CN112204099A - Method for producing styrene series flame-retardant resin composition - Google Patents
Method for producing styrene series flame-retardant resin composition Download PDFInfo
- Publication number
- CN112204099A CN112204099A CN201980036041.7A CN201980036041A CN112204099A CN 112204099 A CN112204099 A CN 112204099A CN 201980036041 A CN201980036041 A CN 201980036041A CN 112204099 A CN112204099 A CN 112204099A
- Authority
- CN
- China
- Prior art keywords
- resin composition
- flame retardant
- retardant resin
- flame
- styrene
- 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.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 77
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000011342 resin composition Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 20
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 18
- 239000008158 vegetable oil Substances 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 229920001890 Novodur Polymers 0.000 claims abstract description 4
- -1 alkyl phosphite Chemical compound 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000002516 radical scavenger Substances 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 230000031709 bromination Effects 0.000 claims description 6
- 238000005893 bromination reaction Methods 0.000 claims description 6
- 238000002411 thermogravimetry Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 3
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 230000004580 weight loss Effects 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- 235000006708 antioxidants Nutrition 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010459 dolomite Substances 0.000 description 6
- 229910000514 dolomite Inorganic materials 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 description 6
- 229960001545 hydrotalcite Drugs 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- FVEAIIZMVQXSQE-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=CC(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O FVEAIIZMVQXSQE-UHFFFAOYSA-N 0.000 description 1
- TVWGHFVGFWIHFN-UHFFFAOYSA-N 2-hexadecan-2-yl-4,6-dimethylphenol Chemical compound CCCCCCCCCCCCCCC(C)C1=CC(C)=CC(C)=C1O TVWGHFVGFWIHFN-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 241000579895 Chlorostilbon Species 0.000 description 1
- 235000001815 DL-alpha-tocopherol Nutrition 0.000 description 1
- 239000011627 DL-alpha-tocopherol Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical class [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- 229910020038 Mg6Al2 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229910052876 emerald Inorganic materials 0.000 description 1
- 239000010976 emerald Substances 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- FGDAXMHZSNXUFJ-UHFFFAOYSA-N ethene;prop-1-ene;prop-2-enenitrile Chemical group C=C.CC=C.C=CC#N FGDAXMHZSNXUFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
Provided is a method for producing a flame-retardant resin composition containing a styrene resin and a brominated polymer flame retardant and having excellent thermal stability. When a styrenic flame retardant resin composition is produced using (A) a brominated polymer type flame retardant, (B) a styrenic resin, (C) a stabilizer, and (D) liquid paraffin or epoxidized vegetable oil, at least (A) the brominated polymer type flame retardant and (D) the liquid paraffin or epoxidized vegetable oil are mixed, and then melt-kneaded at a resin temperature of less than 210 ℃ by an extruder.
Description
Technical Field
The present invention relates to a method for producing a flame-retardant resin composition comprising a styrenic resin and a brominated polymer-type flame retardant.
Background
Hexabromocyclododecane (HBCD) is generally used as a flame retardant for imparting flame retardancy to a styrene resin molded article, but HBCD has in vivo accumulation properties, is toxic to aquatic organisms, and is not easily decomposed, and a brominated polymer type flame retardant has been studied as a substitute (see patent document 1).
In addition, as a stabilizer for a brominated polymer type flame retardant, an alkyl phosphite and an epoxy compound are known (see patent document 2).
As the use, for extrusion molding use. In extrusion molding, a flame retardant master batch composition having a high concentration is used in consideration of dispersibility (see patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese Kokai publication No. 2009-516019
Patent document 2: japanese Kohyo publication No. 2012-512942
Patent document 3: japanese patent laid-open publication No. 2013-23508
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a method for producing a flame-retardant resin composition containing a styrene resin and a brominated polymer-type flame retardant and having excellent thermal stability.
Means for solving the problems
The present inventors have conducted intensive studies on the above problems, and as a result: in the production of a flame-retardant resin composition (melt) using a brominated polymer type flame retardant, a styrene-based resin, a stabilizer and liquid paraffin or epoxidized vegetable oil, at least the brominated polymer type flame retardant and the liquid paraffin or epoxidized vegetable oil are mixed and then melt-kneaded at a resin temperature of less than 210 ℃ by an extruder, thereby completing the present invention.
Namely, the present invention is as follows.
1. A method for producing a styrene-based flame-retardant resin composition, characterized in that it comprises a step of mixing a styrenic flame-retardant resin composition with a solvent,
the styrene flame-retardant resin composition comprises (A) a brominated polymer flame retardant, (B) a styrene resin, (C) a stabilizer, and (D) liquid paraffin or epoxidized vegetable oil, wherein the bromine content is 18 to 42 mass%,
mixing at least the brominated polymer flame retardant (A) and the liquid paraffin or epoxidized vegetable oil (D), and then melt-kneading the resulting mixture in an extruder at a resin temperature of less than 210 ℃.
2. The method for producing a styrene-based flame-retardant resin composition according to claim 1, wherein the stabilizer (C) is at least two or more selected from the group consisting of an antioxidant, a halogen scavenger, a novolak-type epoxy resin and an alkyl phosphite.
3. The method for producing a styrene-based flame-retardant resin composition according to claim 1 or 2, wherein the stabilizer (C) is contained in an amount of 5 to 30 parts by mass and the liquid paraffin or epoxidized vegetable oil (D) is contained in an amount of 1 to 8 parts by mass, based on 100 parts by mass of the total of the brominated polymer-based flame retardant (a) and the styrene-based resin (B).
4. The method for producing a styrenic flame retardant resin composition according to any of the preceding 1 to 3, wherein the brominated polymer-type flame retardant (A) is as follows:
(a) is a copolymer having butadiene and a vinyl aromatic hydrocarbon as monomer components,
(b) the content of the vinyl aromatic hydrocarbon monomer in the copolymer before bromination is 5 to 90 mass% inclusive,
(c) the butadiene contains 1, 2-butadiene,
(d) a weight-average molecular weight (Mw) of 1000 or more,
(e) based on1The non-brominated non-aromatic double bond content of the H-NMR spectrum method is less than 50 percent based on the non-aromatic double bond content of the copolymer before bromination,
(f) the 5% weight loss temperature based on Thermogravimetric Analysis (TGA) is 200 ℃ or higher.
5. The method for manufacturing a styrenic flame retardant resin composition according to any of the preceding 1 to 4, wherein the extruder is a twin-screw extruder.
6. A flame-retardant resin molded body, characterized by comprising: a styrenic flame retardant resin composition produced by the method for producing a styrenic flame retardant resin composition described in any one of the above 1 to 5.
7. A flame-retardant resin molded body, characterized by comprising: a styrenic flame retardant resin composition produced by the method for producing a styrenic flame retardant resin composition described in any one of the above 1 to 5, and a styrenic resin.
ADVANTAGEOUS EFFECTS OF INVENTION
The extrusion method for producing a styrenic flame retardant resin composition according to the present invention can stabilize a brominated polymer-based flame retardant, can produce a thermoplastic resin composition having a high concentration of the brominated polymer-based flame retardant, and can provide an extrusion-molded article having a good appearance, and therefore, has a great industrial value.
Detailed Description
(A) brominated polymeric flame retardants
The brominated polymer type flame retardant (a) used in the present invention is a conventionally known flame retardant, and the flame retardants disclosed in patent documents 1 and 2 can be used as they are. It is preferable to use a brominated copolymer having the following characteristics (a) to (f).
(a) Is a copolymer having butadiene and a vinyl aromatic hydrocarbon as monomer components.
(b) The content of the vinyl aromatic hydrocarbon monomer in the copolymer before bromination is 5 to 90 mass% inclusive.
(c) The butadiene contains 1, 2-butadiene.
(d) The weight average molecular weight (Mw) is 1000 or more.
(e) Based on1The non-brominated non-aromatic double bond content of the H-NMR spectrum is less than 50% based on the non-aromatic double bond content of the copolymer before bromination.
(f) The 5% weight loss temperature based on Thermogravimetric Analysis (TGA) is 200 ℃ or higher.
Among them, brominated styrene/butadiene block copolymers, brominated styrene/butadiene random copolymers, brominated styrene/butadiene graft copolymers, and the like, which have the characteristics of the above-mentioned (a) to (f) and in which the vinyl aromatic hydrocarbon is styrene, are more preferable. Particularly preferred is a brominated styrene/butadiene block copolymer, and specifically, commercially available products such as "EMERALD INNOVATION 3000" by LANXESS Corporation, "FR 122P" by ICL Corporation, and "GREEN CREST" by Albemarle Corporation are exemplified.
In the present invention, the amount of the brominated polymer flame retardant is adjusted so that the bromine content in the resin composition is 18 mass% or more and 42 mass% or less.
Styrene resin (B)
The styrene-based resin (B) used in the resin composition of the present invention includes homopolymers of styrene, copolymers of styrene and a monomer copolymerizable therewith, and rubber-reinforced styrene-based resins obtained by reinforcing these. For example, polystyrene, rubber-reinforced polystyrene (HIPS), acrylonitrile-styrene copolymer resin (AS), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-acrylic rubber-styrene copolymer resin (AAS), acrylonitrile-ethylene propylene rubber-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, styrene-butadiene copolymer resin, and the like. These styrene resins may be used alone or in combination of two or more. Most preferred is polystyrene.
(C) stabilizers
The stabilizer (C) is not particularly limited, and examples thereof include antioxidants, halogen scavengers, novolak-type epoxy resins, alkyl phosphites, and the like. (C) The stabilizer is preferably at least two or more selected from the group consisting of an antioxidant, a halogen scavenger, a novolak type epoxy resin and an alkyl phosphite.
The antioxidant includes a phenol antioxidant, a sulfur antioxidant, a phosphorus antioxidant, and the like, and preferably a phenol antioxidant, particularly a hindered phenol antioxidant. Examples of the hindered phenol-based antioxidant include octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis [ 3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ], 4, 6-bis (octylthiomethyl) -o-cresol, 4, 6-bis [ (dodecylthio) methyl ] -o-cresol, 2, 4-dimethyl-6- (1-methylpentadecyl) phenol, tetrakis [ methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane, DL- α -tocopherol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, and mixtures thereof, 2- [ 1- (2-hydroxy-3, 5-di-tert-pentylphenyl) ethyl ] -4, 6-di-tert-pentylphenyl acrylate, 4 '-thiobis (6-tert-butyl-3-methylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4' -butylidenebis (3-methyl-6-tert-butylphenol), and the like.
The halogen scavenger is a component that traps free halogen generated in the process of producing the resin composition. Examples thereof include magnesium carbonate compounds (e.g., dolomite compounds and hydrotalcite compounds), magnesium perchlorate compounds, aluminosilicate compounds (e.g., zeolite), and organotin compounds. Wherein,from the viewpoint of suppressing the effect of generating black foreign matter, dolomite-based compounds and hydrotalcite-based compounds are preferable. The dolomite compound is CaMg (CO)3)2Or a compound containing the same, the hydrotalcite-based compound being Mg6Al2(OH)16CO3·nH2O, etc. is one of the naturally occurring clay minerals. These halogen scavengers can be used alone, but when a dolomite compound and a hydrotalcite compound are used in combination, the occurrence of discoloration can be effectively suppressed in addition to the effect of suppressing the occurrence of black foreign matter. The mass ratio of the dolomite-based compound to the hydrotalcite-based compound is preferably 10/90 to 90/10, and more preferably 30/70 to 70/30.
The novolak type epoxy resin can be used commercially. For example, cresol novolac type epoxy resins and phenol novolac type epoxy resins. Cresol novolac type epoxy resins are preferred.
Commercially available alkyl phosphites can be used. For example, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite and bis- (2, 4-di- (tert-butyl) phenyl) pentaerythritol diphosphite.
(C) The amount of the stabilizer added is preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total of the brominated polymer flame retardant (a) and the styrene resin (B). The amount of the antioxidant added is preferably 0.8 parts by mass or more and 7 parts by mass or less. The amount of the halogen scavenger added is preferably 0.8 to 15 parts by mass, more preferably 5 to 10 parts by mass. The amount of the novolac epoxy resin added is preferably 4 parts by mass or more and 25 parts by mass or less. The amount of the alkyl phosphite to be added is preferably 4 parts by mass or more and 25 parts by mass or less. When the amount is within the above range, the thermal stability of the brominated polymer type flame retardant in the resin composition is improved, and the occurrence of black foreign matter and discoloration due to thermal deterioration of the brominated polymer type flame retardant can be effectively suppressed.
(D) liquid Paraffin or epoxidized vegetable oil
The liquid paraffin used in the present invention may be any known liquid paraffin (referred to as white oil) defined as a mixture of liquid saturated hydrocarbons having extremely high purity and boiling points belonging to lubricating oil fractions.
As the epoxidized vegetable oil used in the present invention, commercially available ones can be used. For example, epoxidized soybean oil, epoxidized linseed oil. Preferably epoxidized soybean oil.
(D) The amount of the liquid paraffin or the epoxidized vegetable oil to be added is preferably 1 part by mass or more and 8 parts by mass or less, and more preferably 3 parts by mass or more and 6 parts by mass or less, based on 100 parts by mass of the total of the brominated polymer flame retardant (a) and the styrene resin (B). When the amount is within the above range, the thermal stability of the brominated polymer flame retardant (a) in the resin composition is improved, and the occurrence of black foreign matter and discoloration due to thermal deterioration of the brominated polymer flame retardant (a) can be effectively suppressed.
Other additives
Other additives may be added to the resin composition of the present invention within a range not impairing the effects of the present invention. For example, fatty acid-based lubricants such as stearic acid and palmitic acid, fatty acid amide-based lubricants such as stearic acid amide and ethylene bis-stearic acid amide, lubricants such as metal soap-based lubricants such as zinc stearate and magnesium stearate, fillers such as talc, mica and silica, reinforcing agents such as glass fiber, colorants such as pigments and dyes, flame retardant aids such as antimony trioxide, antistatic agents such as nonionic surfactants and cationic surfactants.
Method for producing
The method for producing a resin composition of the present invention comprises the steps of: at least a preblending (preblending) of thoroughly mixing (a) the brominated polymeric flame retardant and (D) the liquid paraffin or epoxidized vegetable oil is carried out before melt-kneading. When the styrene resin (B) and the stabilizer (C) are premixed, the styrene resin (B) and the stabilizer (C) may be added as long as they can be sufficiently mixed. (D) The liquid paraffin or epoxidized vegetable oil may be added from other feeders separately from the premixing, but if (a) the brominated polymer type flame retardant is not premixed with (D) the liquid paraffin or epoxidized vegetable oil but added from other feeders and melt-kneaded, black foreign matter, discoloration due to thermal deterioration of (a) the brominated polymer type flame retardant may be generated. Examples of the method of mixing the preliminary mixing include a method using a mixing device such as a stirring mixer, a V-type mixer, or a drum mixer.
The method for producing the resin composition of the present invention comprises a step of melt-kneading the premixed blend at a resin temperature of less than 210 ℃ by an extruder. The extrusion melt-kneading method is not particularly limited, and a known melting technique can be used. Suitable melt kneading apparatuses include a single screw extruder, a special single screw extruder, and a twin screw extruder. Preferably a twin screw extruder. As a melting technique of an extruder, there are the following methods: a method of feeding the blend from the middle of the kneading apparatus by means of a side feeder; and a method of supplying a liquid from a feed nozzle at a discharge pressure equal to or higher than the resin pressure by a known liquid-feeding pump.
Molded article
The first molded article of the present invention is obtained by molding the styrene-based flame-retardant resin composition obtained by the production method of the present invention. The second molded article of the present invention is obtained by molding the styrene-based flame-retardant resin composition obtained by the production method of the present invention and further a styrene-based resin. The second molded article of the present invention is a molded article using the styrenic flame retardant resin composition produced by the production method of the present invention as a master batch. As a further styrene resin, the styrene resin described as the styrene resin (B) can be mentioned. As the molding method, known methods such as injection molding and extrusion molding can be applied.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[ (A) brominated polymeric flame retardant ]
"EMERAL INVOLVATION 3000" manufactured by LANXESS corporation (brominated styrene/butadiene block copolymer having the characteristics of (a) to (f), bromine content: 60% by mass)
[ (B) styrene series resin ]
A homopolymer (polystyrene) of styrene having a weight average molecular weight (Mw) of 20 ten thousand and a methanol-soluble component content of 1.2 mass% was used. The weight average molecular weight (Mw) and the amount of methanol-soluble components were measured by the following methods.
Measurement of weight average molecular weight (Mw)
The measurement was performed under the following conditions using Gel Permeation Chromatography (GPC).
GPC type: shodex GPC-101 manufactured by Showa Denko K.K.) "
Column: polymer Laboratories Ltd. "PLgel 10 μm MIXED-C"
Mobile phase: chloroform
Sample concentration: 0.2% by mass
Temperature: 40 deg.C (baking oven)
A detector: differential refractometer
The molecular weight of each component in the present invention is measured by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene and calculating the molecular weight as a molecular weight in terms of polystyrene.
Measurement of soluble component amount of methanol
1g of the sample was dissolved in 40ml of a solvent (methyl ethyl ketone), and polystyrene was reprecipitated with 400ml of a 10-fold amount of a poor solvent (methanol), and the mass of the reprecipitated polystyrene was determined, with the balance being the amount of a methanol-soluble component.
[ (C) stabilizer ]
C-1: antioxidant BASF Japan Ltd. "Irganox 1076" (octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate)
C-2: halogen scavenger Ajinomoto Fine-Techno Co., product of Inc. "PLENLIZER HC-100B" (dolomite series compound)
C-3: halogen scavenger "MC-63A" (hydrotalcite compound) manufactured by Nitto Kabushiki Kaisha
C-4: cresol novolac type epoxy resin Huntsman K.K. "ARALDITE (registered trade Mark) ECN 1280" manufactured by "
[ (D) liquid Paraffin or epoxidized vegetable oil ]
D-1: "Crystol N352" manufactured by liquid Paraffin Exxon Mobil Corporation "
D-2: "NEW SIZER 510R" manufactured by epoxidized soybean oil Japan oil K.K.) "
(examples 1 to 4 and comparative examples 1 to 6)
The respective components were put into a mixer at the compounding amounts shown in Table 1 to be preblended (preblended) (in comparative examples 1 and 2, preblended without the component (A) and the component (D)), and the blend was fed to a twin-screw extruder (TEM 26 SS: No. 14 cylinder, manufactured by Toshiba Co., Ltd.) by using a quantitative feeder and melt-kneaded under extrusion conditions of a cylinder temperature of 180 ℃ (220 ℃ in comparative example 3), a total feeding amount of 30 kg/hr, and a screw rotation speed of 300 rpm. In comparative examples 1 and 2, the styrene-based resin (B), the stabilizer (C), and the liquid paraffin or epoxidized vegetable oil (D) were preblended, but the brominated polymer-based flame retardant (a) was separately fed. The extruded strand was water-cooled and introduced into a pelletizer to obtain pellets of the resin composition. For the measurement of the resin temperature, a resin thermometer was inserted into a die hole of an extruder to measure. The bromine content in the pellets of the obtained resin composition was measured by the following method, and the following foreign matter evaluation was performed. The results are shown in Table 1.
[ method for measuring bromine content ]
The bromine content in the pellets of the resin composition was measured by combustion-ion chromatography under the following conditions.
Model: "AQF-100" manufactured by Mitsubishi chemical Corporation and "DX-120" manufactured by Dionex Corporation "
Temperature of the combustion tube: 1000 deg.C
A detector: conductivity detector
Column: AS12A
Flow rate: 1.5 ml/min
The eluent composition is as follows: 2.7mM-Na2CO3+0.3mM-NaHCO3
Sample introduction amount: 5 μ l
Sample amount: 3mg of
[ evaluation of foreign matter ]
Pellets of the resin composition were molded into a molded article having a height × width × thickness of 90mm × 90mm × 2mm at a resin temperature of 180 ℃ and a mold temperature of 40 ℃ by an injection molding machine ("J100E-P" manufactured by japan steel-making corporation). The state of generation of black foreign matter was visually observed, and evaluated according to the following criteria.
O: 0 or more and 4 or less black foreign matters are generated.
X: more than 5 black foreign matters are generated.
[ Table 1]
As is clear from table 1, according to the examples of the present invention, foreign matter generation due to deterioration of the brominated polymer-based flame retardant did not occur to those who satisfied the present invention. However, in the comparative examples which do not satisfy the specification of the present invention, the manufacturer was found to generate foreign matter due to deterioration of the brominated polymer-based flame retardant.
Claims (7)
1. A method for producing a styrene-based flame-retardant resin composition, characterized in that it comprises a step of mixing a styrenic flame-retardant resin composition with a solvent,
the styrene flame-retardant resin composition comprises (A) a brominated polymer flame retardant, (B) a styrene resin, (C) a stabilizer, and (D) liquid paraffin or epoxidized vegetable oil, wherein the bromine content is 18 to 42 mass%,
after mixing at least the (A) brominated polymeric flame retardant and the (D) liquid paraffin or epoxidized vegetable oil, melt-kneading is conducted with an extruder at a resin temperature of less than 210 ℃.
2. The method for producing a styrenic flame retardant resin composition according to claim 1, wherein the stabilizer (C) is at least two or more selected from the group consisting of an antioxidant, a halogen scavenger, a novolac epoxy resin and an alkyl phosphite.
3. The method for producing a styrene-based flame-retardant resin composition according to claim 1 or 2, wherein the stabilizer (C) is contained in an amount of 5 to 30 parts by mass and the liquid paraffin or epoxidized vegetable oil (D) is contained in an amount of 1 to 8 parts by mass, based on 100 parts by mass of the total of the brominated polymer-based flame retardant (a) and the styrene-based resin (B).
4. The method for producing a styrenic flame retardant resin composition according to any of claims 1 to 3, wherein the (A) brominated polymeric flame retardant is as follows:
(a) is a copolymer having butadiene and a vinyl aromatic hydrocarbon as monomer components,
(b) the content of the vinyl aromatic hydrocarbon monomer in the copolymer before bromination is 5 to 90 mass% inclusive,
(c) the butadiene contains 1, 2-butadiene,
(d) a weight-average molecular weight (Mw) of 1000 or more,
(e) based on1The non-brominated non-aromatic double bond content of the H-NMR spectrum method is less than 50 percent based on the non-aromatic double bond content of the copolymer before bromination,
(f) the 5% weight loss temperature based on Thermogravimetric Analysis (TGA) is 200 ℃ or higher.
5. The method of manufacturing a styrenic flame retardant resin composition according to any of claims 1 to 4, wherein the extruder is a twin screw extruder.
6. A flame-retardant resin molded body, characterized by comprising: a styrenic flame retardant resin composition produced by the method for producing a styrenic flame retardant resin composition according to any one of claims 1 to 5.
7. A flame-retardant resin molded body, characterized by comprising: a styrenic flame retardant resin composition produced by the method for producing a styrenic flame retardant resin composition according to any one of claims 1 to 5, and a styrenic resin.
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| PCT/JP2019/021715 WO2019235378A1 (en) | 2018-06-04 | 2019-05-31 | Method for producing styrene-based flame retardant resin composition |
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| CN103890083A (en) * | 2011-10-21 | 2014-06-25 | 东洋苯乙烯股份有限公司 | Flame retardant master batch and method for producing styrene-based flame-retardant resin composition with use of same |
| CN107892780A (en) * | 2016-10-03 | 2018-04-10 | 东洋苯乙烯股份有限公司 | Fire retardant resin composition and flame-retardant-resin formed body |
| CN107892779A (en) * | 2016-10-03 | 2018-04-10 | 东洋苯乙烯股份有限公司 | Fire retardant resin composition and flame-retardant-resin formed body |
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| CN103890083A (en) * | 2011-10-21 | 2014-06-25 | 东洋苯乙烯股份有限公司 | Flame retardant master batch and method for producing styrene-based flame-retardant resin composition with use of same |
| CN107892780A (en) * | 2016-10-03 | 2018-04-10 | 东洋苯乙烯股份有限公司 | Fire retardant resin composition and flame-retardant-resin formed body |
| CN107892779A (en) * | 2016-10-03 | 2018-04-10 | 东洋苯乙烯股份有限公司 | Fire retardant resin composition and flame-retardant-resin formed body |
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