CN110746756B - Flame-retardant polycarbonate composite material and preparation method thereof - Google Patents
Flame-retardant polycarbonate composite material and preparation method thereof Download PDFInfo
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- CN110746756B CN110746756B CN201910882520.2A CN201910882520A CN110746756B CN 110746756 B CN110746756 B CN 110746756B CN 201910882520 A CN201910882520 A CN 201910882520A CN 110746756 B CN110746756 B CN 110746756B
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- flame retardant
- polycarbonate
- flame
- molecular weight
- retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 101
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 94
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 94
- 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 80
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 5
- 230000008859 change Effects 0.000 claims abstract description 25
- 238000009826 distribution Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims description 28
- 239000000314 lubricant Substances 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- -1 alkali metal salts Chemical class 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005227 gel permeation chromatography Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 claims description 2
- NQXBRQZPHIYOKB-UHFFFAOYSA-N [F].[Ag] Chemical compound [F].[Ag] NQXBRQZPHIYOKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002479 acid--base titration Methods 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 claims description 2
- WFRUBUQWJYMMRQ-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WFRUBUQWJYMMRQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 16
- 239000004431 polycarbonate resin Substances 0.000 description 13
- 229920005668 polycarbonate resin Polymers 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 9
- 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 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000032683 aging Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002386 leaching Methods 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
- 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
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- OWQPOVKKUWUEKE-UHFFFAOYSA-N 1,2,3-benzotriazine Chemical compound N1=NN=CC2=CC=CC=C21 OWQPOVKKUWUEKE-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- UDKBLXVYLPCIAZ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-3,6-di(propan-2-yl)phenyl]phenol Chemical compound C=1C=C(O)C=CC=1C=1C(C(C)C)=CC=C(C(C)C)C=1C1=CC=C(O)C=C1 UDKBLXVYLPCIAZ-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)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 BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- GCXUHGZBBGZTII-UHFFFAOYSA-N a828071 Chemical compound ClC(Cl)=O.ClC(Cl)=O GCXUHGZBBGZTII-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- GGRIQDPLLHVRDU-UHFFFAOYSA-M potassium;2-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 GGRIQDPLLHVRDU-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 230000007704 transition Effects 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant polycarbonate composite material which comprises the following components in parts by weight: 60-100 parts of polycarbonate; 1-25 parts of a flame retardant; the weight average molecular weight of the polycarbonate is more than 26000, the molecular weight distribution index PDI is less than 2.2, the pH of the polycarbonate solution is 6.7-7.1, and the temperature change of Tg is realized through multiple cycles. It has been found in the present invention that when the polycarbonate is within the above parameters, the flame retardant has less effect on the stability of the polycarbonate.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant polycarbonate composite material and a preparation method thereof.
Background
Currently, Polycarbonate (PC) is widely used for producing various industrial and civil articles (such as various transparent articles, lamp covers, instrument panels, etc.). In order to expand the range of applications of polycarbonates, flame retardant modifications are required. However, since the polycarbonate is in a weak acid stable state, the addition of the flame retardant can change the overall pH value to affect the stability of the polycarbonate, and particularly, the alkali metal element (such as antimony dioxide) contained in the flame retardant and free bromine in the bromine flame retardant can cause the weak acid polycarbonate to be decomposed in the melt processing process, so that the performance of the polycarbonate is reduced, and even the performance of the polycarbonate cannot meet the application standard.
Generally, the method for improving the thermal stability of the flame retardant polycarbonate is to add a substance, for example, Chinese patent application 2018107637061 discloses a polycarbonate composition, wherein siloxane is added to improve the thermal stability of the flame retardant polycarbonate composition. Or, in order to ensure the stability of the flame-retardant polycarbonate, only some neutral and mild flame retardants can be added, so that the addition amount is large and the other properties of the material are greatly influenced.
There has been no report of a method for improving the stability of polycarbonate after adding a flame retardant by controlling the synthesis of polycarbonate to obtain polycarbonate within a specific parameter range.
Disclosure of Invention
The invention aims to provide a flame-retardant polycarbonate composite material which has the advantage of good thermal stability.
The invention also aims to provide a preparation method of the flame-retardant polycarbonate composite material.
The invention is realized by the following technical scheme:
the flame-retardant polycarbonate composite material comprises the following components in parts by weight:
60-100 parts of polycarbonate;
1-25 parts of a flame retardant;
the weight average molecular weight of the polycarbonate is more than 26000, the molecular weight distribution index PDI is less than 2.2, the pH of the polycarbonate solution is 6.7-7.1, and the temperature change of the multi-cycle Tg is less than 3.3 ℃.
Preferably, the polycarbonate has a weight average molecular weight of greater than 26000, a molecular weight distribution index PDI of less than 2.0, a polycarbonate solution pH of 6.8 to 6.9, and a multiple cycle Tg temperature change of less than 2.1 ℃.
Generally, the weight average molecular weight of more than 26000 belongs to the range from medium molecular weight to high molecular weight, and products with the molecular weight distribution index PDI of less than 2.2 and the temperature change of multiple cycle Tg of less than 3.3 ℃ are harder to obtain in the range; in general, the pH of the polycarbonate solution without pH adjustment is in the range of 6.3 to 7.3. The invention obtains the polycarbonate with corresponding molecular weight range and molecular weight distribution by refined and programmed reaction parameter control; the pH of the polycarbonate is also adjusted to 6.7-7.1 by adding hydroxide or acidic substances and the temperature change of the multi-cycle Tg is controlled to be less than 3.3 ℃ according to the relation between different molecular weights, molecular weight distribution and pH.
Polycarbonate resins which meet the above-mentioned parametric characteristics may be branched thermoplastic polymers or copolymers obtained by reaction of dihydroxy compounds or mixtures thereof with small amounts of polyhydroxy compounds with phosgene (phosgene) or carbonic acid diesters. The production method of the polycarbonate resin is not particularly limited, and polycarbonate resins produced by a phosgene method (interfacial polymerization method) or a melting method (transesterification method) known so far may be used. An aromatic dihydroxy compound is preferable as the starting dihydroxy compound, and may be exemplified by 2, 2-bis (4-hydroxyphenyl) propane (═ bisphenol a), tetramethylbisphenol a, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4-dihydroxybiphenyl and the like, of which bisphenol a is preferable. A compound in which at least one tetraalkylphosphonium sulfonate (tetraalkylphosphonium sulfonate) is bound to the aforementioned aromatic dihydroxy compound can also be used. Of the foregoing, the polycarbonate resin is preferably an aromatic polycarbonate resin derived from 2, 2-bis (4-hydroxyphenyl) propane, or an aromatic polycarbonate copolymer derived from 2, 2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds. The polycarbonate resin may also be a copolymer in which the main component is an aromatic polycarbonate resin, for example, a copolymer with a polymer or oligomer containing a siloxane structure. Further, a mixture of two or more of the above polycarbonate resins may be used. The monohydric aromatic hydroxy compounds may be used to adjust the molecular weight of the polycarbonate resin, for example, m-methylphenol, p-methylphenol, m-propylphenol, p-t-butylphenol, and p- (long chain alkyl) -substituted phenols.
The method for producing the polycarbonate resin is not particularly limited in the present invention, and a polycarbonate resin produced by a phosgene method (interfacial polymerization method) or a melt method (transesterification method) can be used. The parameters of the polycarbonate product prepared by the process may be adjusted to meet the above-mentioned ranges of parameters.
The molecular weight and molecular weight distribution index of the polycarbonate are mainly controlled by controlling the process conditions (such as feeding ratio, secondary feeding or multiple feeding, polymerization temperature and polymerization time).
The method for testing the pH value of the polycarbonate solution comprises the steps of dissolving polycarbonate in a dichloromethane solvent, filtering the solution, and carrying out acid-base titration on an organic phase to test the pH value; the method of molecular weight distribution index PDI is gel permeation chromatography.
The gel permeation chromatography analysis method specifically comprises the steps of respectively selecting 2mg of standard sample and a sample to be detected to be dissolved in 2ml of dichloromethane, filtering the solution by using a filter of a microporous filter membrane with the aperture of 0.45um after the solution is dissolved, setting the leaching flow rate to be 1.0ml/min, setting the column temperature and the detection temperature to be 30 ℃, successively adding the standard solution and the sample to be detected into a sample injection syringe after a baseline is stable, leaching the sample injection amount to be 100ul by using an isochromatography, and obtaining the final PDI result after the sample to be detected and the standard sample are compared with data.
Generally, the pH of the polycarbonate solution is in the range of 6.3 to 7.3; the pH value range influencing the solution is mainly hydroxide in the raw materials, wherein the type of the hydroxide and the content of the hydroxide are the most critical factors, and the pH value range influencing the solution can be controlled by selecting and adding the hydroxide and can also be obtained by post-treatment and neutralization by added acid. The acid may be an organic acid such as citric acid, sulfonic acid, etc., or an organic acid such as phosphoric acid, phosphorous acid, etc.
The molecular weight distribution index PDI of polycarbonate, the purity of monomers in the polymerization process, catalyst residues, polymerization time, polymerization temperature and purification essence mode and process all have decisive influence on the molecular weight and the molecular weight distribution thereof, and on the same molecular weight level, the distribution index PDI =1 indicates that the molecular weight is uniform, generally, the PDI of the polymer is more than 1, the larger the PDI is, the distribution is wide, the smaller the PDI is, the distribution is approximately 1, and the distribution is narrow.
Multiple cycles Tg temperature change, glass transition, is a reversible transition of an amorphous region in an amorphous polymer or semi-crystalline polymer from a hard, relatively brittle glassy state to a viscous state or rubbery state during temperature rise, the glass transition temperature being the temperature at which the glass transition occurs. The uniformity of the polycarbonate can thus be verified by the Tg temperature change over a number of cycles. The uniformity of the polycarbonate resin means that the mobility of the macromolecular segment tends to be consistent in the process of repeatedly heating for many times, and the Tg temperature change is small, which indicates that the polycarbonate resin has good uniformity.
Tg temperature change test: on a relaxation-resistant polyma DSC214 NETSZSCH instrument, according to the D3418-15 ASTM standard, a temperature raising program is carried out after the temperature is set to be 20 ℃ and is kept for 30min, the temperature raising rate is 10 ℃/min, the temperature is immediately lowered after being raised to 200 ℃, after 3 times of round trip, one-time differential processing is carried out according to a heat signal of a curve, the initial Tg temperature and the third Tg temperature are obtained, and the two temperature differences are recorded as the change of the Tg temperature. Wherein, the smaller the Tg temperature change is, the better the stability of the composition is; conversely, the greater the change in Tg temperature, the less stable.
The flame retardant is at least one selected from C1-C16 alkyl sulfonate flame retardant, carbonate flame retardant, phosphorus flame retardant, metal hydroxide flame retardant, borate flame retardant and fluorine-silver ion compound.
The C1-C16 alkyl sulfonate flame retardant is selected from at least one of potassium perfluorobutyl sulfonate, potassium perfluorooctane sulfonate, tetraethylammonium perfluoroethane sulfonate and potassium diphenylsulfone sulfonate;
the carbonate flame retardant is selected from at least one of sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate and barium carbonate;
the phosphorus flame retardant is at least one selected from phosphine flame retardants, hypophosphite flame retardants, phosphonite flame retardants, phosphite flame retardants, phosphine oxide flame retardants, hypophosphite flame retardants, phosphonate flame retardants, phosphate flame retardants, and polyphosphate flame retardants;
wherein the phosphine flame retardant may be phenoxyphosphazene; the phosphate ester flame retardant may be bisphenol a bis (diphenyl phosphate); the polyphosphate flame retardant may be melamine polyphosphate.
The metal hydroxide flame retardant is selected from at least one of magnesium hydroxide and aluminum hydroxide; the borate flame retardant is at least one of anhydrous zinc borate, 3.5 hydrated zinc borate, alkali metal salts of boric acid and alkaline earth metal salts of boric acid.
The flame retardant is at least one selected from C1-C16 alkyl sulfonate flame retardants.
0.1-5 parts of assistant is also included according to the parts by weight; the auxiliary agent is at least one selected from a lubricant, an antioxidant and an ultraviolet absorbent.
The lubricant is at least one selected from stearate lubricant, fatty acid lubricant and stearate lubricant; the stearate lubricant is at least one selected from calcium stearate, magnesium stearate and zinc stearate; the fatty acid lubricant is at least one selected from fatty acid, fatty acid derivative and fatty acid ester; the stearate lubricant is at least one selected from pentaerythritol stearate; preferably, the lubricant is at least one selected from fatty acid lubricants and stearate lubricants.
The ultraviolet absorbent is at least one selected from benzo triazine ultraviolet absorbent, bibenzoic acid ultraviolet absorbent and HALS compound.
The antioxidant can be hindered phenol antioxidant, phosphite antioxidant.
Phosphite antioxidants such as antioxidant 168, antioxidant PEPQ, antioxidant PEP-36, antioxidant 9228, and the like.
The preparation method of the flame-retardant polycarbonate composite material comprises the following steps: weighing the polycarbonate, the flame retardant and the auxiliary agent according to the proportion, uniformly mixing, adding into a double-screw extruder, and extruding and granulating (the temperature range of the screw is 200-280 ℃) to obtain the flame-retardant polycarbonate composite material.
Compared with the prior art, the invention has the following beneficial effects
The invention discovers that the stability of the polycarbonate (good flame retardant stability) can be reduced by overcoming the addition of a flame retardant when the polycarbonate meets a specific range by adjusting the weight average molecular weight, the molecular weight distribution index PDI, the pH value of a polycarbonate solution and the temperature change of multiple cycle Tg. Compared with the method for obtaining the stable flame-retardant polycarbonate composite material by adding other substances, the method has the advantages of lower cost, smaller influence on the performance of the polycarbonate and more contribution to further other modifications.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
The sources of the raw materials used in the present invention are as follows, but are not limited by the following raw materials.
The following synthetic monomers for polycarbonate are bisphenol A and derivatives thereof
Polycarbonate A: the weight average molecular weight is about 27500, the molecular weight distribution index PDI is 2.1, the pH of a polycarbonate solution is 7.0, the temperature change of multi-cycle Tg is 3.0 ℃, the polycarbonate is prepared by a phosgene method, the set weight average molecular weight and PDI are obtained by controlling reaction parameters, and the pH value is adjusted and controlled by acid-base to obtain the temperature change of multi-cycle Tg;
polycarbonate B: the weight average molecular weight is about 28000, the molecular weight distribution index PDI is 1.7, the pH of a polycarbonate solution is 6.9, the temperature change of multi-cycle Tg is 2.0 ℃, the polycarbonate is prepared by a phosgene method, the set weight average molecular weight and PDI are obtained by controlling reaction parameters, and the pH is adjusted by acid-base to obtain the temperature change of multi-cycle Tg;
polycarbonate C: the weight average molecular weight is about 25000, the molecular weight distribution index PDI is 1.5, the pH of a polycarbonate solution is 7.0, the temperature change of multi-cycle Tg is 3.1 ℃, the polycarbonate is prepared by a phosgene method, the set weight average molecular weight and PDI are obtained by controlling reaction parameters, and the pH is regulated and controlled by acid-base to obtain the temperature change of multi-cycle Tg;
polycarbonate D: the weight average molecular weight is about 27000, the molecular weight distribution index PDI is 2.5, the pH of a polycarbonate solution is 7.2, the temperature change of multi-cycle Tg is 3.2 ℃, the polycarbonate is prepared by a phosgene method, the set weight average molecular weight and PDI are obtained by controlling reaction parameters, and the pH is adjusted and controlled by acid-base to obtain the temperature change of multi-cycle Tg;
polycarbonate E: the weight average molecular weight is about 28000, the molecular weight distribution index PDI is 2.6, the pH of a polycarbonate solution is 7.2, the temperature change of multi-cycle Tg is 4.0 ℃, the polycarbonate is prepared by a phosgene method, the set weight average molecular weight and PDI are obtained by controlling reaction parameters, and the pH is adjusted by acid-base to obtain the temperature change of multi-cycle Tg;
flame retardant A: a phenoxyphosphazene;
and (3) a flame retardant B: bisphenol a bis (diphenyl phosphate);
lubricant: stearate lubricants, PETS;
antioxidant: antioxidant 168, phosphite antioxidant;
examples and comparative examples a method of preparing a flame retardant polycarbonate composite: weighing the polycarbonate, the flame retardant and the auxiliary agent according to the proportion, uniformly mixing, adding into a double-screw extruder, and extruding and granulating (the temperature range of the screw is 200-280 ℃) to obtain the flame-retardant polycarbonate composite material.
The performance test method comprises the following steps:
(1) flame retardant rating: according to UL-94 standard, 1.5 mm.
(2) Flame retardant stability: putting the composition into an aging oven with the temperature set to 85 ℃ and the humidity set to 85 percent for accelerated aging for 500 hours, and testing the flame retardant property according to the UL-94 standard and 1.5 mm; the better the flame retardant stability, indicating the better the stability of the alloy.
(3) Long-term performance stability: according to f1 standard of UL 746B.
Table 1: EXAMPLES Components and Performance test results of flame-retardant polycarbonate composites
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Polycarbonate A | 100 | 100 | 100 | |
| Polycarbonate B | 100 | |||
| Flame retardant A | 10 | 20 | 10 | |
| Flame retardant B | 10 | |||
| Lubricant agent | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant agent | 0.01 | 0.01 | 0.01 | 0.01 |
| Flame retardant rating, 1.5mm | V-0 | V-0 | V-0 | V-0 |
| Stability of flame retardance | A- | A- | A- | A |
| Stability of long term performance | f1 | f1 | f1 | f1 |
Table 2: component proportion and performance test results of comparative example flame-retardant polycarbonate composite material
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Polycarbonate C | 100 | ||
| Polycarbonate D | 100 | ||
| Polycarbonate E | 100 | ||
| Flame retardant A | 10 | 10 | 10 |
| Lubricant agent | 0.5 | 0.5 | 0.5 |
| Antioxidant agent | 0.01 | 0.01 | 0.01 |
| Flame retardant rating, 1.5mm | V-2 | V-2 | V-2 |
| Stability of flame retardance | NG | NG | NG |
| Stability of long term performance | NG | NG | NG |
NG means the test failed.
As can be seen from examples 1 and 4, the preferred polycarbonates B are more flame-resistant and stable.
It can be seen from comparative examples 1-3 that the stability is poor when a flame retardant is added, which is reflected in poor flame retardancy, flame retardant stability and long term performance stability, without selecting polycarbonate in the range of the present invention.
Claims (8)
1. The flame-retardant polycarbonate composite material is characterized by comprising the following components in parts by weight:
60-100 parts of polycarbonate;
1-25 parts of a flame retardant;
the weight average molecular weight of the polycarbonate is more than 26000, the molecular weight distribution index PDI is less than 2.0, the pH of the polycarbonate solution is 6.7-7.1, and the temperature change of the multi-cycle Tg is less than 2.1 ℃.
2. The flame retardant polycarbonate composite of claim 1, wherein the polycarbonate has a pH of 6.8 to 6.9.
3. The flame retardant polycarbonate composite of claim 1 or 2, wherein the polycarbonate solution is tested for pH by dissolving the polycarbonate in a methylene chloride solvent, filtering the solution, and performing acid-base titration of the organic phase to test the pH; the method of molecular weight distribution index PDI is gel permeation chromatography.
4. The flame retardant polycarbonate composite of claim 1 or 2, wherein the flame retardant is at least one selected from the group consisting of a C1-C16 alkyl sulfonate flame retardant, a carbonate-based flame retardant, a phosphorus-based flame retardant, a metal hydroxide flame retardant, a borate flame retardant, and a fluorine-silver ion complex.
5. The flame retardant polycarbonate composite of claim 4, wherein the C1-C16 alkyl sulfonate flame retardant is selected from at least one of potassium perfluorobutyl sulfonate, potassium perfluorooctane sulfonate, tetraethylammonium perfluoroethane sulfonate; the carbonate flame retardant is selected from at least one of sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate and barium carbonate; the phosphorus flame retardant is at least one selected from phosphine flame retardants, hypophosphite flame retardants, phosphonite flame retardants, phosphite flame retardants, phosphine oxide flame retardants, hypophosphite flame retardants, phosphonate flame retardants, phosphate flame retardants, and polyphosphate flame retardants;
the metal hydroxide flame retardant is selected from at least one of magnesium hydroxide and aluminum hydroxide; the borate flame retardant is at least one of anhydrous zinc borate, 3.5 hydrated zinc borate, alkali metal salts of boric acid and alkaline earth metal salts of boric acid.
6. The flame retardant polycarbonate composite of claim 4, wherein the flame retardant is at least one selected from the group consisting of C1-C16 alkyl sulfonate flame retardants.
7. The flame retardant polycarbonate composite of claim 1 or 2, further comprising 0.1 to 5 parts by weight of an auxiliary; the auxiliary agent is at least one selected from a lubricant, an antioxidant and an ultraviolet absorbent.
8. The method of preparing a flame retardant polycarbonate composite of claim 7, comprising the steps of: weighing the polycarbonate, the flame retardant and the auxiliary agent according to the proportion, uniformly mixing, adding into a double-screw extruder, and extruding and granulating, wherein the temperature range of the screw is 200-280 ℃, so as to obtain the flame-retardant polycarbonate composite material.
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