0.00 0.00 0.00 BPADP 19.90 17.91 15.92 19.90 22.89 Glass fiber 19.90 19.90 19.90 19.90 19.90 LLDPE 1.49 1.49 1.49 1.49 1.49 AO 168 0.10 0.10 0.10 0.10 0.10 ZnS 0.15 0.15 0.15 0.15 0.15 MgO 0.15 0.15 0.15 0.15 0.15 Carbon black 0.50 0.50 0.50 0.50 0.50 PROPERTIES UL 94 rating at V-0 V-0 V-0 V-1 V-1 0.75 mm HDT (° C.) 113 121 128 119 109 Flex. modulus 6094 6178 6104 6530 6570 (MPa) Flex. strength (MPa) 155 158 158 160 155 C. Ex. 33 C. Ex. 34 C. Ex. 35 C. Ex. 36 COMPOSITIONS PPE-Si 0.00 0.00 0.00 0.00 PPE 0.40 51.84 0.00 0.00 0.00 PPE 0.46 0.00 57.81 54.83 51.84 BPADP 25.87 19.90 22.89 25.87 Glass fiber 19.90 19.90 19.90 19.90 LLDPE 1.49 1.49 1.49 1.49 AO 168 0.10 0.10 0.10 0.10 ZnS 0.15 0.15 0.15 0.15 MgO 0.15 0.15 0.15 0.15 Carbon black 0.50 0.50 0.50 0.50 PROPERTIES UL 94 rating at 0.75 mm V-1 V-1 V-1 V-0 HDT (° C.) 100 120 110 100 Flex. modulus (MPa) 6661 6638 6539 6717 Flex. strength (MPa) 145 161 153 146 - These examples illustrate the attainment of a UL 94 V-0 rating at a thickness of 1.5 millimeters by compositions comprising as little as 0.5 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product. They further illustrate compositions comprising a first poly(phenylene ether) (derived from the poly(phenylene ether)-polysiloxane block copolymer reaction product) and a second poly(phenylene ether) (separately added; see Examples 28-43).
- Notched Izod values and unnotched Izod values, each expressed in units of joules/meter, were determined according to ASTM D256-08 at 25° C. using a hammer energy of 2 foot-pounds (2.71 joules), and bar cross-sectional dimensions of 3.2 by 12.7 millimeters. Flexural modulus, flexural stress at yield, and flexural stress at break values, each in units of megapascals, were determined at 23° C. according to ASTM D 790-07e1 using 6.4 millimeter thick bars, a support span of 101.6 millimeters, a test speed of 2.54 millimeters/minute (0.1 inch/minute; Procedure A), and three specimens per composition. Tensile modulus and tensile stress at break values, each expressed in units of megapascals, and tensile elongation at break values, expressed in units of percent, were determined according to ASTM D 638-08 at 23° C. using a Type I bar having a thickness of 3.2 millimeters, a gage length of 50 millimeters, and a testing speed of 5 millimeters per minute.
- The results demonstrate that compositions with 0.5 to 40 weight percent poly(phenylene ether)-polysiloxane block copolymer reaction product exhibit a UL 94 V-0 rating at a thickness of 1.5 millimeters. Although physical properties were not measured for all samples, the available results show that compositions with 2 to 40 weight percent poly(phenylene ether)-polysiloxane block copolymer reaction product further exhibit a heat deflection temperature of at least 150° C. determined according to ASTM D 648-07 using a stress of 1.82 megapascals (MPa) and a sample thickness of 6.4 millimeters, and a flexural modulus of at least 5,000 megapascals measured at 23° C. according to ASTM D 790-07e1 using a sample thickness of 6.4 millimeters. Comparative Examples 37 and 38, without poly(phenylene ether)-polysiloxane block copolymer, and Comparative Example 39, with only 0.4 weight percent poly(phenylene ether)-polysiloxane block copolymer, do not achieve a UL 94 V-0 rating at a thickness of 1.5 millimeters.
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TABLE 10 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Ex. 31 COMPOSITIONS PPE-Si 68.2 40.0 30.0 20.0 10.0 PPE 0.33 0.0 0.0 0.0 0.0 0.0 PPE 0.30 0.0 30.8 39.3 48.8 56.8 PDMS/silica 0.0 0.0 0.0 0.0 0.0 PDMS 0.0 0.0 0.0 0.0 0.0 HCR 4.0 0.0 0.0 0.0 0.0 SEBS 0.0 1.0 2.0 2.0 3.0 AO 626 0.8 0.0 0.0 0.0 0.0 AO 168 0.0 0.2 0.2 0.2 0.2 BPADP 7.0 8.0 8.5 9.0 10.0 Glass fiber 20.0 20.0 20.0 20.0 20.0 Polysiloxane content 3.4 2.0 1.5 1.0 0.5 PROPERTIES UL Rating at 1.5 mm V-0 V-0 V-0 V-0 V-0 UL Rating at 1.0 mm V-0 V-0 V-0 V-0 V-0 HDT (° C.) 153 159 159 157 153 Notched Izod (J/m) 69.8 87.8 95.2 90.8 96 Unnotched Izod (J/m) 338 466 478 492 457 Flex. modulus (MPa) 5460 5240 5210 5090 5180 Flex. stress at yield (MPa) 131 140 143 140 143 Flex. stress at break (MPa) 132 141 140 140 143 Tens. modulus (MPa) 6900 6818 6784 6768 6784 Tensile stress at break (MPa) 114 119 118 120 120 Tens. elong. at break (%) 2.2 2.5 2.5 2.5 2.5 C. Ex. 37 Ex. 32 Ex. 33 Ex. 34 Ex. 35 COMPOSITIONS PPE-Si 0.0 20.0 10.0 8.0 6.0 PPE 0.33 0.0 0.0 0.0 0.0 0.0 PPE 0.30 65.8 47.8 57.8 59.8 61.8 PDMS/silica 0.0 0.0 0.0 0.0 0.0 PDMS 0.0 0.0 0.0 0.0 0.0 HCR 0.0 0.0 0.0 0.0 0.0 SEBS 4.0 2.0 2.0 2.0 2.0 AO 626 0.0 0.0 0.0 0.0 0.0 AO 168 0.2 0.20 0.20 0.20 0.20 BPADP 10.0 10.0 10.0 10.0 10.0 Glass fiber 20.0 20.0 20.0 20.0 20.0 Polysiloxane content 0.0 1.0 0.5 0.4 0.3 PROPERTIES UL Rating at 1.5 mm V-1 V-0 V-0 V-0 V-0 UL Rating at 1.0 mm V-1 — — — — HDT (° C.) 153 153 154 155 155 Notched Izod (J/m) 101 79.8 82.0 86.6 83.3 Unnotched Izod (J/m) 515 495 516 503 511 Flex. modulus (MPa) 5270 5330 5390 5400 5400 Flex. stress at yield (MPa) 147 — — — — Flex. stress at break (MPa) 144 133 135 134 138 Tens. modulus (MPa) 6694 — — — — Tensile stress at break (MPa) 117 — — — — Tens. elong. at break (%) 2.5 — — — — Ex. 36 Ex. 37 C. Ex. 38 Ex. 38 Ex. 39 COMPOSITIONS PPE-Si 4.0 2.0 0.0 4.0 2.0 PPE 0.33 0.0 0.0 0.0 63.8 65.8 PPE 0.30 63.8 65.8 67.8 0.0 0.0 PDMS/silica 0.0 0.0 0.0 0.0 0.0 PDMS 0.0 0.0 0.0 0.0 0.0 HCR 0.0 0.0 0.0 0.0 0.0 SEBS 2.0 2.0 2.0 2.0 2.0 AO 626 0.0 0.0 0.0 0.0 0.0 AO 168 0.2 0.20 0.20 0.20 0.20 BPADP 10.0 10.0 10.0 10.0 10.0 Glass fiber 20.0 20.0 20.0 20.0 20.0 Polysiloxane content 0.2 0.1 0.0 0.2 0.1 PROPERTIES UL Rating at 1.5 mm V-0 V-0 V-1 V-0 V-0 UL Rating at 1.0 mm — — — — — HDT (° C.) 155 155 156 — — Notched Izod (J/m) 81.1 79.5 81.3 — — Unnotched Izod (J/m) 496 475 475 — — Flex. modulus (MPa) 5460 5490 5560 — — Flex. stress at yield (MPa) — — — — — Flex. stress at break (MPa) 133 138 135 — — Tens. modulus (MPa) — — — — — Tensile stress at break (MPa) — — — — — Tens. elong. at break (%) — — — — — Ex. 40 Ex. 41 Ex. 42 Ex. 43 C. Ex. 39 COMPOSITIONS PPE-Si 1.0 0.50 1.60 0.80 0.40 PPE 0.33 66.8 67.3 66.2 67.0 67.4 PPE 0.30 0.0 0.0 0.0 0.0 0.0 PDMS/silica 0.0 0.0 0.0 0.0 0.0 PDMS 0.0 0.0 0.0 0.0 0.0 HCR 0.0 0.0 0.0 0.0 0.0 SEBS 2.0 2.0 2.0 2.0 2.0 AO 626 0.0 0.0 0.0 0.0 0.0 AO 168 0.2 0.20 0.20 0.20 0.20 BPADP 10.0 10.0 10.0 10.0 10.0 Glass fiber 20.0 20.0 20.0 20.0 20.0 Polysiloxane content 0.05 0.025 0.08 0.04 0.02 PROPERTIES UL Rating at 1.5 mm V-0 V-0 V-0 V-0 V-1 UL Rating at 1.0 mm — — — — — HDT (° C.) — — — — — Notched Izod (J/m) — — — — — Unnotched Izod (J/m) — — — — — Flex. modulus (MPa) — — — — — Flex. stress at yield (MPa) — — — — — Flex. stress at break (MPa) — — — — — Tens. modulus (MPa) — — — — — Tensile stress at break (MPa) — — — — — Tens. elong. at break (%) — — — — — - This example illustrates a composition exhibiting high flame retardancy, heat resistance, and melt flow.
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TABLE 11 Ex. 44 COMPOSITION PPE-Si 5.97 PPE 0.33 65.46 SEBS 1.99 AO 168 0.20 BPADP 10.95 Carbon black 0.50 Glass fiber 14.93 Polysiloxane content 0.30 PROPERTIES UL Rating at 1.5 mm V-0 HDT (° C.) 152 Flex. modulus (MPa) 4790 Flex. strength (MPa) 132 MVR (cc/10 min) 24
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2014
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US10113055B2 (en) | 2014-05-06 | 2018-10-30 | Sabic Global Technologies B.V. | Article comprising poly(phenylene ether)-polysiloxane copolymer composition |
US10294369B2 (en) | 2015-05-13 | 2019-05-21 | Sabic Global Technologies B.V. | Reinforced poly(phenylene ether) compositions, and articles prepared therefrom |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
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WO2021186252A1 (en) * | 2020-03-20 | 2021-09-23 | Shpp Global Technologies B.V. | Poly(phenylene ether) composition, method for the manufacture thereof, and articles made therefrom |
Also Published As
Publication number | Publication date |
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CN106459583B (en) | 2019-08-09 |
CN106459583A (en) | 2017-02-22 |
WO2015171293A1 (en) | 2015-11-12 |
US20160009902A1 (en) | 2016-01-14 |
US9193868B1 (en) | 2015-11-24 |
JP2017514970A (en) | 2017-06-08 |
EP3140351A4 (en) | 2017-11-29 |
KR102320672B1 (en) | 2021-11-02 |
EP3140351A1 (en) | 2017-03-15 |
KR20170005055A (en) | 2017-01-11 |
JP6357249B2 (en) | 2018-07-11 |
US10113055B2 (en) | 2018-10-30 |
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