CN101412843A - Flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin compositions - Google Patents
Flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin compositions Download PDFInfo
- Publication number
- CN101412843A CN101412843A CNA2007100470539A CN200710047053A CN101412843A CN 101412843 A CN101412843 A CN 101412843A CN A2007100470539 A CNA2007100470539 A CN A2007100470539A CN 200710047053 A CN200710047053 A CN 200710047053A CN 101412843 A CN101412843 A CN 101412843A
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- CN
- China
- Prior art keywords
- flame retardant
- butadiene
- acrylonitrile
- composition
- retardant
- 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.)
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 142
- 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 134
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 46
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 46
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 45
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title claims abstract description 44
- 239000011342 resin composition Substances 0.000 title claims description 13
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- -1 monophosphate ester Chemical class 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004609 Impact Modifier Substances 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002216 antistatic agent Substances 0.000 claims description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 5
- 239000004328 sodium tetraborate Substances 0.000 claims description 5
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 5
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 claims description 3
- UHFOGRFLWQICFT-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-1,1-diphenylpropane-1,3-diol phosphono dihydrogen phosphate Chemical compound OP(O)(=O)OP(=O)(O)O.C1(=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=CC=CC=C1 UHFOGRFLWQICFT-UHFFFAOYSA-N 0.000 claims description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 3
- 229940122361 Bisphosphonate Drugs 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- WZUGHHFBGWGCAT-UHFFFAOYSA-N P(O)(O)=O.P(O)(O)=O.C1(O)=CC(O)=CC=C1 Chemical group P(O)(O)=O.P(O)(O)=O.C1(O)=CC(O)=CC=C1 WZUGHHFBGWGCAT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 125000005340 bisphosphate group Chemical group 0.000 claims description 3
- 150000004663 bisphosphonates Chemical class 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000554 ionomer Polymers 0.000 claims description 3
- HBEXMKJUVPFPEZ-UHFFFAOYSA-N isocyanic acid;1,3,5-triazine-2,4,6-triamine Chemical compound N=C=O.NC1=NC(N)=NC(N)=N1 HBEXMKJUVPFPEZ-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000007974 melamines Chemical class 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920013716 polyethylene resin Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 150000005691 triesters Chemical class 0.000 claims description 3
- 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 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims description 2
- 239000001177 diphosphate Substances 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000779 smoke Substances 0.000 abstract description 13
- 239000002341 toxic gas Substances 0.000 abstract description 7
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 6
- 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 12
- 238000000034 method Methods 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 7
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- LDQYTDPXIMNESL-UHFFFAOYSA-N 2-methyl-4-propylphenol Chemical compound CCCC1=CC=C(O)C(C)=C1 LDQYTDPXIMNESL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- KWQPWOQUXSQDNN-UHFFFAOYSA-N (2,3,4-trimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=C(OP(O)(O)=O)C(C)=C1C KWQPWOQUXSQDNN-UHFFFAOYSA-N 0.000 description 1
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- BCMLMVXTJIMQTK-UHFFFAOYSA-N 2-[(4-phenoxyphenyl)sulfinylmethyl]thiirane Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1S(=O)CC1CS1 BCMLMVXTJIMQTK-UHFFFAOYSA-N 0.000 description 1
- BIICHPZAXGBDCH-UHFFFAOYSA-N 2-cyclohexyl-4-propylphenol Chemical compound CCCC1=CC=C(O)C(C2CCCCC2)=C1 BIICHPZAXGBDCH-UHFFFAOYSA-N 0.000 description 1
- UEZQPLQZAUVRDZ-UHFFFAOYSA-N 2-tert-butyl-4-propylphenol Chemical compound CCCC1=CC=C(O)C(C(C)(C)C)=C1 UEZQPLQZAUVRDZ-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- JNAUIOQFUDVUJP-UHFFFAOYSA-N 4-cyclododecylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCCCCCCCC1 JNAUIOQFUDVUJP-UHFFFAOYSA-N 0.000 description 1
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 description 1
- SNBKPVVDUBFDEJ-UHFFFAOYSA-N 4-cyclopentylphenol Chemical compound C1=CC(O)=CC=C1C1CCCC1 SNBKPVVDUBFDEJ-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXIKRTCSSLJURC-UHFFFAOYSA-N Dihydroeugenol Chemical compound CCCC1=CC=C(O)C(OC)=C1 PXIKRTCSSLJURC-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 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 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 125000005028 dihydroxyaryl group Chemical group 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a composition of flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin. The composition comprises the following components and weight percentage (based on the total weight of the composition): 40 to 80 percent of polycarbonate, 5 to 45 percent of acrylonitrile-butadiene-styrene resin, 5 to 40 percent of halogen-free main flame retardant and 1 to 5 percent of boron-containing auxiliary flame retardant. The composition of flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin can not emit a large amount of dense smoke, corrosive gas or toxic gas during combustion, and improves the processability of materials.
Description
Technical Field
The invention belongs to the field of polymer modification, and particularly relates to a flame-retardant polycarbonate and acrylonitrile-butadiene-styrene thermoplastic resin composition.
Background
Polycarbonate (PC) is an amorphous thermoplastic engineering plastic with excellent mechanical, electrical and heat resistance properties in combination, especially known for its excellent impact strength and creep resistance. The polycarbonate and the blend (or alloy) of the polycarbonate and other high polymers, in particular the composition of acrylonitrile-butadiene-styrene are widely used in the fields of electronics, electricity, machinery, automobiles, aerospace, construction, office work and the like.
Household appliances and office supplies have requirements on heat resistance and flame retardance, and halogen flame retardants are usually added for flame retardance. For example, US4810739 discloses a flame retardant thermoplastic composition comprising an aromatic polycarbonate, an acrylonitrile-butadiene-styrene graft copolymer, a styrene-acrylonitrile copolymer, a halide, a flame retardant synergist and polytetrafluoroethylene; for another example, CN1978528A discloses a special material for low-smoke flame-retardant polycarbonate/acrylonitrile-butadiene-styrene alloy sheet, which is mainly prepared by adding triphenyl phosphate, decabromodiphenyl oxide and activated zinc borate. However, the halogen flame retardant is added, so that a large amount of toxic gas and dense smoke are released during combustion of the material, the material is not environment-friendly, and secondary disasters can be caused.
The RoHS directive published in the European Union requires that the products of exported electronic and electric appliances put on the market do not contain harmful substances such as polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) from the 7 th and 1 st of 2006, and the products exported from the European Union of enterprises need to meet the limit requirements, so that the use of the halogen flame retardant is increasingly limited. In the above fields, with the increase of the usage of flame retardant and flame retardant material, the environmental protection halogen-free flame retardant will be gradually changed in the future.
Some patent documents also report methods of halogen-free flame retardant polycarbonate/acrylonitrile-butadiene-styrene alloy, such as CN1435445, which discloses a halogen-free flame retardant polycarbonate/styrene-based resin composition. Polycarbonate/acrylonitrile-butadiene-styrene alloy generates a large amount of smoke when burning, and the flame retardant polycarbonate/acrylonitrile-butadiene-styrene alloy is more so, so that a large amount of toxic smoke threatens the life safety of people in case of fire of the manufactured product. The single use of phosphorus-nitrogen flame retardant has a non-optimal flame retardant effect and cannot well solve the problem of smoke suppression. In view of the above, there is a lack in the art of an environmentally friendly halogen-free flame retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition. Therefore, there is an urgent need in the art to develop an environment-friendly halogen-free flame retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition which does not emit a large amount of smoke, corrosive gas, or toxic gas when burned and improves the processability of the material.
Disclosure of Invention
The invention aims to obtain an environment-friendly halogen-free flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition which does not emit a large amount of dense smoke, corrosive gas and toxic gas during combustion and improves the processability of materials.
The invention also aims to obtain a flame-retardant material prepared from the composition, which does not emit a large amount of smoke, corrosive gas and toxic gas during combustion and improves the processability of the material.
Still another object of the present invention is to obtain the use of a composite flame retardant which does not give off a large amount of smoke, corrosive gases, toxic gases during combustion and which improves the processability of the material.
In a first aspect of the present invention, there is provided a flame retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition comprising:
40-80% by weight of a polycarbonate,
5-45 wt% of an acrylonitrile-butadiene-styrene resin,
5-40% by weight of a halogen-free primary flame retardant, and
1-5 wt% of boron-based auxiliary flame retardant.
In one embodiment of the present invention,
the halogen-free main flame retardant consists of a phosphorus flame retardant and a nitrogen flame retardant,
the weight ratio of the phosphorus flame retardant to the nitrogen flame retardant is 0.4: 1-4: 1.
In one embodiment of the present invention, the weight ratio of the halogen-free main flame retardant to the boron-based flame retardant is 2: 1-30: 1.
in one embodiment of the present invention, the phosphorus-based flame retardant is selected from the group consisting of a monophosphate ester, a diphosphate ester, or a combination thereof.
Preferably, the monophosphate ester is selected from the group consisting of triphenyl phosphate, triethyl phosphate, tributyl phosphate, or combinations thereof.
Preferably, the bisphosphate is selected from resorcinol bisphosphonates, bisphenol a bisphosphonates, diphenyl pentaerythritol diphosphate or combinations thereof.
In one embodiment of the present invention, the nitrogen-based flame retardant is selected from dicyandiamide, melamine salt, melamine isocyanate or a combination thereof.
In one embodiment of the present invention, the boron-based secondary flame retardant is selected from zinc borate, borax, phenyl boronic acid compounds, or combinations thereof.
Preferably, the boron-based auxiliary flame retardant is a phenyl boric acid compound, borax or a combination thereof.
More preferably, the phenyl boronic acid compound is p-phenylboronic acid, m-phenylboronic acid, or a combination thereof.
In one embodiment of the invention, the composition further comprises the following components: 0.1-5% of antioxidant, 1-10% of impact modifier, 0.1-5% of compatibilizer, 0.1-5% of flame-retardant acceptable auxiliary agent or the combination thereof.
In one embodiment of the present invention, the antioxidant is selected from the group consisting of pentaerythrityl tetrakis-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl propionate), 2, 6-di-tert-butyl-4-methylphenol, octadecyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, di (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, 2' -methylene-bis (4-methyl-6-tert-butylphenol), tris (3, 5-di-tert-butyl-4-hydroxybenzyl) triisocyanurate, triester of 2, 4-di-tert-butylphenyl) phosphite, or a combination thereof.
In one embodiment of the present invention, the impact modifier is selected from the group consisting of acrylate copolymer resin (ACR resin), methyl methacrylate/butadiene/styrene copolymer, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene high rubber powder, or a combination thereof.
In one embodiment of the present invention, the compatibilizer is selected from polycarbonate grafted styrene/acrylonitrile copolymer, polyethylene grafted maleic anhydride, polymethyl methacrylate, ethylene-methacrylic acid-sodium methacrylate ionomer, styrene-butadiene copolymer, or a combination thereof.
In one embodiment of the invention, the other flame retardant chemically acceptable auxiliary agent is selected from lubricants, stabilizers, antistatic agents or combinations thereof.
The invention also provides a flame-retardant material prepared from the composition; and a flame-retardant product made of the flame-retardant material.
Preferably, the flame retardant article is an electronic and electrical material; more preferably, a printed circuit board.
In a further aspect, the present invention provides the use of a composite flame retardant for the preparation of flame retardant polycarbonate and acrylonitrile-butadiene-styrene resin materials;
wherein,
the composite flame retardant consists of a halogen-free main flame retardant and a boron flame retardant,
the weight ratio of the halogen-free main flame retardant to the boron flame retardant is 2: 1-30: 1;
the halogen-free main flame retardant consists of a phosphorus flame retardant and a nitrogen flame retardant, and the weight ratio of the phosphorus flame retardant to the nitrogen flame retardant is 0.4: 1-4: 1.
Detailed Description
The present inventors have extensively and intensively studied to obtain a composite flame retardant suitable for polycarbonate and acrylonitrile-butadiene-styrene resin compositions by improving the preparation process, and found that a large amount of smoke, corrosive gas and toxic gas are not emitted during combustion and the processability of the material is improved. It is particularly suitable as a flame retardant additive for polycarbonate and acrylonitrile-butadiene-styrene resin compositions. The present invention has been completed based on this finding.
As used herein, the term "alkyl", unless otherwise specified, refers to a straight or branched chain alkane containing 2 to 20 carbon atoms. Preferred are alkanes having 2 to 10 carbon atoms, for example, alkyl groups including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
As used herein, the term "aryl", unless otherwise specified, refers to monocyclic aromatic hydrocarbons containing 6 carbon atoms, bicyclic aromatic hydrocarbons containing 10 carbon atoms, tricyclic aromatic hydrocarbons containing 14 carbon atoms, and may have 1 to 4 substituents, such as 1 to 4 alkyl groups, on each ring. For example, aryl groups include, but are not limited to, phenyl, naphthyl, anthracenyl.
Various aspects of the invention are described in detail below:
polycarbonate and acrylonitrile-butadiene-styrene resin composition
The polycarbonate of the present invention is not particularly limited. Specifically, for example, there are aromatic polycarbonates obtained by reacting various dihydroxyaryl compounds with phosgene, or aromatic polycarbonates obtained by transesterification of a dihydroxyaryl compound with diphenyl carbonate. Specifically, for example, bisphenol A type aromatic polycarbonate.
In particular, the dihydroxyaryl compound is a bisphenol based on formula (III)
Wherein:
a represents a single bond, C1-C5 alkylene, C2-C5 alkylidene, C5-C6 cycloalkyl, -S-, -SO2-, -O-, -CO-, or C6-C12 arylene, which groups may optionally be condensed with other aromatic rings containing heteroatoms,
b independently of one another represents C1-C8 alkylene, C6-C10 aryl, preferably phenyl, C7-C12 cycloalkyl,
y independently of one another represents 0, 1 or 2,
p represents 1 or 0.
Suitable diphenols are bis (4-hydroxyphenyl) methane, 1 '-bis (4-hydroxyphenyl) ethane, 2' -bis (4-hydroxyphenyl) propane ("bisphenol A"), 2 '-bis (4-hydroxyphenyl) butane, 2' -bis (4-hydroxy-3-methylphenyl) propane, 2 '-bis (4-hydroxy-3-methoxyphenyl) propane, 2' -bis (4-hydroxy-3-tert-butylphenyl) propane, 2 '-bis (4-hydroxy-3-cyclohexylphenyl) propane, 1' -bis (4-hydroxyphenyl) cyclopentane, 1 '-bis (4-hydroxyphenyl) cyclohexane, 1' -bis (4-hydroxyphenyl) cyclododecane, 4, 4 ' -dihydroxyphenyl ether, 4 ' -dihydroxydiphenyl sulfoxide, 4 ' -dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) ketone, 2, 6-dihydroxynaphthalene, and the like.
Bis (4-hydroxyphenyl) methane, 2 '-bis (4-hydroxyphenyl) propane ("bisphenol A"), 2' -bis (4-hydroxy-3-methylphenyl) propane are preferred. Bisphenol A is particularly preferred.
The production method of the polycarbonate of the present invention is not particularly limited, and can be produced according to a method known in the literature, and can be obtained from a plurality of commercial sources. Specifically, for example, transesterification, interfacial polymerization, solution polymerization, and bulk polymerization.
The acrylonitrile-butadiene-styrene resin (ABS) according to the present invention is not particularly limited as long as it achieves desired performance characteristics. By changing the ratio of the three monomers and adopting different polymerization methods, products with various specifications can be prepared, and the structure of the products comprises a graft copolymer taking an elastomer as a main chain and a graft copolymer taking resin as a main chain. Specifically, for example, the weight ratio of the three monomers ranges from 25% to 35% acrylonitrile, 25% to 30% butadiene and 40% to 50% styrene.
The method for producing the acrylonitrile-butadiene-styrene resin (ABS) according to the present invention is not particularly limited, and can be produced according to a method known in the literature and can be obtained from various commercial sources.
The polycarbonate content in the composition of the invention is 40 to 80% by weight, preferably 50 to 70% by weight.
The acrylonitrile-butadiene-styrene resin content in the composition of the present invention is 5 to 45% by weight, preferably 5 to 40% by weight.
Halogen-free main flame retardant
Phosphorus flame retardant
The phosphorus flame retardant is an organic phosphorus compound shown as a formula (I):
wherein said R1、R2、R3、R4Independently of one another, C1-C8 alkyl, or C5-C6 cycloalkyl, C6-C20 aryl or C7-C12 aralkyl, each of which is optionally substituted by C1-C4 alkyl, preferably phenyl, tolyl, xylyl, C1-C4 alkyl, cyclohexane, particularly preferably phenyl.
n represents independently of one another 0 or 1, preferably 1.
N is from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 5.
X represents a monocyclic or polycyclic aromatic group having 6 to 30 carbon atoms, which may be p-phenyl, m-phenyl, bisphenol A, hydroquinone or the like, preferably m-phenyl, bisphenol A.
Preferably, the phosphorus-based flame retardant is selected from the group consisting of monophosphate esters, diphosphate esters, or a combination thereof. Examples of corresponding organophosphorus compounds of the formula (I) include: triphenyl phosphate (i.e., triphenyl phosphate), triethyl phosphate, tributyl phosphate, trimethylphenyl phosphate, tris (2, 4-dimethylphenyl) phosphate, resorcinol bis- (diphenyl phosphate), bisphenol a bis- (diphenyl phosphate), or combinations thereof.
More preferably, the monophosphate ester is selected from triphenyl phosphate, triethyl phosphate, tributyl phosphate, or combinations thereof; the bisphosphate is selected from resorcinol bisphosphonates, bisphenol a bisphosphonates, diphenyl pentaerythritol diphosphate, or combinations thereof.
Nitrogen-containing flame retardant
The nitrogen-based flame retardant of the invention is a compound represented by the general formula (II),
wherein R is5、R6、R7Selected from hydrogen atom, amino group, aryl group or alkoxy group with 1-3 carbon atoms, R5、R6、R7The same or different.
When said R is5、R6、R7When selected from amino groups, the nitrogen-containing compounds also include salts of amino groups with acids or condensates of amino groups with aldehydes.
The acid is not particularly limited as long as it does not limit the object of the present invention. Specifically, for example, uric acid and phosphoric acid.
The aldehydes are not particularly limited as long as they do not limit the object of the present invention. Specifically, for example, formaldehyde.
Preferably, R in said compound of formula (II)7Selected from amino groups and salts thereof.
More preferably, R in said compound of formula (II)6、R7Are both amino and salts thereof.
Most preferably, the nitrogen-based flame retardant is selected from dicyandiamide, melamine salt, melamine isocyanate or a combination thereof.
The halogen-free type main flame retardant of the present invention is usually 5 to 40% by weight, preferably 10. + -.3% by weight, based on the flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition.
In the halogen-free flame retardant of the present invention, the weight ratio of the phosphorus-containing flame retardant to the nitrogen-containing flame retardant in the mixture is usually (1: 10) to (10: 1), preferably 0.4: 1-4: 1, more preferably 0.5: 1-2: 1, more preferably 1.5: 1.
the boron-based auxiliary flame retardant of the invention
The boron-based auxiliary flame retardant is selected from zinc borate, borax, phenyl boric acid compounds or a combination thereof.
Specific examples of the phenyl boronic acid compound are p-phenylboronic acid, m-phenyltriboric acid, or a combination thereof, with m-phenyltriboric acid being preferred.
The content of the boron-based auxiliary flame retardant is 1-5 wt% based on the total weight of the composition.
The weight ratio of the halogen-free main flame retardant to the boron flame retardant is 2: 1-30: 1, typically 2: 1-15: 1, most preferably 3: 1-10: 1.
the inventor of the invention finds that the halogen-free flame retardant and the boron auxiliary flame retardant in a specific ratio are added into the composition of polycarbonate and acrylonitrile-butadiene-styrene system, so that a synergistic effect can be obtained to achieve a good flame retardant effect. After the two flame retardants are compounded in proportion, the mixture loses water at a processing temperature to form a network structure, and when the material is combusted and decomposed, a protective layer is formed on the surface of the material to play a role in heat insulation and oxygen inhibition and prevent the material from continuing to combust. Particularly, when the phenylboronic acid compound is adopted, the smoke suppression effect is better.
Antioxidant agent
An antioxidant may be added to the composition of the present invention. Typically, the antioxidant is selected from pentaerythritol tetrakis-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl propionate), 2, 6-di-tert-butyl-4-methylphenol, octadecyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, di-2, 4-di-tert-butylphenyl pentaerythritol diphosphite, 2' -methylene-bis- (4-methyl-6-tert-butylphenol), tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) triisocyanurate, triester of 2, 4-di-tert-butylphenyl phosphite, or combinations thereof.
The antioxidants of the present invention are generally used in amounts of 0.1 to 5 percent, based on the total weight of the composition.
Impact modifier
Impact modifiers may be added to the compositions of the present invention. Generally, the impact modifier of the present invention is selected from an acrylate copolymer (ACR resin), a methyl methacrylate/butadiene/styrene copolymer (MBS resin), a chlorinated polyethylene resin (CPE resin), an ethylene-vinyl acetate copolymer (EVA resin), an acrylonitrile-butadiene-styrene high rubber powder, or a combination thereof.
The type or brand of the resin is not particularly limited as long as it does not limit the object of the present invention.
The impact modifier of the present invention is used in an amount of 1 to 10% by weight, based on the total weight of the composition.
Compatibilizer
Compatibilizers may be added to the compositions of the present invention. Typically, the compatibilizer is selected from polycarbonate grafted styrene/acrylonitrile copolymer (PC-g-SAN), polyethylene grafted maleic anhydride (PE-g-MAH), polymethyl methacrylate (PMMA), ethylene-methacrylic acid-sodium methacrylate ionomer, styrene-butadiene copolymer, or combinations thereof.
The polymerization degree, molecular weight distribution, and segment distribution (for example, as a copolymer) of the compatibilizer are not particularly limited as long as the object of the present invention is not limited.
The compatibilizer of the present invention is used in an amount of 0.1 to 5% based on the total weight of the composition.
Other auxiliaries suitable for use
The composition of the present invention may also optionally contain one or more other suitable auxiliaries, the kind of which is not particularly limited as long as it does not limit the object of the present invention. Such as additives, in particular heat stabilizers, light stabilizers, pigments, mold release agents, lubricants, flow promoters, inorganic reinforcing materials, carbon fibers, small particles and/or antistatic agents.
Preferably, the further auxiliary agent is selected from lubricants, stabilizers, antistatic agents or combinations thereof.
The amount of the other auxiliary agents applicable to the present invention is not particularly limited as long as it does not limit the object of the present invention. Specifically, for example, 0.1 to 5% by weight based on the total weight of the composition.
Flame retardant material or flame retardant article
The flame retardant composition of the present invention can be prepared into flame retardant materials by methods commonly used in the art.
The invention also provides a flame-retardant product prepared from the flame-retardant material.
For example, polycarbonate, acrylonitrile-butadiene-styrene resin, phosphorus-nitrogen main flame retardant, boron auxiliary flame retardant, antioxidant, impact modifier, compatibilizer and other auxiliary agents are mixed by a high-speed mixer according to a certain proportion, and then are mixed and extruded by a double-screw extruder, and then are granulated to obtain the flame retardant material.
The flame retardant material can be prepared into flame retardant products by adopting a method commonly used in the field. Preferably, the flame retardant article is an electronic and electrical material; more preferably, a printed circuit board.
Use of
The invention also provides the application of the composite flame retardant, which is used for preparing flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin materials.
Preferably, the composite flame retardant comprises a phosphorus-based main flame retardant, a nitrogen-based main flame retardant and a boron-based auxiliary flame retardant, and the weight ratio is as follows: phosphorus-based main flame retardant: nitrogen-based main flame retardant: boron-based auxiliary flame retardant (2-20): (2-20): (1-5), and the total weight of the phosphorus-based main flame retardant and the nitrogen-based main flame retardant accounts for 5-40 wt% of the composition.
Preferably, the weight ratio of the carbonate to the acrylonitrile-butadiene-styrene resin in the polycarbonate and acrylonitrile-butadiene-styrene resin material is (40-80): (5-45).
The invention has the advantages that:
(1) the composition has excellent flame-retardant and smoke-suppressing effects, does not harm the environment, can reach UL941.6V-0 level standard, has excellent physical properties and improves the processing performance of materials.
The compound provided by the invention can be synthesized by using commercially available raw materials and a traditional chemical conversion mode.
Other aspects of the invention will be apparent to those skilled in the art in view of the disclosure herein.
The present invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures in the following examples, in which the specific conditions are not specified, are generally carried out under conventional conditions, for example, those in the handbook of organic chemistry of Belstein (chemical industry Press, 1996), or under the conditions recommended by the manufacturers. Proportions and percentages are by weight unless otherwise indicated.
Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
Examples 1 to 18
The polycarbonate, the acrylonitrile-butadiene-styrene resin, the phosphorus-nitrogen main flame retardant, the boron auxiliary flame retardant, the antioxidant, the impact modifier, the compatibilizer and other auxiliaries are mixed by a high-speed mixer according to the following proportion to obtain the composition, and the composition is mixed and extruded by a double-screw extruder (210-240 ℃) and granulated to obtain the flame-retardant material. Injection molded specimens can be tested for performance.
The following measurement methods were used in the present invention:
method for measuring combustibility: the UL-94 standard. UL-94 is the vertical burn test: the fire tests were carried out in class V according to UL94 test for flammability of Plastic materials for Equipment and appliance parts.
Method for measuring tensile strength: GB/T1040-1992
Method for measuring impact strength: GB/T1843-1996
The smoke density measuring method comprises the following steps: GB/T8323-87 Performance results for examples 1-9 are shown in Table 1
Table 1: detailed description of the examples and testing of the Properties of the materials
Note:
the polycarbonates used in examples 1 to 9 and comparative examples 1 to 2 were 3103, which was produced by Bayer AG in Germany.
The acrylonitrile-butadiene styrene resin (ABS resin) is composed of 25-35 wt% of acrylonitrile, 25-30 wt% of butadiene and 40-50 wt% of styrene, based on the total weight of the acrylonitrile-butadiene-styrene resin.
And the antioxidants adopted in the embodiments 1 to 9 and the comparative examples 1 to 2 are commonly called antioxidant 1010 and antioxidant 168 respectively.
(iv) the impact modifiers used in examples 1 to 9 and comparative examples 1 to 2 were ACR-401 resin (acrylate copolymer) from Zhuhai Polyfeng technologies, Inc. and A1218 from Guangdong Heizhou repulping chemical Co., Ltd.
The other auxiliary agents adopted in the embodiments 1-9 and the comparative examples 1-2 are equal amount of the light stabilizer EH-770 of Shanghai Hui chemical science and technology Limited and the antistatic agent KJD-730 of Shanghai Ningyi chemical industry Limited.
The composition is prepared by mixing polycarbonate, acrylonitrile-butadiene-styrene resin, a phosphorus-nitrogen main flame retardant, a boron auxiliary flame retardant, an antioxidant, an impact modifier, a compatibilizer and other auxiliaries according to the following proportion by a high-speed mixer, mixing and extruding by a double-screw extruder (210-240 ℃), and granulating. Injection molded specimens can be tested for performance. The performance results for examples 10 to 18 are shown in Table 2.
Table 2: detailed description of the examples and testing of the Properties of the materials
Note:
the polycarbonates used in examples 10 to 18 were all polycarbonates 3103 produced by Bayer AG in Germany.
The acrylonitrile-butadiene-styrene resin is prepared from 25-35 wt% of acrylonitrile, 25-30 wt% of butadiene and 40-50 wt% of styrene, based on the total weight of the acrylonitrile-butadiene-styrene resin.
③ 1076 is used as the antioxidant in the above examples 10 to 18.
(iv) impact modifier used in examples 10 to 18 above: the methyl methacrylate/butadiene/styrene copolymer (MBS resin) LB-22 was obtained from Shanghai bamboo chemical Co., Ltd, and the ethylene-vinyl acetate copolymer (EVA)4260 was obtained from Wuhanhui Hupu chemical New materials Co., Ltd.
The other additives adopted in the above embodiments 10 to 18 are equal amounts of the light stabilizer EH-770 of Shanghai chemical science and technology Limited and the antistatic agent KJD-730 of Shanghai Ningyi chemical industry Limited.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A flame retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition comprising:
40-80% by weight of a polycarbonate,
5-45 wt% of an acrylonitrile-butadiene-styrene resin,
5-40% by weight of a halogen-free primary flame retardant, and
1-5 wt% of boron-based auxiliary flame retardant.
2. The composition of claim 1,
the halogen-free main flame retardant consists of a phosphorus flame retardant and a nitrogen flame retardant,
the weight ratio of the phosphorus flame retardant to the nitrogen flame retardant is 0.4: 1-4: 1.
3. The composition of claim 1, wherein the weight ratio of the halogen-free main flame retardant to the boron-based flame retardant is 2: 1-30: 1.
4. the composition of claim 2, wherein the phosphorus-based flame retardant is selected from the group consisting of a monophosphate ester, a diphosphate ester, or a combination thereof;
preferably, the monophosphate ester is selected from triphenyl phosphate, triethyl phosphate, tributyl phosphate, or combinations thereof;
preferably, the bisphosphate is selected from resorcinol bisphosphonates, bisphenol a bisphosphonates, diphenyl pentaerythritol diphosphate or combinations thereof.
5. The composition of claim 2, wherein the nitrogen-based flame retardant is selected from the group consisting of dicyandiamide, melamine salt, melamine isocyanate, and combinations thereof.
6. The composition of claim 1,
the boron auxiliary flame retardant is selected from zinc borate, borax, phenyl boric acid compounds or the combination thereof;
preferably a phenyl boronic acid compound, borax, or a combination thereof;
more preferably, the phenyl boronic acid compound is p-phenylboronic acid, m-phenylboronic acid, or a combination thereof.
7. The composition of claim 1, further comprising the following components: 0.1-5% of antioxidant, 1-10% of impact modifier, 0.1-5% of compatibilizer, 0.1-5% of flame-retardant acceptable auxiliary agent or the combination thereof.
8. The composition of claim 7,
preferably, the antioxidant is selected from pentaerythritol tetrakis-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl propionate), 2, 6-di-tert-butyl-4-methylphenol, octadecyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, di- (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, 2' -methylene-bis- (4-methyl-6-tert-butylphenol), tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) triisocyanurate, triester of 2, 4-di-tert-butylphenyl) phosphite, or a combination thereof;
preferably, the impact modifier is selected from acrylate copolymer resin (ACR resin), methyl methacrylate/butadiene/styrene copolymer, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene high rubber powder or combination thereof;
preferably, the compatibilizer is selected from polycarbonate grafted styrene/acrylonitrile copolymer, polyethylene grafted maleic anhydride, polymethyl methacrylate, ethylene-methacrylic acid-sodium methacrylate ionomer, styrene-butadiene copolymer or a combination thereof;
preferably, the other flame retardant chemically acceptable auxiliary agent is selected from a lubricant, a stabilizer, an antistatic agent or a combination thereof.
9. A flame retardant material made from the composition of any of claims 1 to 8; and a flame-retardant article made of the flame-retardant material;
preferably, the flame retardant article is an electronic and electrical material; more preferably, a printed circuit board.
10. The application of the composite flame retardant is characterized in that the composite flame retardant is used for preparing flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin materials;
wherein,
the composite flame retardant consists of a halogen-free main flame retardant and a boron flame retardant,
the weight ratio of the halogen-free main flame retardant to the boron flame retardant is 2: 1-30: 1;
the halogen-free main flame retardant consists of a phosphorus flame retardant and a nitrogen flame retardant, and the weight ratio of the phosphorus flame retardant to the nitrogen flame retardant is 0.4: 1-4: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100470539A CN101412843A (en) | 2007-10-16 | 2007-10-16 | Flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin compositions |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100470539A CN101412843A (en) | 2007-10-16 | 2007-10-16 | Flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin compositions |
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| CN101412843A true CN101412843A (en) | 2009-04-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2007100470539A Pending CN101412843A (en) | 2007-10-16 | 2007-10-16 | Flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin compositions |
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| CN101967274A (en) * | 2010-10-11 | 2011-02-09 | 余林华 | Permanent antistatic polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) composite material and preparation method thereof |
| CN102093690A (en) * | 2010-12-30 | 2011-06-15 | 佛山市顺德区圆融新材料有限公司 | Cold-resistant flame-retardant polycarbonate alloy material and preparation method thereof |
| CN102241881A (en) * | 2010-11-30 | 2011-11-16 | 深圳市科聚新材料有限公司 | Halogen-free, flame-retarding and high glowing filament resistant PC/ABS alloy and preparation method thereof |
| CN102382436A (en) * | 2010-09-02 | 2012-03-21 | 天津大沽化工股份有限公司 | Preparation method for polycarbonate/acrylonitrile-butadiene-styrene alloy |
| CN102516732A (en) * | 2011-12-02 | 2012-06-27 | 四川长虹电器股份有限公司 | Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof |
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| CN103525059A (en) * | 2013-10-25 | 2014-01-22 | 安徽省富光实业股份有限公司 | ABS (acrylonitrile-butadiene-styrene)-modified composite polycarbonate material for water cup shell and preparation method of ABS-modified composite polycarbonate material |
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| CN101967274A (en) * | 2010-10-11 | 2011-02-09 | 余林华 | Permanent antistatic polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) composite material and preparation method thereof |
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| CN102093690A (en) * | 2010-12-30 | 2011-06-15 | 佛山市顺德区圆融新材料有限公司 | Cold-resistant flame-retardant polycarbonate alloy material and preparation method thereof |
| CN102516732A (en) * | 2011-12-02 | 2012-06-27 | 四川长虹电器股份有限公司 | Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof |
| CN103087495A (en) * | 2013-01-24 | 2013-05-08 | 李顺平 | Alloy plastic particle |
| CN103333481A (en) * | 2013-07-19 | 2013-10-02 | 上海锦湖日丽塑料有限公司 | Wear-resisting PC/ABS alloy material and preparation method thereof |
| CN103333481B (en) * | 2013-07-19 | 2015-10-28 | 上海锦湖日丽塑料有限公司 | A kind of wear-resisting PC/ABS alloy material and preparation method thereof |
| CN103525059A (en) * | 2013-10-25 | 2014-01-22 | 安徽省富光实业股份有限公司 | ABS (acrylonitrile-butadiene-styrene)-modified composite polycarbonate material for water cup shell and preparation method of ABS-modified composite polycarbonate material |
| CN110358278A (en) * | 2019-07-01 | 2019-10-22 | 武汉市太行冶金材料有限公司 | A kind of packaging steel coils flame retardant type plastic sheet PP Pipe Compound and preparation method thereof |
| CN113214598A (en) * | 2021-05-10 | 2021-08-06 | 安徽亚强节能科技有限公司 | Modified phenolic foam and application thereof in wall thermal insulation material |
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| CN117801495B (en) * | 2023-12-29 | 2024-09-03 | 青岛中新华美塑料有限公司 | Environment-friendly flame-retardant PC material and preparation method thereof |
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Application publication date: 20090422 |