CN116813840A - Flame-retardant polyvinyl chloride resin and preparation method thereof - Google Patents
Flame-retardant polyvinyl chloride resin and preparation method thereof Download PDFInfo
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- CN116813840A CN116813840A CN202211340452.5A CN202211340452A CN116813840A CN 116813840 A CN116813840 A CN 116813840A CN 202211340452 A CN202211340452 A CN 202211340452A CN 116813840 A CN116813840 A CN 116813840A
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- China
- Prior art keywords
- polyvinyl chloride
- chloride resin
- parts
- flame
- reaction
- 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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- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 108
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 108
- 229920005989 resin Polymers 0.000 title claims abstract description 107
- 239000011347 resin Substances 0.000 title claims abstract description 107
- 239000003063 flame retardant Substances 0.000 title claims abstract description 90
- 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 89
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 239000003999 initiator Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 N-substituted maleimide Chemical class 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 112
- 238000000034 method Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 25
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 15
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 14
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 claims description 6
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 claims description 6
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 claims description 6
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 claims description 4
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 claims description 4
- KIKBJYQCJJXCBZ-UHFFFAOYSA-N 1-octylpyrrole-2,5-dione Chemical compound CCCCCCCCN1C(=O)C=CC1=O KIKBJYQCJJXCBZ-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- UETPRJJVZPVPQI-UHFFFAOYSA-N (2-propan-2-ylphenyl) dihydrogen phosphate Chemical compound CC(C)C1=CC=CC=C1OP(O)(O)=O UETPRJJVZPVPQI-UHFFFAOYSA-N 0.000 claims description 2
- GJVWMPQFNARTPN-UHFFFAOYSA-N (3-propan-2-ylphenyl) dihydrogen phosphate Chemical compound CC(C)C1=CC=CC(OP(O)(O)=O)=C1 GJVWMPQFNARTPN-UHFFFAOYSA-N 0.000 claims description 2
- JMEROBIHUFJHHG-UHFFFAOYSA-N (4-propan-2-ylphenyl) dihydrogen phosphate Chemical compound CC(C)C1=CC=C(OP(O)(O)=O)C=C1 JMEROBIHUFJHHG-UHFFFAOYSA-N 0.000 claims description 2
- NBIYKOUEZOEMMC-UHFFFAOYSA-N 1-(2-methylpropyl)pyrrole-2,5-dione Chemical compound CC(C)CN1C(=O)C=CC1=O NBIYKOUEZOEMMC-UHFFFAOYSA-N 0.000 claims description 2
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 claims description 2
- YEKDUBMGZZTUDY-UHFFFAOYSA-N 1-tert-butylpyrrole-2,5-dione Chemical compound CC(C)(C)N1C(=O)C=CC1=O YEKDUBMGZZTUDY-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
- RLRILSHEPYHXOG-UHFFFAOYSA-N 3-methoxybutoxycarbonyloxy 3-methoxybutyl carbonate Chemical compound COC(C)CCOC(=O)OOC(=O)OCCC(C)OC RLRILSHEPYHXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- CWINGZLCRSDKCL-UHFFFAOYSA-N ethoxycarbonyloxy ethyl carbonate Chemical compound CCOC(=O)OOC(=O)OCC CWINGZLCRSDKCL-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- UNCRSFLCCHQPCM-UHFFFAOYSA-J tris(2-sulfanylpropanoyloxy)stannyl 2-sulfanylpropanoate Chemical compound SC(C(=O)[O-])C.[Sn+4].SC(C(=O)[O-])C.SC(C(=O)[O-])C.SC(C(=O)[O-])C UNCRSFLCCHQPCM-UHFFFAOYSA-J 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 238000006136 alcoholysis reaction Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- MJXOOPBZYCWYIF-UHFFFAOYSA-N dimethylcarbamodithioic acid;sodium Chemical compound [Na].CN(C)C(S)=S MJXOOPBZYCWYIF-UHFFFAOYSA-N 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 4
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- LMGRLFJILWFEMN-UHFFFAOYSA-N diphenoxyphosphoryl phenyl phosphono phosphate Chemical compound C1=CC=C(C=C1)OP(=O)(OC2=CC=CC=C2)OP(=O)(OC3=CC=CC=C3)OP(=O)(O)O LMGRLFJILWFEMN-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 description 1
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- QEJPOEGPNIVDMK-UHFFFAOYSA-N 3-bromo-2,2-bis(bromomethyl)propan-1-ol Chemical compound OCC(CBr)(CBr)CBr QEJPOEGPNIVDMK-UHFFFAOYSA-N 0.000 description 1
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 1
- CRGHZGPGIPFJID-UHFFFAOYSA-N 4,5,6-tris(2,3,4-tribromophenoxy)triazine Chemical compound BrC1=C(Br)C(Br)=CC=C1OC1=NN=NC(OC=2C(=C(Br)C(Br)=CC=2)Br)=C1OC1=CC=C(Br)C(Br)=C1Br CRGHZGPGIPFJID-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- FFYPMLJYZAEMQB-UHFFFAOYSA-N diethyl pyrocarbonate Chemical compound CCOC(=O)OC(=O)OCC FFYPMLJYZAEMQB-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
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- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application provides a flame-retardant polyvinyl chloride resin and a preparation method thereof, wherein the flame-retardant polyvinyl chloride resin is prepared by taking general polyvinyl chloride resin as a raw material, adding a flame retardant, a stabilizer, an initiator, a dispersing agent and the like for in-situ polymerization, and the flame-retardant polyvinyl chloride resin comprises the following components in parts by weight: 100-200 parts of deionized water, 100 parts of polyvinyl chloride resin, 0.5-6 parts of alkylated triphenyl phosphate monomer as a flame retardant, 0.5-5 parts of N-substituted maleimide monomer as a heat-resistant modifier, 0.1-1 part of dialkyl tin mercaptopropionate as a stabilizer and other components.
Description
Technical Field
The application relates to the field of synthesis of polyvinyl chloride resin, in particular to an in-situ polymerization flame-retardant polyvinyl chloride resin and a preparation method thereof.
Background
The chlorine content of the common polyvinyl chloride resin is about 56%, the oxygen index is about 40, and the bulk flame retardance is good. However, when the polyvinyl chloride resin is used for soft products such as sheets, thin, flexible pipes, cables and the like, the plasticizer is required to be added to improve the toughness, and in the case of cable materials, 30-50% of the plasticizer is usually required to be added, and in order to improve the flame retardance, a flame retardant is usually added to modify the polyvinyl chloride resin to prepare the flame retardant polyvinyl chloride resin.
Mechanical blending, which is a blend obtained by mixing melts of different polymers by means of rollers, extruders or intensive mixers, is often used, the blending temperature being higher than the viscous flow temperature of the amorphous polymer components contained in the mixture and higher than the melting point of the crystalline polymer components contained therein. The high shear stress upon mechanical blending can lead to polymer degradation. The flame retardant, usually magnesium hydroxide, aluminum hydroxide and other conventional inorganic flame retardants, is added in the mixing process, the addition amount is more than 30%, the physical properties of the material are affected, and the mechanical properties of the cable material are reduced. In addition, in the physical blending process, the flame retardant is unevenly distributed, and when a fire disaster occurs, the part with low flame retardant content is a weak link, so that potential safety hazards exist. A foamable flame-retardant polyethylene composite material and a preparation method thereof, as in the patent CN 101735503A. The composite material consists of the following components in parts by mass: 100 parts of low-density polyethylene, 5-20 parts of polyvinyl chloride, 1-3 parts of chlorinated polyethylene, 10-20 parts of flame retardant and 5-10 parts of flame retardant synergist. The application adopts skillful matching of low-density ethylene, polyvinyl chloride, flame retardant synergist and chlorinated polyethylene. The flame retardant is one or more of decabromodiphenylethane, decabromodiphenyl ether, tri (tribromophenoxy) triazine, brominated epoxy resin, ethylene bis tetrabromophthalimide, tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, tetrabromobisphenol S bis (2, 3-dibromopropyl) ether, tri (tribromoneopentyl alcohol) phosphate and tri (2, 3-dibromopropyl) isocyanatoester. The flame retardant synergist is antimony trioxide. The flame retardant synergist is 2, 3-dimethyl-2, 3-diphenyl butane. The addition amount of the flame retardant is more than 25 parts, the uniformity of the mixture of the flame retardant and other components is not good, the foaming performance of the product is also influenced, and the flame retardant product obtained by adopting a physical blending mode has poor quality stability.
Such as patent CN104327348A, which relates to a flame-retardant polyethylene-polypropylene composite plastic, in particular to the field of plastic formula preparation. The flame-retardant polyethylene-polypropylene composite plastic comprises the following components in parts by weight, polyethylene, polyvinyl chloride, dimethylaminopropylamine, melamine, antimony oxide, glycerol triacetate, an antioxidant, benzophenone, ammonium polyphosphate, triphenyl triphosphate and glass fibers. The composite plastic has the advantages of high mechanical strength, good fireproof performance, good corrosion resistance, good antistatic performance, low cost and long service life. The patent uses triphenyl triphosphate as a flame retardant, but does not describe specific flame retardant performance indexes, compatibility among various auxiliary agents, and flame retardant effect.
The high-transmittance low-smoke low-halogen high-flame-retardance polyvinyl chloride plastic disclosed in the patent CN109957189A comprises the following raw materials in parts by weight: 100 parts of PVC resin, 40-60 parts of plasticizer, 70-90 parts of flame retardant, 8-12 parts of heat stabilizer, 10-20 parts of smoke suppressant, 1.2-2.5 parts of processing aid and 0.3-0.6 part of antioxidant. The method has the advantages of high flame retardant addition amount up to more than 70, high cost and problematic product quality uniformity.
In addition, a suspension polymerization process is conventionally adopted, and the suspension polymerization method refers to a polymerization process in which a vinyl chloride monomer is dispersed into droplets under the action of mechanical stirring or vibration and a dispersing agent, and is suspended in water. The suspension polymerization process of vinyl chloride and flame retardant produces flame-retardant polyvinyl chloride, and the components such as vinyl chloride monomer and flame retardant react, so that the boiling point of the vinyl chloride is low, the volatile vinyl chloride gas is more at the reaction temperature, the pressure is higher, the reaction is unstable, the explosion polymerization phenomenon easily occurs in the reaction process, potential safety hazards exist, the quality is fluctuated, and the thermal stability of the resin is poor. According to the preparation method of the polyvinyl chloride resin for the flame-retardant cable disclosed in the patent CN102432732A, a suspension polymerization method is adopted, vinyl chloride monomer, a stabilizer, a dispersing agent, a novel flame retardant, a chain extender, an auxiliary agent and deionized water are added into a polymerization kettle, cold stirring is carried out for 30 minutes, the reaction is carried out at the temperature of 50-60 ℃ for 5-6.5 hours, the pressure is reduced by 0.1MPa, and then a terminator is added, so that the aqueous suspension of the polyvinyl chloride resin for the flame-retardant cable is obtained. And removing unreacted vinyl chloride monomer, and centrifugally dehydrating and drying to obtain a finished product. The polyvinyl chloride resin for the flame-retardant cable manufactured by the application does not need to additionally add flame retardant in the formula of the product, and the flame retardant property of the material is obviously improved. The flame retardant is added in the polymerization process, so that the polymerization reaction is influenced, the components such as the added flame retardant and the like are subjected to grafting reaction with the vinyl chloride because the vinyl chloride is inflammable and explosive, the reaction pressure is high, the reaction is unstable, the explosion polymerization phenomenon is easy to occur in the reaction process, potential safety hazards exist, fluctuation of quality occurs, and the thermal stability of the resin is poor.
Obviously, the obvious defect of the mechanical blending method is that the quality stability of the prepared product is poor, while the obvious defect of the suspension polymerization process is that the reaction pressure is high, the reaction is unstable, and the quality of the product is further influenced. Therefore, finding a method for preparing flame-retardant polyvinyl chloride resin, which is easy to control the reaction and can effectively ensure the product quality, becomes a problem to be solved urgently.
Disclosure of Invention
In view of the above, the application provides a formula of flame-retardant polyvinyl chloride resin and a preparation method thereof, wherein the formula solves the problem of unstable product quality, and the method solves the problem of controllable reaction conditions, particularly controllable reaction pressure, ensures stable reaction, and further ensures the comprehensive quality of products.
The application provides a flame-retardant polyvinyl chloride resin, which comprises polyvinyl chloride resin, deionized water, a flame retardant and other auxiliary agents, and comprises the following components in parts by weight: 100-200 parts of deionized water, 100 parts of polyvinyl chloride resin, 0.5-6 parts of alkylated triphenyl phosphate monomer, 0.5-5 parts of N-substituted maleimide monomer and 0.1-1 part of dialkyltin mercaptopropionate, wherein the alkylated triphenyl phosphate monomer is a flame retardant, the N-substituted maleimide is a heat-resistant modifier, and the dialkyltin mercaptopropionate is a stabilizer;
the application also comprises the following components in parts by weight: 0.009-0.032 parts of dispersing agent, 0.01-0.35 parts of initiator, 0.01-0.05 parts of pH regulator and 0.01-0.3 parts of terminator.
Wherein the polyvinyl chloride resin is a suspension method or a bulk method polyvinyl chloride resin, and the polymerization degree is 700-3000;
the alkylated triphenyl phosphate monomer of the flame retardant is one or more of monomers such as 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, 2-isopropylphenyl phosphate, 3-isopropylphenyl phosphate, 4-isopropylphenyl phosphate, methyltrimolyl phosphate and the like;
the heat-resistant modifier N-substituted maleimide monomer is one or more of N-ethylmaleimide, N-isopropyl maleimide, N-N-butyl maleimide, N-isobutyl maleimide, N-tert-butyl maleimide, N-N-amyl maleimide, N-N-octyl maleimide, N-benzyl maleimide and other monomers;
the initiator is selected from one or more of water-soluble or oil-soluble bis (2-ethyl) dicarbonate, dicyclohexyl peroxydicarbonate, bis (3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, di-tert-butyl peroxybenzoate, cumyl peroxyneodecanoate, dibenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, lauroyl peroxide, acetyl cyclohexane sulfonyl peroxide, bis (3, 5-trimethylhexanoyl) peroxide, dicumyl peroxide, sodium persulfate, potassium persulfate and the like;
the dispersing agent is selected from one or the combination of two of polyvinyl alcohol with the polymerization degree of 900-2500, hydroxypropyl methyl cellulose with the gel temperature of 48-85 ℃, and the like;
the pH regulator is one or more selected from sodium hydride, ammonium bicarbonate and sodium bicarbonate;
the terminator is one or more selected from alpha-methyl styrene, N-diethyl hydroxylamine, asymmetric hindered phenol antioxidant 245, p-tertiary butyl catechol, hydroquinone, nonylphenol and the like.
The application also provides a method for preparing the flame-retardant polyvinyl chloride resin, which comprises the following steps:
(1) Weighing deionized water according to the formula, putting the deionized water into a reaction kettle, weighing polyvinyl chloride resin according to the formula, adding the polyvinyl chloride resin into the reaction kettle, starting stirring, and controlling the rotating speed to be 45-90 r/min;
(2) After the polyvinyl chloride resin is soaked for 3 to 6 hours, adding an alkylated triphenyl phosphate monomer, an N-substituted maleimide monomer and a dispersing agent, continuously soaking for 1 to 3 hours, and adding a first part of initiator;
(3) Continuously stirring for 15-35 minutes, adding dialkyltin mercaptopropionate, heating a jacket to a reaction temperature of 38-75 ℃, entering a polymerization reaction stage, and automatically adjusting the reaction temperature to be within a range of 40-70 ℃ by a reaction kettle;
(4) Adding a second part of initiator after reacting for 1-4 hours;
(5) Then the mixture reacts for 1 to 3 hours, and a pH regulator is added;
(6) Raising the reaction temperature by 5-10 ℃ 1 hour before the reaction is finished, and continuing the reaction;
(7) The reaction time is 5 to 12 hours, a terminator is added, stirring is continued for 10 to 20 minutes, and the reaction is finished;
(8) And discharging the material from the reaction kettle, stripping to remove residual monomers, and centrifugally drying to remove water to obtain the flame-retardant polyvinyl chloride resin.
Wherein, the mode of the polymerization reaction is an in-situ polymerization method, and the in-situ polymerization method is to add the reactive monomer (or the soluble prepolymer thereof) and the catalyst into a disperse phase (or a continuous phase), and the core material is the disperse phase. Since the monomer (or prepolymer) is soluble in a single phase, while its polymer is insoluble throughout the system, the polymerization occurs on the dispersed phase core. The reaction starts, the monomer is prepolymerized, the prepolymer is polymerized, and when the polymerization size of the prepolymer is gradually increased, the prepolymer is deposited on the surface of the core material.
The initiator is added in a multi-step method, and the first part of the initiator added before the polymerization reaction and the second part of the initiator added after a certain period of reaction can be the same initiator or different initiators;
wherein the polymerization reaction pressure is normal pressure or nitrogen is introduced to keep micro-positive pressure, and the micro-positive pressure is 0.01-0.1 MPa.
According to the application, polyvinyl chloride is selected as an original material, alkylated triphenyl phosphate monomer is selected as a flame retardant, N-substituted maleimide is selected as a heat-resistant modifier, and dialkyltin mercaptopropionate is selected as a stabilizer; the flame retardant alkylated triphenyl phosphate has good flame retardant property, long hydrocarbon group and difficult volatilization; the chain section is long and has good toughness; the phosphate selected by the application is not easy to volatilize, stress fracture can be reduced during processing, and phenolic groups in the terminator can be the connecting groups of the diphosphoric acid quinone, so that the flame retardance can be improved, and the flame retardance of the resin is better; meanwhile, the selected N-substituted maleimide contains a planar five-membered ring, and in the reaction process of the structure and polyvinyl chloride and alkylated triphenyl phosphate, the internal rotation resistance of a molecular chain can be increased, the internal rotation resistance is increased, and the synergistic dialkyl tin mercaptopropionate inhibits the polyvinyl chloride resin to have better colorability and good fluidity in the earlier stage of processing, so that the thermal stability and transparency of the resin are improved, and the transmittance of a product is improved.
When in fire, the plastic products burn to generate smoke, toxic gas, combustible gas and burning solution drops, which brings difficulty to the extinguishment and escape. Therefore, the flame-retardant polyvinyl chloride resin product prepared by the application has stable and uniform quality, improved thermal stability, good transmittance of the product and good flame-retardant effect.
In addition, the application adopts an in-situ polymerization process, takes the general polyvinyl chloride resin as a raw material, adds the flame retardant, the stabilizer, the initiator, the dispersing agent and the like, and reacts under the condition of normal pressure or micro-positive pressure, has low reaction pressure, mild and stable reaction, does not generate the phenomenon of bursting and aggregation, and further ensures the characteristics of stable and uniform product quality, improved thermal stability and good flame retardant effect.
Detailed Description
The term "comprising" and variants thereof as used herein is intended to be open ended, i.e., including, but not limited to. The term "according to" is based, at least in part, on. The term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one additional embodiment". Related definitions of other terms will be given in the description below.
Example 1:
taking the following production raw materials in parts by weight: 160 parts of deionized water, 100 parts of polyvinyl chloride, 4 parts of alkylated triphenyl phosphate monomer, 3 parts of N-substituted maleimide monomer, 0.8 part of dialkyltin mercaptopropionate, 0.01 part of dispersing agent, 0.014 part of initiator, 0.02 part of pH regulator and 0.006 part of terminator.
Wherein the polyvinyl chloride resin adopts common SG5 resin. The alkylated triphenyl phosphate monomer is added from 2-ethylhexyl diphenyl phosphate in an amount of 4 parts. N-ethylmaleimide monomer, 3 parts by weight. 0.8 parts of dialkyl tin mercaptopropionate. The dispersing agent consists of 0.003 part of KH-20 with the alcoholysis degree of 81, 0.004 part of L-10 with the alcoholysis degree of 72 and 0.003 part of F-50 hydroxypropyl methyl cellulose; the composite initiator consists of 0.006 parts of di (2-ethyl) hexyl peroxydicarbonate and 0.008 parts of sodium persulfate; the pH regulator adopts ammonium bicarbonate, and the addition amount is 0.02 part. The compound terminator consists of 0.002 parts of N, N-diethyl hydroxylamine, 0.003 parts of dimethyl dithiocarbamic acid sodium and 0.001 part of p-tertiary butyl catechol.
The method comprises the following steps:
(1) Weighing deionized water according to a formula, putting the deionized water into a reaction kettle, weighing polyvinyl chloride resin according to the formula, adding the polyvinyl chloride resin into the reaction kettle, starting stirring, and controlling the rotating speed at 50r/min;
(2) Soaking polyvinyl chloride resin for 3.5 hours, adding a 2-ethylhexyl diphenyl phosphate monomer, an N-ethylmaleimide monomer and a composite dispersing agent, continuously soaking for 1.5 hours, and adding an initiator sodium persulfate;
(3) Continuously stirring for 20 minutes, adding dialkyltin mercaptopropionate, heating a jacket to a reaction temperature of 57.5 ℃, entering a reaction stage, and automatically adjusting the reaction temperature to 57.5 ℃ by a reaction kettle;
(4) Adding initiator di (2-ethyl) hexyl peroxydicarbonate into the mixture after 1 hour of reaction, and adding a pH regulator after 2.5 hours of reaction;
(5) The reaction temperature is increased by 8 ℃ for 1 hour before the reaction is finished;
(6) The reaction time is 7.5 hours, 0.002 parts of compound terminator N, N-diethyl hydroxylamine, 0.003 parts of dimethyl dithiocarbamic acid sodium and 0.001 parts of p-tertiary butyl catechol are added, stirring is continued for 20 minutes, and the reaction is finished;
(7) And discharging the material from the reaction kettle, removing residual monomers by a stripping device, and centrifugally drying to remove water to obtain a flame-retardant polyvinyl chloride resin finished product.
Example 2:
taking the following production raw materials in parts by weight: 160 parts of deionized water, 100 parts of polyvinyl chloride, 5 parts of alkylated triphenyl phosphate monomer, 4 parts of N-substituted maleimide monomer, 0.8 part of dialkyltin mercaptopropionate, 0.01 part of dispersing agent, 0.014 part of initiator, 0.02 part of pH regulator and 0.006 part of terminator.
Wherein the polyvinyl chloride resin adopts common SG5 resin. The alkylated triphenyl phosphate monomer is added from 2-ethylhexyl diphenyl phosphate in an amount of 5 parts. N-ethylmaleimide monomer, 4 parts by weight. 0.8 parts of dialkyl tin mercaptopropionate. The dispersant consisted of 0.003 parts of KH-20 with an alcoholysis degree of 81, 0.004 parts of L-10 with an alcoholysis degree of 72, and 0.003 parts of F-50 hydroxypropyl methylcellulose. The composite initiator consisted of 0.006 parts of di (2-ethyl) hexyl peroxydicarbonate and 0.008 parts of sodium persulfate. The pH regulator adopts ammonium bicarbonate, and the addition amount is 0.02 part. The compound terminator consists of 0.002 parts of N, N-diethyl hydroxylamine, 0.003 parts of p-tert-butyl catechol and 0.001 parts of dimethyl dithiocarbamic acid sodium.
The method comprises the following steps:
(1) Weighing deionized water according to a formula, putting the deionized water into a reaction kettle, weighing polyvinyl chloride resin according to the formula, adding the polyvinyl chloride resin into the reaction kettle, starting stirring, and controlling the rotating speed at 60r/min;
(2) Soaking polyvinyl chloride resin for 4 hours, adding a 2-ethylhexyl diphenyl phosphate monomer, an N-ethylmaleimide monomer and a composite dispersing agent, continuously soaking for 1.5 hours, and adding an initiator sodium persulfate;
(3) Continuously stirring for 20 minutes, adding dialkyltin mercaptopropionate, heating a jacket to a reaction temperature of 57.5 ℃, entering a reaction stage, and automatically adjusting the reaction temperature to 57.5 ℃ by a reaction kettle;
(4) Adding initiator di (2-ethyl) hexyl peroxydicarbonate into the mixture after 1 hour of reaction, and adding a pH regulator after 2.5 hours of reaction;
(5) The reaction temperature is increased by 8 ℃ for 1 hour before the reaction is finished;
(6) The reaction time was 7.5 hours, 0.002 parts of N, N-diethylhydroxylamine, 0.003 parts of p-tert-butylcatechol and 0.001 parts of sodium dimethyldithiocarbamate as a composite terminator were added, and stirring was continued for 20 minutes to complete the reaction.
(7) And discharging the material from the reaction kettle, removing residual monomers by a stripping device, and centrifugally drying to remove water to obtain a flame-retardant polyvinyl chloride resin finished product.
Example 3:
taking the following production raw materials in parts by weight: 160 parts of deionized water, 100 parts of polyvinyl chloride, 5 parts of alkylated triphenyl phosphate monomer, 4 parts of N-substituted maleimide monomer, 0.8 part of dialkyltin mercaptopropionate, 0.01 part of dispersing agent, 0.014 part of initiator, 0.02 part of pH regulator and 0.006 part of terminator.
Wherein the polyvinyl chloride resin adopts common SG5 resin. The alkylated triaryl phosphate monomer was added from isodecyl diphenyl phosphate in an amount of 5 parts. N-N-amyl maleimide monomer, 4 parts by weight. 0.8 parts of dialkyl tin mercaptopropionate. The dispersant consisted of 0.003 parts of KH-20 with an alcoholysis degree of 81, 0.004 parts of L-10 with an alcoholysis degree of 72, and 0.003 parts of F-50 hydroxypropyl methylcellulose. The composite initiator consisted of 0.008 parts dicyclohexyl peroxydicarbonate and 0.009 parts sodium persulfate. The pH regulator adopts ammonium bicarbonate, and the addition amount is 0.02 part. The compound terminator consists of 0.003 part of N, N-diethyl hydroxylamine, 0.004 part of p-tert-butyl catechol and 0.001 part of dimethyl dithiocarbamic acid sodium.
The method comprises the following steps:
(1) Weighing deionized water according to a formula, putting the deionized water into a reaction kettle, weighing polyvinyl chloride resin according to the formula, adding the polyvinyl chloride resin into the reaction kettle, starting stirring, and controlling the rotating speed at 70r/min;
(2) Soaking polyvinyl chloride resin for 4.5 hours, adding isodecyl diphenyl phosphate monomer, N-N-amyl maleimide monomer and composite dispersing agent, continuously soaking for 1.5 hours, and adding initiator sodium persulfate;
(3) Continuously stirring for 20 minutes, adding dialkyltin mercaptopropionate, heating a jacket to a reaction temperature of 50 ℃, entering a reaction stage, and automatically adjusting the reaction temperature to 50 ℃ by a reaction kettle;
(4) Adding initiator dicyclohexyl peroxydicarbonate after 1 hour of reaction, and adding pH regulator after 2.5 hours of reaction;
(5) The reaction temperature is increased by 8 ℃ for 1 hour before the reaction is finished;
(6) The reaction time was 9 hours, 0.003 part of N, N-diethylhydroxylamine, 0.004 part of p-tert-butylcatechol and 0.001 part of sodium dimethyldithiocarbamate as a composite terminator were added, and stirring was continued for 20 minutes to complete the reaction.
(7) And discharging the material from the reaction kettle, removing residual monomers by a stripping device, and centrifugally drying to remove water to obtain a flame-retardant polyvinyl chloride resin finished product.
Example 4:
taking the following production raw materials in parts by weight: 160 parts of deionized water, 100 parts of polyvinyl chloride, 5 parts of alkylated triphenyl phosphate monomer, 4 parts of N-substituted maleimide monomer, 0.8 part of dialkyltin mercaptopropionate, 0.01 part of dispersing agent, 0.014 part of initiator, 0.02 part of pH regulator and 0.006 part of terminator.
Wherein the polyvinyl chloride resin adopts common SG5 resin. The alkylated triphenyl phosphate monomer is added from isodecyl diphenyl phosphate in an amount of 5 parts. N-N-octyl maleimide monomer, 4 parts by weight. 0.8 parts of dialkyl tin mercaptopropionate. The dispersant consisted of 0.003 parts of KH-20 with an alcoholysis degree of 81, 0.004 parts of L-10 with an alcoholysis degree of 72, and 0.003 parts of F-50 hydroxypropyl methylcellulose. The composite initiator consisted of 0.005 part of di (2-ethyl) hexyl peroxydicarbonate and 0.007 part of sodium persulfate. The pH regulator adopts ammonium bicarbonate, and the addition amount is 0.02 part. The compound terminator consists of 0.002 parts of N, N-diethyl hydroxylamine, 0.003 parts of p-tert-butyl catechol and 0.001 parts of dimethyl dithiocarbamic acid sodium.
The method comprises the following steps:
(1) Weighing deionized water according to a formula, putting the deionized water into a reaction kettle, weighing polyvinyl chloride resin according to the formula, adding the polyvinyl chloride resin into the reaction kettle, starting stirring, and controlling the rotating speed at 80r/min;
(2) Soaking polyvinyl chloride resin for 4.5 hours, adding isodecyl diphenyl phosphate, N-N-octyl maleimide monomer and composite dispersing agent, continuously soaking for 1.5 hours, and adding initiator sodium persulfate;
(3) Continuously stirring for 20 minutes, adding dialkyltin mercaptopropionate, heating a jacket to a reaction temperature of 65 ℃, entering a reaction stage, and automatically adjusting the reaction temperature to 65 ℃ by a reaction kettle;
(4) Adding initiator di (2-ethyl) hexyl peroxydicarbonate into the mixture after 1 hour of reaction, and adding a pH regulator after 2.5 hours of reaction;
(5) The reaction temperature is increased by 8 ℃ for 1 hour before the reaction is finished;
(6) The reaction time is 6.5 hours, 0.002 parts of compound terminator N, N-diethyl hydroxylamine, 0.003 parts of p-tertiary butyl catechol and 0.001 parts of dimethyl dithiocarbamic acid sodium are added, stirring is continued for 20 minutes, and the reaction is finished.
(7) And discharging the material from the reaction kettle, removing residual monomers by a stripping device, and centrifugally drying to remove water to obtain a flame-retardant polyvinyl chloride resin finished product.
Example 5:
taking the following production raw materials in parts by weight: 160 parts of deionized water, 100 parts of polyvinyl chloride, 5 parts of alkylated triphenyl phosphate monomer, 4 parts of N-substituted maleimide monomer, 0.5 part of dialkyltin mercaptopropionate, 0.01 part of dispersing agent, 0.014 part of initiator, 0.02 part of pH regulator and 0.006 part of terminator.
Wherein the polyvinyl chloride resin adopts common SG5 resin. Alkylated triphenyl phosphate is added from 2-cumyl phosphate in an amount of 4.5 parts. N-butyl maleimide monomer, 4 parts by weight. 0.8 parts of dialkyl tin mercaptopropionate. The dispersant consisted of 0.003 parts of KH-20 with an alcoholysis degree of 81, 0.004 parts of L-10 with an alcoholysis degree of 72, and 0.003 parts of F-50 hydroxypropyl methylcellulose. The composite initiator consists of 0.006 parts of cumyl peroxyneodecanoate and 0.008 parts of sodium persulfate. The pH regulator adopts ammonium bicarbonate, and the addition amount is 0.02 part. The compound terminator consists of 0.002 parts of N, N-diethyl hydroxylamine, 0.003 parts of p-tert-butyl catechol and 0.001 parts of dimethyl dithiocarbamic acid sodium.
The method comprises the following steps:
(1) Weighing deionized water according to a formula, putting the deionized water into a reaction kettle, weighing polyvinyl chloride resin according to the formula, adding the polyvinyl chloride resin into the reaction kettle, starting stirring, and controlling the rotating speed at 90r/min;
(2) Soaking polyvinyl chloride resin for 4.5 hours, adding 2-isopropyl phenyl phosphate, N-butyl maleimide monomer and composite dispersing agent, continuously soaking for 2 hours, and adding initiator sodium persulfate;
(3) Continuously stirring for 20 minutes, adding dialkyltin mercaptopropionate, heating a jacket to a reaction temperature of 55.5 ℃, entering a reaction stage, and automatically adjusting the reaction temperature to 55.5 ℃ by a reaction kettle;
(4) Adding an initiator of cumyl peroxyneodecanoate into the mixture after 1 hour of reaction, and adding a pH regulator after 2.5 hours of reaction;
(5) The reaction temperature is increased by 8 ℃ for 1 hour before the reaction is finished;
(6) The reaction time is 8 hours, 0.002 parts of compound terminator N, N-diethyl hydroxylamine, 0.003 parts of p-tertiary butyl catechol and 0.001 parts of dimethyl dithiocarbamic acid sodium are added, and stirring is continued for 20 minutes, and the reaction is finished.
(7) And discharging the material from the reaction kettle, removing residual monomers by a stripping device, and centrifugally drying to remove water to obtain a flame-retardant polyvinyl chloride resin finished product.
Example 6:
taking the following production raw materials in parts by weight: 160 parts of deionized water, 100 parts of polyvinyl chloride, 5 parts of alkylated triphenyl phosphate monomer, 5 parts of N-substituted maleimide monomer, 0.5 part of dialkyltin mercaptopropionate, 0.01 part of dispersing agent, 0.014 part of initiator, 0.02 part of pH regulator and 0.006 part of terminator.
Wherein the polyvinyl chloride resin adopts common SG5 resin. The alkylated triphenyl phosphate is added from 3-isopropyl phenyl phosphate in an amount of 5 parts. N-benzyl maleimide monomer, 5 parts. 0.8 parts of dialkyl tin mercaptopropionate. The dispersant consisted of 0.003 parts of KH-20 with an alcoholysis degree of 81, 0.004 parts of L-10 with an alcoholysis degree of 72, and 0.003 parts of F-50 hydroxypropyl methylcellulose. The composite initiator consists of 0.006 parts of cumyl peroxyneodecanoate and 0.008 parts of sodium persulfate. The pH regulator adopts ammonium bicarbonate, and the addition amount is 0.02 part. The compound terminator consists of 0.002 parts of N, N-diethyl hydroxylamine, 0.003 parts of p-tert-butyl catechol and 0.001 parts of dimethyl dithiocarbamic acid sodium.
The method comprises the following steps:
(1) Weighing deionized water according to a formula, putting the deionized water into a reaction kettle, weighing polyvinyl chloride resin according to the formula, adding the polyvinyl chloride resin into the reaction kettle, starting stirring, and controlling the rotating speed at 45r/min;
(2) Soaking polyvinyl chloride resin for 4.5 hours, adding 3-isopropyl phenyl phosphate, N-benzyl maleimide monomer and composite dispersing agent, continuously soaking for 1.5 hours, and adding initiator sodium persulfate;
(3) Continuously stirring for 20 minutes, adding dialkyltin mercaptopropionate, heating a jacket to the reaction temperature of 60 ℃, entering a reaction stage, and automatically adjusting the reaction temperature to 60 ℃ by a reaction kettle;
(4) Adding an initiator of cumyl peroxyneodecanoate into the mixture after 1 hour of reaction, and adding a pH regulator after 2.5 hours of reaction;
(5) The reaction temperature is increased by 8 ℃ for 1 hour before the reaction is finished;
(6) The reaction time was 7.5 hours, 0.002 parts of N, N-diethylhydroxylamine, 0.003 parts of p-tert-butylcatechol and 0.001 parts of sodium dimethyldithiocarbamate as a composite terminator were added, and stirring was continued for 20 minutes to complete the reaction.
(7) And discharging the material from the reaction kettle, removing residual monomers by a stripping device, and centrifugally drying to remove water to obtain a flame-retardant polyvinyl chloride resin finished product.
Comparative example 1 and comparative example 2:
two samples of commercially available suspension polyvinyl chloride resin having a degree of polymerization of 1000 were purchased for performance comparison.
The test performed by the application:
1. routine index detection
Detecting viscosity, apparent density, fish eyes and whiteness according to a suspension method universal polyvinyl chloride resin detection standard QB/T5761-2018, and determining combustion behavior part 2 by an oxygen index method for plastics according to GB/T2406.2-2009: room temperature test the oxygen index was measured and the results of the measurements for examples 1-6 and comparative examples 1-2 are shown in table 1.
Table 1 examples and comparative examples comparative table
| Project | Viscosity number (mg/l) | Apparent Density (l/mg) | Fish eye (personal/cm) 2 ) | Whiteness/% |
| Comparative example 1 | 113 | 0.54 | 16 | 83 |
| Comparative example 2 | 114 | 0.55 | 18 | 82 |
| Example 1 | 115 | 0.54 | 14 | 84 |
| Example 2 | 114 | 0.54 | 16 | 84 |
| Example 3 | 114 | 0.53 | 16 | 85 |
| Example 4 | 113 | 0.53 | 14 | 85 |
| Example 5 | 113 | 0.54 | 16 | 85 |
| Example 6 | 114 | 0.54 | 16 | 85 |
As can be seen from Table 1, the effects of example 5 and example 6 are relatively good, the "fish eyes" are small, the whiteness is high, the apparent density is moderate, and the viscosity is normal. The flame-retardant polyvinyl chloride resin is produced by an in-situ polymerization mode, and the flame-retardant polyvinyl chloride resin with better quality indexes is obtained.
2. Flame retardant performance detection
Determination of the Combustion behavior according to GB/T2406.2-2009 Plastic oxygen index method part 2: room temperature test for oxygen index, the flame retardant polyvinyl chloride resins obtained in examples 1 to 6 and comparative examples 1 to 2 were respectively taken for oxygen index detection, the specific processing formula is shown in table 2, and the oxygen index detection results are shown in table 3.
TABLE 2
1. Oxygen index detection
150g of the dry blend was initially plasticized on an open mill at 165 ℃. Cutting the test piece into blocks, placing into 200mm×200mm×4mm mold, entering into plate vulcanizing press, plasticizing at 175 deg.C for 10min, hot pressing for 4min, cooling for 3min, taking out 100mm×10mm×4mm sample, and detecting oxygen index according to GB/T2406.2-2009.
Results: the oxygen index test results of the 8 bars are shown in Table 3. The oxygen index of the example 5 is highest and reaches 59% higher than that of the comparative example, and the flame retardant property is good.
TABLE 3 oxygen index of the resins of examples 1-6 and comparative example
3. Processability test
Raw materials are weighed according to the formula of Table 2, and are respectively mixed in a high-speed mixer, discharged into a low-speed mixer when the temperature reaches 110 ℃, stirred and cooled to 50 ℃ and discharged to obtain a dry mixed material. The dry blends obtained in examples 1-6 and comparative examples 1-2 were tested using a Hark torque rheometer, the heating temperature in the 3 zones was 165℃and the rotor speed was 35r/min, the dry blend addition was 71.5g. The rheological test data are shown in Table 4. As can be seen from Table 4, the properties of the molded dry blends of flame retardant polyvinyl chloride resins obtained in examples 1 to 6 are greatly prolonged with respect to those of comparative examples 1 to 2, the decomposition time is prolonged by about 20% or more at maximum, the plasticizing time is reduced by 10%, and the other properties of the resins are not greatly changed, and the best results of example 5 are obtained by comprehensive comparison. Therefore, the flame-retardant polyvinyl chloride resin prepared by the application has better heat stability and processability.
Table 4 hash rheology data
4. Thermal stability test
The dry blends of examples 1 to 6 and comparative examples 1 to 2 were prepared without adding a plasticizer dioctyl terephthalate to the formulation of Table 2, and the obtained dry blends were kneaded on a rubber mixer to prepare PVC test pieces having a thickness of 1mm, respectively. According to GB/T2917.1-2002 standard, cutting a PVC sample into 2mm×2mm, loading into a test tube, placing a piece of Congo red test paper on the test tube, plugging the test paper by a plug, respectively heating the test paper in constant-temperature oil baths with the temperature of 170 ℃ and 180 ℃, and determining the time required for changing the Congo red test paper from red to blue, namely the thermal stability time. The test results are shown in Table 5. From table 5: the flame retardant polyvinyl chloride resins of examples 1 to 6 have improved heat stability times relative to the resins of comparative examples 1 to 2, wherein the resin of example 6 is optimal, the heat stability time at 170℃is improved by about 17% or more than that of the comparative examples, and the heat stability time at 180℃is improved by 25% than that of the comparative examples, so that the flame retardant polyvinyl chloride resin prepared by the present application has a good heat stability effect.
TABLE 5
| Formulation of | Temperature/. Degree.C | Thermal stability time/S | Temperature/. Degree.C | Thermal stability time/S |
| Comparative example 1 | 170 | 1255 | 180 | 860 |
| Example 1 | 170 | 1272 | 180 | 915 |
| Example 2 | 170 | 1413 | 180 | 990 |
| Example 3 | 170 | 1439 | 180 | 1017 |
| Example 4 | 170 | 1454 | 180 | 1045 |
| Example 5 | 170 | 1498 | 180 | 1116 |
| Example 6 | 170 | 1477 | 180 | 1090 |
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (15)
1. The flame-retardant polyvinyl chloride resin comprises polyvinyl chloride resin, deionized water, a flame retardant and other auxiliary agents, and is characterized by comprising the following components in parts by weight: 100-200 parts of deionized water, 100 parts of polyvinyl chloride resin, 0.5-6 parts of alkylated triphenyl phosphate monomer, 0.5-5 parts of N-substituted maleimide monomer and 0.1-1 part of dialkyltin mercaptopropionate, wherein the alkylated triphenyl phosphate monomer is a flame retardant, the N-substituted maleimide is a heat-resistant modifier, and the dialkyltin mercaptopropionate is a stabilizer.
2. The flame-retardant polyvinyl chloride resin according to claim 1, further comprising the following components in parts by weight: 0.009-0.032 parts of dispersing agent, 0.01-0.35 parts of initiator, 0.01-0.05 parts of pH regulator and 0.01-0.3 parts of terminator.
3. The flame-retardant polyvinyl chloride resin according to claim 1, wherein the polyvinyl chloride resin is a suspension method or a bulk method polyvinyl chloride resin, and has a polymerization degree of 700 to 3000.
4. The flame-retardant polyvinyl chloride resin as claimed in claim 1, wherein the alkylated triphenyl phosphate monomer of the flame retardant is one or more of 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, 2-isopropylphenyl phosphate, 3-isopropylphenyl phosphate, 4-isopropylphenyl phosphate, methyltrimolyl phosphate and the like.
5. The flame-retardant polyvinyl chloride resin as claimed in claim 1, wherein the heat-resistant modifier N-substituted maleimide monomer is one or more of N-ethylmaleimide, N-isopropylmaleimide, N-N-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-N-pentylmaleimide, N-N-octylmaleimide, N-benzylmaleimide and the like.
6. The flame-retardant polyvinyl chloride resin according to claim 1, wherein the initiator is selected from one or more of water-soluble or oil-soluble bis (2-ethyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, di-tert-butyl peroxybenzoate, cumyl peroxyneodecanoate, dibenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, acetyl cyclohexane sulfonyl peroxide, bis (3, 5-trimethylhexanoyl) peroxide, dicumyl peroxide, sodium persulfate, potassium persulfate and the like.
7. The flame-retardant polyvinyl chloride resin according to claim 1, wherein the dispersant is selected from one or a combination of two of polyvinyl alcohol with a degree of polymerization of 900-2500, hydroxypropyl methylcellulose with a gel temperature of 48-85 ℃.
8. The flame-retardant polyvinyl chloride resin according to claim 1, wherein the pH regulator is one or more selected from sodium hydride, ammonium bicarbonate and sodium bicarbonate.
9. The flame-retardant polyvinyl chloride resin as claimed in claim 1, wherein the terminator is one or more selected from a-methylstyrene, N-diethylhydroxylamine, an asymmetric hindered phenol antioxidant 245, p-t-butylcatechol, hydroquinone, nonylphenol, etc.
10. The method for preparing a flame retardant polyvinyl chloride resin according to claim 1 or 2, characterized by comprising the steps of:
(1) Weighing deionized water according to a formula, adding polyvinyl chloride resin according to the formula into a reaction kettle, starting stirring, and controlling the rotating speed at 45-90 r/min;
(2) After the polyvinyl chloride resin is soaked for 3 to 6 hours, adding an alkylated triphenyl phosphate monomer, an N-substituted maleimide monomer and a dispersing agent, continuously soaking for 1 to 3 hours, and adding a first part of initiator;
(3) Continuously stirring for 15-35 minutes, adding dialkyltin mercaptopropionate, heating a jacket to a reaction temperature of 38-75 ℃, entering a polymerization reaction stage, and automatically adjusting the reaction temperature to be within a range of 40-70 ℃ by a reaction kettle;
(4) Adding a second part of initiator after reacting for 1-4 hours;
(5) Then the mixture reacts for 1 to 3 hours, and a pH regulator is added;
(6) Raising the reaction temperature by 5-10 ℃ 1 hour before the reaction is finished, and continuing the reaction;
(7) The reaction time is 5 to 12 hours, a terminator is added, stirring is continued for 10 to 20 minutes, and the reaction is finished;
(8) And discharging the material from the reaction kettle, stripping to remove residual monomers, and centrifugally drying to remove water to obtain the flame-retardant polyvinyl chloride resin.
11. The method for preparing flame retardant polyvinyl chloride resin according to claim 10, wherein the polymerization reaction mode is in-situ polymerization.
12. The method for preparing flame-retardant polyvinyl chloride resin according to claim 10, wherein the initiator is added in a multi-step method, and the first part of the initiator added before the polymerization reaction and the second part of the initiator added after a certain time of the reaction can be the same initiator.
13. The method for preparing flame-retardant polyvinyl chloride resin according to claim 10, wherein the initiator is added in a multi-step method, and the first part of the initiator added before the polymerization reaction and the second part of the initiator added after a certain time of the reaction can be different initiators.
14. The method for preparing a flame retardant polyvinyl chloride resin according to claim 10, wherein the polymerization reaction pressure is normal pressure or nitrogen is introduced to maintain micro positive pressure.
15. The method for preparing a flame retardant polyvinyl chloride resin according to claim 10, wherein said micro positive pressure is 0.01-0.1 MPa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166271A (en) * | 1988-09-12 | 1992-11-24 | Mitsui Toatsu Chemicals, Inc. | Heat resistant polyvinyl chloride copolymer and preparation process of the copolymer |
| CN110218401A (en) * | 2019-05-22 | 2019-09-10 | 宁波先锋新材料股份有限公司 | A kind of soft PVC composite material and preparation method of flame-retardant smoke inhibition and good mechanical properties |
| CN111761772A (en) * | 2020-05-26 | 2020-10-13 | 宜宾天亿新材料科技有限公司 | Preparation method of high-flame-retardant smoke-suppression LVT floor wear-resistant layer |
| CN112126015A (en) * | 2020-09-30 | 2020-12-25 | 宜宾海丰和锐有限公司 | Extinction polyvinyl chloride resin and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166271A (en) * | 1988-09-12 | 1992-11-24 | Mitsui Toatsu Chemicals, Inc. | Heat resistant polyvinyl chloride copolymer and preparation process of the copolymer |
| CN110218401A (en) * | 2019-05-22 | 2019-09-10 | 宁波先锋新材料股份有限公司 | A kind of soft PVC composite material and preparation method of flame-retardant smoke inhibition and good mechanical properties |
| CN111761772A (en) * | 2020-05-26 | 2020-10-13 | 宜宾天亿新材料科技有限公司 | Preparation method of high-flame-retardant smoke-suppression LVT floor wear-resistant layer |
| CN112126015A (en) * | 2020-09-30 | 2020-12-25 | 宜宾海丰和锐有限公司 | Extinction polyvinyl chloride resin and preparation method thereof |
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