CN113801320B - Bio-based block polymer, preparation method and application thereof, and flame-retardant compound and preparation method thereof - Google Patents
Bio-based block polymer, preparation method and application thereof, and flame-retardant compound and preparation method thereof Download PDFInfo
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- CN113801320B CN113801320B CN202010484924.9A CN202010484924A CN113801320B CN 113801320 B CN113801320 B CN 113801320B CN 202010484924 A CN202010484924 A CN 202010484924A CN 113801320 B CN113801320 B CN 113801320B
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- flame retardant
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- block polymer
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 109
- 229920000642 polymer Polymers 0.000 title claims abstract description 106
- -1 flame-retardant compound Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 87
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 11
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 34
- 239000011230 binding agent Substances 0.000 claims description 34
- 239000002131 composite material Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 21
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229920001155 polypropylene Polymers 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 17
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229940126062 Compound A Drugs 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000002608 ionic liquid Substances 0.000 claims description 12
- SOGYZZRPOIMNHO-UHFFFAOYSA-N [2-(hydroxymethyl)furan-3-yl]methanol Chemical compound OCC=1C=COC=1CO SOGYZZRPOIMNHO-UHFFFAOYSA-N 0.000 claims description 11
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 10
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 9
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 9
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- JQRZRTHUGRAVGS-UHFFFAOYSA-N P(=O)(O)(O)O.C(C)C=1N(C(N(C1)CC)CC)C Chemical compound P(=O)(O)(O)O.C(C)C=1N(C(N(C1)CC)CC)C JQRZRTHUGRAVGS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- JXBHQYZANKJVGW-UHFFFAOYSA-N [2-(aminomethyl)furan-3-yl]methanamine Chemical compound NCC=1C=COC=1CN JXBHQYZANKJVGW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 4
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 claims description 3
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- OWGJXSYVHQEVHS-UHFFFAOYSA-N 1-dichlorophosphorylethane Chemical compound CCP(Cl)(Cl)=O OWGJXSYVHQEVHS-UHFFFAOYSA-N 0.000 claims description 2
- YZBOZNXACBQJHI-UHFFFAOYSA-N 1-dichlorophosphoryloxyethane Chemical compound CCOP(Cl)(Cl)=O YZBOZNXACBQJHI-UHFFFAOYSA-N 0.000 claims description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- SNVCRNWSNUUGEA-UHFFFAOYSA-N dichlorophosphoryloxymethane Chemical compound COP(Cl)(Cl)=O SNVCRNWSNUUGEA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- SCLFRABIDYGTAZ-UHFFFAOYSA-N methylphosphonic acid dichloride Chemical compound CP(Cl)(Cl)=O SCLFRABIDYGTAZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000000243 solution Substances 0.000 description 31
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000000203 mixture Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- JAMQTHFDMABXGQ-UHFFFAOYSA-N CNC.O1C=CC=C1 Chemical compound CNC.O1C=CC=C1 JAMQTHFDMABXGQ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 102220357434 c.88T>A Human genes 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
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- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention relates to the field of polymer chemistry, and discloses a bio-based block polymer, a preparation method and application thereof, a flame-retardant compound and a preparation method thereof. The biobased block polymer comprises: structural unit AAnd structural unit BWherein R is 1 At least one selected from the group consisting of methyl, methoxy, ethyl, ethoxy, phenyl and phenoxy; wherein R is 2 At least one selected from the group consisting of a structure represented by formula (11), a structure represented by formula (12), a structure represented by formula (13), a structure represented by formula (14), and a structure represented by formula (15); R 3 at least one selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted naphthene group; wherein the weight average molecular weight of the bio-based block polymer is 400-100000. The bio-based block polymer and the flame-retardant compound prepared from the bio-based block polymer have good flame-retardant property.
Description
Technical Field
The invention relates to the field of polymer chemistry, in particular to a bio-based block polymer, a preparation method and application thereof, a flame-retardant compound and a preparation method thereof.
Background
PP is one of the general plastics with the largest yield at present, has the advantages of good mechanical strength, easy molding and processing, chemical corrosion resistance and the like, and has wide application in the field of production and living. However, the limiting oxygen index of PP is about 17%, which belongs to inflammable materials, and a large amount of molten drops are generated during combustion, which is very easy to cause fire spread, and limits the application of PP in the fields of electronics, transportation and the like. Therefore, the flame retardant modification of PP has important significance. Currently, flame retardants applied to PP mainly include halogen-based flame retardants, inorganic flame retardants, and Intumescent Flame Retardants (IFR). The halogen flame retardant can release a large amount of toxic gas and dense smoke in the combustion process, and does not accord with the development trend of environmental protection of the flame retardant; the inorganic flame retardant has low efficiency and large addition amount, and obviously damages the mechanical properties of the resin; the IFR has the advantages of low smoke, low toxicity, environmental protection, small influence on the mechanical properties of the resin and the like, and has application in PP flame retardance. The IFR can form an expanded carbon layer in the PP combustion process, and the carbon layer has the functions of protecting a matrix, isolating heat, oxygen and transmitting combustible gas. The existing IFR has the defects of large addition amount, large influence on the physical properties of PP and the like, and a novel IFR system needs to be developed.
At present, research on PP flame retardants has been advanced to a certain extent, however, the preparation raw materials of the PP flame retardants mainly come from petrochemical products, and along with the increasing exhaustion of petroleum resources, development of flame retardants based on renewable resources has become an important direction of the development of the present flame retardant technology. The biomass raw material is taken as a renewable green material, has the advantages of abundant reserves, wide sources and renewable, and provides an effective solution for the green flame retardant. Therefore, the biological base material is taken as the raw material, and the research on the green and efficient flame retardant has important significance.
Disclosure of Invention
The invention aims to solve the problems of large IFR addition amount and large influence on the physical properties of PP in the prior art, and provides a bio-based block polymer, a preparation method and application thereof, and a flame-retardant compound and a preparation method thereof.
To achieve the above object, the first aspect of the present invention provides a biobased block polymer comprising:
structural unit AAnd structural unit B->
Wherein R is 1 At least one selected from the group consisting of methyl, methoxy, ethyl, ethoxy, phenyl and phenoxy;
wherein R is 2 At least one selected from the group consisting of a structure represented by formula (11), a structure represented by formula (12), a structure represented by formula (13), a structure represented by formula (14), and a structure represented by formula (15);
R 3 at least one selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted naphthene group;
wherein the weight average molecular weight of the bio-based block polymer is 400-100000.
In a second aspect, the present invention provides a method of preparing a biobased block polymer, the method comprising:
(1) Mixing a first part of compound A with a first acid binding agent in the presence of a first solvent to obtain a mixed material A; adding a compound B into the mixed material A, and then reacting for 6-12 hours at 50-110 ℃ under inert atmosphere to obtain a polymer solution D;
(2) Mixing a second part of compound A with a second acid binding agent in the presence of a second solvent to obtain a mixed material B; adding a compound C into the mixed material B, and then reacting for 6-12 hours at 50-110 ℃ under inert atmosphere to obtain a polymer solution E;
(3) Mixing the polymer solution E with the polymer solution D, and reacting for 6-12 hours at 80-110 ℃ under inert atmosphere to obtain a biological multi-block polymer;
wherein the compound A provides at least one of a structure represented by formula (11), a structure represented by formula (12), a structure represented by formula (13), a structure represented by formula (14) and a structure represented by formula (15);
the compound B provides a structure represented by formula (21);
wherein R is 1 At least one selected from the group consisting of methyl, methoxy, ethyl, ethoxy, phenyl and phenoxy;
wherein the compound C provides a structure represented by formula (22);
wherein R is 3 At least one selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted naphthene group.
The third aspect of the present invention provides the use of a biobased block polymer as described above or a biobased block polymer prepared by a method of preparing a biobased block polymer as described above in a flame retardant.
In a fourth aspect, the present invention provides a flame retardant composite comprising a flame retardant A, a matrix and an antioxidant;
wherein the flame retardant A is at least one selected from the biobased block polymers as described above and the biobased block polymers prepared by the method for preparing the biobased block polymers as described above.
Preferably, the flame retardant compound further comprises a flame retardant B, preferably ammonium polyphosphate and melamine polyphosphate.
Preferably, the flame retardant composite further comprises a synergist; the synergist is preferably at least one selected from diethyl 1-ethyl-3-methylimidazole phosphate, 1-benzyl-3-alkyl benzimidazole, diethyl 1-ethyl-3-methylimidazole phosphate, guanidine sulfamate, heteropolyacid, ionic liquid a, ionic liquid b, ionic liquid c, montmorillonite, silica, molecular sieve and hydrotalcite.
In a fifth aspect, the present invention provides a method of preparing a flame retardant composite as described above, comprising melt blending a flame retardant A, a matrix, an antioxidant, an optional flame retardant B, and an optional synergist to obtain the flame retardant composite.
In the invention, the bio-based block polymer does not contain halogen, has wide raw material sources, is environment-friendly, and has simple and efficient synthesis method and excellent flame retardant property.
Compared with the existing flame-retardant compound, the flame-retardant compound prepared by using the bio-based block polymer has the following advantages: 1) The main raw material (compound A) for preparing the bio-based block polymer is derived from biomass materials, and has the advantages of green environmental protection and sustainability; 2) High flame-retarding efficiency, low smoke and no halogen.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a biobased block polymer comprising:
structural unit AAnd structural unit B->
Wherein R is 1 At least one selected from the group consisting of methyl, methoxy, ethyl, ethoxy, phenyl and phenoxy;
wherein R is 2 At least one selected from the group consisting of a structure represented by formula (11), a structure represented by formula (12), a structure represented by formula (13), a structure represented by formula (14), and a structure represented by formula (15);
R 3 at least one selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted naphthene group;
wherein the weight average molecular weight of the bio-based block polymer is 400-100000.
Preferably, the group employed for substitution is at least one of hydroxyl, halogen and carboxyl.
In the present invention, preferably, R 1 Is phenyl and/or phenoxy.
In the present invention, preferably, R 2 At least one selected from the group consisting of a structure represented by formula (11), a structure represented by formula (12), and a structure represented by formula (13);
in the present invention, preferably, R 3 Is at least one of C4-C12 (C4, C5, C6, C7, C8, C9, C10, C11 or C12) alkylene (or straight chain alkylene). More preferably, R 3 Is a C4-C10 (C4, C5, C6, C7, C8, C9 or C10) linear alkylene group. Further preferred are n-hexyl and/or n-decyl.
In the above preferred case, the biobased block polymer has better flame retardant properties.
In the present invention, the content of the structural unit a and the structural unit B in the bio-based block polymer is in an arbitrary ratio, and preferably, the molar ratio of the structural unit a to the structural unit B is 1: (0.5-1.5), more preferably 1: (0.53-0.82).
At the bookIn the invention, the bio-based block polymer may contain a combination of the above structural units a and B in different combinations. Wherein structures linked in any number of repeating units A or B, such as A, may be included m And B n It is also possible to include structures such as AB, where structural unit A and structural unit B are connected.
In the present invention, the number m of repeating units in the structural unit a is any integer of 1 or more. Preferably, m=1-2000.
In the present invention, the number n of repeating units in the structural unit B is any integer of 1 or more. Preferably, n=1-2000.
Wherein the bio-based block polymer comprises a typical structure as follows:
the numerical values of a1 to a7 are not particularly limited, and are preferably 1 to 2000 as long as they are more than 1.
It should be understood that the above formulas (1) - (7) list only a few of the structures, and those skilled in the art can arbitrarily combine the structures according to the structural units to obtain biobased block polymers of different structures.
In a second aspect, the present invention provides a method of preparing a biobased block polymer, the method comprising:
(1) Mixing a first part of compound A with a first acid binding agent in the presence of a first solvent to obtain a mixed material A; adding a compound B into the mixed material A, and then reacting for 6-12 hours at 50-110 ℃ under inert atmosphere to obtain a polymer solution D;
(2) Mixing a second part of compound A with a second acid binding agent in the presence of a second solvent to obtain a mixed material B; adding a compound C into the mixed material B, and then reacting for 6-12 hours at 50-110 ℃ under inert atmosphere to obtain a polymer solution E;
(3) Mixing the polymer solution E with the polymer solution D, and reacting for 6-12 hours at 80-110 ℃ under inert atmosphere to obtain a biological multi-block polymer;
wherein the compound A provides at least one of a structure represented by formula (11), a structure represented by formula (12), a structure represented by formula (13), a structure represented by formula (14) and a structure represented by formula (15);
the compound B provides a structure represented by formula (21);
wherein R is 1 At least one selected from the group consisting of methyl, methoxy, ethyl, ethoxy, phenyl and phenoxy;
wherein the compound C provides a structure represented by formula (22);
R 3 at least one selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted naphthene group.
Wherein R is 1 、R 2 And R is 3 The preferred ranges of (a) have been described in detail in the first aspect and are not described in detail herein.
In the present invention, preferably, the compound a is at least one selected from the group consisting of 1, 5-pentanediamine, furandimethanol, furandimethylamine, oxybisfurandimethanol and propane bisfurandimethylamine, more preferably at least one selected from the group consisting of 1, 5-pentanediamine, furandimethanol and furandimethylamine.
The source of the compound A in the invention can be a bio-based source, and the bio-based block polymer is prepared by using the compound A of the type, so that the preparation method has the advantages of green, environment protection and sustainability.
In the present invention, preferably, the compound B is at least one selected from the group consisting of phenylphosphonic dichloride, phenyl dichlorophosphate, methylphosphonic dichloride, methyl dichlorophosphate, ethylphosphonic dichloride and ethyl dichlorophosphate, more preferably phenylphosphonic dichloride and/or phenyl dichlorophosphate.
In the present invention, preferably, the compound C is a C4-C12 alkyl diacid chloride, more preferably a C4-C10 linear alkylene diacid chloride, still more preferably adipoyl chloride and/or sebacoyl chloride.
In the case of the preferred compound a, compound B and compound C, the flame retardant properties of the prepared biobased block polymer can be further improved.
In a preferred embodiment of the present invention, the compound a is at least one selected from the group consisting of 1, 5-pentanediamine, furandimethanol and furandimethylamine, the compound B is phenylphosphonic dichloride and/or phenyl dichlorophosphate, and the compound C is adipoyl chloride and/or sebacoyl chloride. In the preferred case, the flame retardant properties of the prepared biobased block polymer can be further improved.
In the present invention, the first solvent and the second solvent may be organic solvents conventionally used in the art, as long as they do not react with the acid chloride. The types of the first solvent and the second solvent may be the same or different.
Preferably, the first solvent is selected from one of toluene, acetonitrile, ethyl acetate, butyl acetate, N-dimethylformamide, butanone, cyclohexanone, tetrahydrofuran, dioxane, petroleum ether, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, carbon disulfide, benzene, xylene, nitrobenzene, chlorobenzene, cyclohexane, and N-hexane.
Preferably, the second solvent is selected from one of toluene, acetonitrile, ethyl acetate, butyl acetate, N-dimethylformamide, butanone, cyclohexanone, tetrahydrofuran, dioxane, petroleum ether, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, carbon disulfide, benzene, xylene, nitrobenzene, chlorobenzene, cyclohexane, and N-hexane.
In the present invention, the first acid-binding agent and the second acid-binding agent may be acid-binding agents conventionally used in the art. The species of the first acid-binding agent and the second acid-binding agent may be the same or different.
Preferably, the first acid binding agent is one of triethylamine, pyridine and N, N-diisopropylethylamine.
Preferably, the second acid binding agent is one of triethylamine, pyridine and N, N-diisopropylethylamine.
In the present invention, preferably, the molar ratio of the first partial compound a, the second partial compound a, the compound B, the compound C, the first acid-binding agent and the second acid-binding agent is 1: (0.7-1.3): (0.8-1.4): (0.7-1.2): (2-2.6): (1.4-3.0), more preferably 1: (0.9-1.1): (1.1-1.3): (0.7-0.9): (2-2.6): (1.8-2.6). In the preferred case, the flame retardant properties of the biobased block polymer can be further improved.
In the present invention, the amounts of the first solvent and the second solvent may be selected within a wide range, as long as the materials can be allowed to react in the presence of the solvents.
Preferably, the first solvent is used in an amount of 800 to 1200 parts by weight, relative to 100 parts by weight of the compound B.
Preferably, the second solvent is used in an amount of 1800 to 2200 parts by weight, relative to 100 parts by weight of compound C.
In the present invention, in the steps (1), (2) and (3), the mixing method may be a technical means conventional in the art, for example, the compound a may be formed into a mixture with the acid-binding agent in the presence of the solvent by stirring, ultrasonic and shaking methods under normal temperature conditions.
In the present invention, in the steps (1), (2) and (3), the method of adding the compound B or the compound C to the mixture a may be a method conventional in the art, and preferably, the compound B or the compound C is added to the mixture a in a dropwise manner.
The rate of the dropping is not particularly limited, and may be adjusted by one skilled in the art according to the size of the reaction system. For example, in a 10L reaction system, it is preferable that the dropping speed is 8 to 12mL/min.
In the present invention, the inert atmosphere may be an atmosphere which does not react with each material, and preferably, the inert atmosphere is nitrogen and/or argon.
In the present invention, in order to obtain a high purity bio-based block polymer, the reaction product may be further post-treated, preferably, in the step (3), the product obtained after the reaction is filtered, washed with water, and dried at 60 to 120 ℃ for 4 to 24 hours to obtain a high purity bio-based block polymer.
The third aspect of the present invention provides the use of a biobased block polymer as described above or a biobased block polymer prepared by a method of preparing a biobased block polymer as described above in a flame retardant.
In a fourth aspect, the present invention provides a flame retardant composite comprising a flame retardant A, a matrix and an antioxidant;
wherein the flame retardant A is at least one selected from the biobased block polymers as described above and the biobased block polymers prepared by the method for preparing the biobased block polymers as described above.
In the present invention, the substrate may be a substrate conventionally used in the art, preferably, the substrate is polypropylene and/or polyethylene; more preferably polypropylene. In the preferred case, the flame retardant is more matched with the thermal decomposition temperature of the matrix, and the flame retardant effect is better.
Wherein the polypropylene may be polypropylene conventionally used in the art, preferably the polypropylene has a melt mass flow rate of (7-30) g/10min.
Wherein the polyethylene may be a polyethylene conventionally used in the art, preferably the polyethylene has a melt mass flow rate of (1-20) g/10min.
In the present invention, the antioxidant may be an antioxidant conventionally used in the art, preferably, the antioxidant is at least one selected from pentaerythritol tetrakis (β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate), N-stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanuric acid, tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, N' -bis- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and triphenyl phosphite.
Wherein, antioxidant 1010 is pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), antioxidant 1076 is N-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, antioxidant CA is 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, antioxidant 3114 is 1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, antioxidant 168 is tris (2, 4-di-tert-butylphenyl) phosphite, antioxidant 626 is bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, antioxidant 1098 is N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and antioxidant TPP is triphenyl phosphite.
In the present invention, the flame retardant compound has good flame retardant property even in the case of the above composition, preferably, the flame retardant compound further contains a flame retardant B, which can further improve the flame retardant effect of the flame retardant compound.
Wherein the flame retardant B may be a flame retardant conventionally used in the art, preferably the flame retardant B is ammonium polyphosphate and/or melamine polyphosphate. In the preferred case, the flame retardant effect of the flame retardant composite can be further improved.
Wherein the ammonium polyphosphate may be an ammonium polyphosphate conventionally used in the art, preferably the ammonium polyphosphate is of type ii, having a degree of polymerization >1500.
In the present invention, preferably, the flame retardant composite further contains a synergist; the synergist is preferably at least one selected from diethyl 1-ethyl-3-methylimidazole phosphate, 1-benzyl-3-alkyl benzimidazole, diethyl 1-ethyl-3-methylimidazole phosphate, guanidine sulfamate, heteropolyacid, ionic liquid a, ionic liquid b, ionic liquid c, montmorillonite, silica, molecular sieve and hydrotalcite. In the preferred case, the flame retardant effect of the flame retardant composite can be further improved.
Wherein the ionic liquid a is diethyl 1-ethyl-3-methylimidazole phosphate, the ionic liquid b is 1-benzyl-3-alkyl benzimidazole, and the ionic liquid c is diethyl 1-ethyl-3-methylimidazole phosphate.
Wherein the montmorillonite is organically modified montmorillonite, such as long carbon chain alkyl quaternary ammonium salt or alkyl amino acid intercalated montmorillonite.
Wherein the molecular sieve may be a 4A or 5A molecular sieve.
In the present invention, the content of each material in the flame retardant composite may be selected within a wide range, and preferably, the content of the matrix is 70 to 90 wt%, the content of the flame retardant a is 3 to 15 wt%, the content of the flame retardant B is 0 to 25 wt%, the content of the synergist is 0 to 5 wt%, and the content of the antioxidant is 0.03 to 1 wt%, based on the total amount of the flame retardant composite.
More preferably, the content of the matrix is 76-90 wt%, the content of the flame retardant A is 4-10 wt%, the content of the flame retardant B is 0-20 wt%, the content of the synergist is 0.8-1.3 wt%, and the content of the antioxidant is 0.03-0.6 wt%, based on the total amount of the flame retardant compound.
In a fifth aspect, the present invention provides a method of preparing a flame retardant composite as described above, comprising melt blending a flame retardant A, a matrix, an antioxidant, an optional flame retardant B, and an optional synergist to obtain the flame retardant composite.
In the present invention, the types and properties of the flame retardant a, the matrix, the antioxidant, the flame retardant B and the synergist are described in detail in the sixth aspect, and will not be described in detail herein.
Preferably, the components are used in such amounts that the matrix is 70-90 wt%, the flame retardant A is 3-15 wt%, the flame retardant B is 0-25 wt%, the synergist is 0-5 wt% and the antioxidant is 0.03-1 wt% in the flame retardant composite.
More preferably, the components are used in such amounts that the matrix is 76-90 wt%, the flame retardant A is 4-10 wt%, the flame retardant B is 0-20 wt%, the synergist is 0.8-1.3 wt% and the antioxidant is 0.03-0.6 wt% of the flame retardant composite.
In the present invention, the conditions of melting may be conventional conditions in the art, preferably, the conditions of melting include: the melting temperature is 180-200 ℃.
Wherein the melting may be carried out in an internal mixer or a twin screw extruder.
In a preferred embodiment of the invention, the preparation method of the flame-retardant compound comprises the steps of uniformly mixing the flame retardant A, the matrix, the antioxidant, the optional flame retardant B and the optional synergist in a high-speed mixer, adding the obtained mixture into a double-screw extruder, controlling the temperature of the extruder and a die to be 180-200 ℃, melting, and then cooling and granulating to obtain the flame-retardant compound.
The present invention will be described in detail by examples.
In the following examples, the Limiting Oxygen Index (LOI) is determined according to ASTM D2863-97, spline dimensions of 100mm by 6.5mm by 3.2mm.
UL-94 burn rating is determined according to ASTM D3801, spline dimensions 100mm by 13mm by 3.2mm.
Polypropylene (PP) is a commercial product with the brand of C30S of China petrochemical and sea-refining company.
Polyethylene (PE) is a commercial product with the trademark of M2320 of China petrochemical sea-refining company.
Ammonium polyphosphate (APP) is a commercially available product of the company Protefosine chemical Co., ltd. Under the trademark EPFR-APP 231.
Other reagents such as 1, 5-pentanediamine were purchased from Aba Ding Shiji company.
Room temperature means 25±5 ℃.
The solvents used in the examples below were all solvents after water removal.
Structural units a and B in the following examples are shown in table 1, respectively.
TABLE 1
Example 1
This example is illustrative of the preparation of the biobased block polymers of the present invention
1.02g (0.010 mol) of 1, 5-pentanediamine is completely dissolved in toluene, stirred uniformly, 2.02g (0.020 mol) of triethylamine as an acid binding agent is added, stirred uniformly, 2.34g (0.012 mol) of phenylphosphonic dichloride is dripped into the system at room temperature, and after the dripping is finished, the reaction is carried out for 8 hours under the protection of nitrogen at 110 ℃ to obtain a polymer solution containing phosphoryl chloride;
1.02g (0.010 mol) of 1, 5-pentanediamine is completely dissolved in toluene, stirred uniformly, 2.02g (0.020 mol) of acid-binding agent is added into triethylamine, stirred uniformly, 1.46g (0.008 mol) of adipoyl chloride is dripped into the system at room temperature, after the dripping is finished, the reaction is carried out for 8 hours under the protection of nitrogen at 110 ℃, the obtained solution after the reaction is added into the polymer solution containing phosphoryl chloride, and the reaction is carried out for 6 hours under the protection of nitrogen at 110 ℃; the biological multi-block polymer is obtained, and the structures of the structural unit A and the structural unit B contained in the biological multi-block polymer are shown in the table 1.
After the reaction, the mixture is filtered by suction, washed by water for multiple times and dried for 24 hours at 80 ℃ to obtain 3.40g of the product with the yield of 77.6 percent.
Example 2
This example is illustrative of the preparation of the biobased block polymers of the present invention
1.28g (0.010 mol) of furandimethanol is completely dissolved in dioxane, evenly stirred, 2.42g (0.024 mol) of acid binding agent triethylamine is added, evenly stirred, 2.14g (0.011 mol) of phenylphosphonic dichloride is dripped into the system at room temperature, and after the dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 50 ℃ to obtain polymer solution containing phosphoryl chloride;
1.28g (0.010 mol) of furandimethanol is completely dissolved in dioxane, evenly stirred, 2.42g (0.024 mol) of acid binding agent is added into triethylamine, evenly stirred, 1.65g (0.009 mol) of adipoyl chloride is dripped into a system at room temperature, after dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 50 ℃, the obtained solution after the reaction is added into the polymer solution containing phosphoryl chloride, and the reaction is carried out for 8 hours under the protection of nitrogen at 100 ℃; the biological multi-block polymer is obtained, and the structures of the structural unit A and the structural unit B contained in the biological multi-block polymer are shown in the table 1.
After the reaction, the mixture is filtered by suction, washed by water for multiple times and dried for 4 hours at 120 ℃ to obtain 4.24g of the product with the yield of 86.7 percent.
Example 3
This example is illustrative of the preparation of the biobased block polymers of the present invention
1.26g (0.010 mol) of furan dimethylamine is completely dissolved in acetonitrile, the mechanical stirring is uniform, 1.74g (0.022 mol) of pyridine as an acid binding agent is added, the stirring is uniform, 2.53g (0.013 mol) of phenylphosphonic dichloride is dripped into the system at room temperature, and after the dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 80 ℃ to obtain a polymer solution containing phosphoryl chloride;
1.26g (0.010 mol) of furan dimethylamine is completely dissolved in acetonitrile, evenly stirred, 1.74g (0.022 mol) of pyridine is added into an acid binding agent, evenly stirred, 1.28g (0.007 mol) of adipoyl chloride is dripped into a system at room temperature, after the dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 80 ℃, the obtained solution after the reaction is added into the polymer solution containing phosphoryl chloride, and the reaction is carried out for 12 hours under the protection of nitrogen at 80 ℃; the biological multi-block polymer is obtained, and the structures of the structural unit A and the structural unit B contained in the biological multi-block polymer are shown in the table 1.
After the reaction, the mixture is filtered by suction, washed by water for multiple times and dried for 24 hours at 60 ℃ to obtain 3.80g of the product with the yield of 78.0 percent.
Example 4
This example is illustrative of the preparation of the biobased block polymers of the present invention
1.02g (0.010 mol) of 1, 5-pentanediamine is completely dissolved in toluene, stirred uniformly, 2.59g (0.020 mol) of N, N-diisopropylethylamine is added into an acid binding agent, stirred uniformly, 2.53g (0.012 mol) of phenyl dichlorophosphate is dripped into a system at room temperature, and the reaction is carried out for 12 hours under the protection of nitrogen at 80 ℃ after the dripping is finished, so as to obtain a polymer solution containing phosphoryl chloride;
1.02g (0.010 mol) of 1, 5-pentanediamine is completely dissolved in toluene, stirred uniformly, 2.59g (0.020 mol) of N, N-diisopropylethylamine is added into an acid binding agent, stirred uniformly, 1.46g (0.008 mol) of adipoyl chloride is dripped into the system at room temperature, after the dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 80 ℃, the obtained solution after the reaction is added into the polymer solution containing phosphoryl chloride, and the reaction is carried out for 8 hours under the protection of nitrogen at 110 ℃; the biological multi-block polymer is obtained, and the structures of the structural unit A and the structural unit B contained in the biological multi-block polymer are shown in the table 1.
After the reaction is finished, the mixture is filtered by suction, washed by water for multiple times and dried for 24 hours at 80 ℃ to obtain 3.89g of product with the yield of 85.2 percent.
Example 5
This example is illustrative of the preparation of the biobased block polymers of the present invention
1.28g (0.010 mol) of furandimethanol is completely dissolved in toluene, stirred uniformly, 2.02g (0.020 mol) of triethylamine as an acid binding agent is added, stirred uniformly, 2.53g (0.012 mol) of phenyl dichlorophosphate is dripped into the system at room temperature, and after the dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 100 ℃ to obtain a polymer solution containing phosphoryl chloride;
1.28g (0.010 mol) of furandimethanol is completely dissolved in toluene, evenly stirred, 2.02g (0.020 mol) of triethylamine as an acid binding agent is added, evenly stirred, 1.46g (0.008 mol) of adipoyl chloride is dripped into a system at room temperature, after the dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 80 ℃, the obtained solution after the reaction is added into the polymer solution containing phosphoryl chloride, and the reaction is carried out for 8 hours under the protection of nitrogen at 110 ℃; the biological multi-block polymer is obtained, and the structures of the structural unit A and the structural unit B contained in the biological multi-block polymer are shown in the table 1.
After the reaction, the mixture is filtered by suction, washed by water for multiple times and dried for 24 hours at 80 ℃ to obtain 3.65g of the product with the yield of 71.7 percent.
Example 6
This example is illustrative of the preparation of the biobased block polymers of the present invention
1.26g (0.010 mol) of furan dimethylamine is completely dissolved in dioxane, stirred uniformly, 2.02g (0.020 mol) of acid binding agent triethylamine is added, stirred uniformly, 2.53g (0.012 mol) of phenyl dichlorophosphate is dripped into the system at room temperature, and after the dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 80 ℃ to obtain polymer solution containing phosphoryl chloride;
completely dissolving 1.26g (0.010 mol) of furan dimethylamine in dioxane, uniformly stirring, adding 2.02g (0.020 mol) of acid-binding agent triethylamine, uniformly stirring, dripping 1.46g (0.008 mol) of adipoyl chloride into the system at room temperature, reacting for 12 hours at 80 ℃ under nitrogen protection after the dripping is finished, adding the reacted solution into the polymer solution containing phosphoryl chloride, and reacting for 8 hours at 100 ℃ under nitrogen protection; the biological multi-block polymer is obtained, and the structures of the structural unit A and the structural unit B contained in the biological multi-block polymer are shown in the table 1.
After the reaction, the mixture is filtered by suction, washed by water for multiple times and dried for 24 hours at 80 ℃ to obtain 4.35g of the product with the yield of 86.1 percent.
Example 7
This example is illustrative of the preparation of the biobased block polymers of the present invention
1.28g (0.010 mol) of furandimethanol is completely dissolved in toluene, stirred uniformly, 2.02g (0.020 mol) of triethylamine as an acid binding agent is added, stirred uniformly, 2.53g (0.012 mol) of phenyl dichlorophosphate is dripped into the system at room temperature, and after the dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 100 ℃ to obtain a polymer solution containing phosphoryl chloride;
1.28g (0.010 mol) of furan dimethanol is completely dissolved in toluene, evenly stirred, 2.02g (0.020 mol) of triethylamine as an acid binding agent is added, evenly stirred, 1.91g (0.008 mol) of sebacoyl chloride is dripped into the system at room temperature, after dripping is finished, the reaction is carried out for 12 hours under the protection of nitrogen at 80 ℃, the obtained solution after reaction is added into the polymer solution containing phosphoryl chloride, and the reaction is carried out for 8 hours under the protection of nitrogen at 110 ℃; the biological multi-block polymer is obtained, and the structures of the structural unit A and the structural unit B contained in the biological multi-block polymer are shown in the table 1.
After the reaction, the mixture is filtered by suction, washed by water for multiple times and dried for 24 hours at 80 ℃ to obtain 3.80g of the product with the yield of 68.5 percent.
Application example
This application is illustrative of the flame retardant composite of the present invention
According to the formulation shown in Table 2, the components were uniformly mixed using a high-speed mixer, and the obtained mixture was fed into a twin-screw extruder, the extruder and die temperature were controlled at 190℃and cooled to pelletize to obtain a flame retardant composite. And (5) manufacturing test sample bars by an injection molding machine, and testing.
TABLE 2
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The flame retardant composite was tested for flame retardant properties, and the specific results are shown in Table 3.
TABLE 3 Table 3
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As can be seen from the results of Table 3, the biobased block polymer of the present invention can have a better flame retardant effect through UL-94V-0 grade.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (21)
1. A biobased block polymer, characterized in that the biobased block polymer comprises:
structural unit AAnd structural unit B->；
Wherein R is 1 At least one selected from the group consisting of methyl, methoxy, ethyl, ethoxy, phenyl and phenoxy;
wherein R is 2 At least one selected from the group consisting of a structure represented by formula (11), a structure represented by formula (12), a structure represented by formula (13), and a structure represented by formula (15);
formula (11);
formula (12);
formula (13);
formula (15);
R 3 selected from the group consisting of substituted or unsubstituted alkylene groups and substituted or unsubstituted naphthene groupsAt least one of;
wherein the weight average molecular weight of the bio-based block polymer is 400-100000.
2. The biobased block polymer of claim 1, wherein R 3 Wherein the group adopted for substitution is at least one of hydroxyl, halogen and carboxyl; and/or
The molar ratio of structural unit A to structural unit B is 1: (0.5-1.5).
3. The biobased block polymer of claim 1 or 2, wherein R 1 Is phenyl and/or phenoxy; and/or
R 2 At least one selected from the group consisting of a structure represented by formula (11), a structure represented by formula (12), and a structure represented by formula (13); and/or
R 3 Is at least one of C4-C12 alkylene groups.
4. A method of preparing a biobased block polymer, the method comprising:
(1) Mixing a first part of compound A with a first acid binding agent in the presence of a first solvent to obtain a mixed material A; adding a compound B into the mixed material A, and then reacting for 6-12 hours at 50-110 ℃ under inert atmosphere to obtain a polymer solution D;
(2) Mixing a second part of compound A with a second acid binding agent in the presence of a second solvent to obtain a mixed material B; adding a compound C into the mixed material B, and then reacting for 6-12 hours at 50-110 ℃ under inert atmosphere to obtain a polymer solution E;
(3) Mixing the polymer solution E with the polymer solution D, and reacting for 6-12 hours at 80-110 ℃ under inert atmosphere to obtain a biological multi-block polymer;
wherein the compound A provides at least one of a structure represented by formula (11), a structure represented by formula (12), a structure represented by formula (13) and a structure represented by formula (15);
formula (11);
formula (12);
formula (13);
formula (15);
the compound B provides a structure represented by formula (21);
formula (21);
wherein R is 1 At least one selected from the group consisting of methyl, methoxy, ethyl, ethoxy, phenyl and phenoxy;
wherein the compound C provides a structure represented by formula (22);
formula (22);
R 3 at least one selected from the group consisting of a substituted or unsubstituted alkylene group and a substituted or unsubstituted naphthene group.
5. The method according to claim 4, wherein the compound a is selected from at least one of 1, 5-pentanediamine, furandimethanol, furandimethylamine, and propane bisfurandimethylamine; and/or
The compound B is at least one selected from phenylphosphonic dichloride, phenyl dichlorophosphate, methylphosphonic dichloride, methyl dichlorophosphate, ethylphosphonic dichloride and ethyl dichlorophosphate; and/or
The compound C is C4-C12 alkyl diacid chloride.
6. The method according to claim 5, wherein the compound a is selected from at least one of 1, 5-pentanediamine, furandimethanol, and furandimethylamine; and/or
The compound B is phenylphosphonic dichloride and/or phenyl dichlorophosphate; and/or
The compound C is adipoyl chloride and/or sebacoyl chloride.
7. The method of claim 4, wherein the first solvent is selected from one of toluene, acetonitrile, ethyl acetate, butyl acetate, N-dimethylformamide, butanone, cyclohexanone, tetrahydrofuran, dioxane, petroleum ether, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, carbon disulfide, benzene, xylene, nitrobenzene, chlorobenzene, cyclohexane, and N-hexane.
8. The method of claim 4, wherein the second solvent is selected from one of toluene, acetonitrile, ethyl acetate, butyl acetate, N-dimethylformamide, butanone, cyclohexanone, tetrahydrofuran, dioxane, petroleum ether, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, carbon disulfide, benzene, xylene, nitrobenzene, chlorobenzene, cyclohexane, and N-hexane.
9. The method of claim 4, wherein the first acid binding agent is one of triethylamine, pyridine, N-diisopropylethylamine.
10. The method of claim 4, wherein the second acid binding agent is one of triethylamine, pyridine, N-diisopropylethylamine.
11. The method of claim 4, wherein the molar ratio of the first portion of compound a, the second portion of compound a, the compound B, the compound C, the first acid-binding agent, and the second acid-binding agent is 1: (0.7-1.3): (0.8-1.4): (0.7-1.2): (2-2.6): (1.4-3.0).
12. Use of the biobased block polymer of any one of claims 1-3 or the biobased block polymer prepared by the method of preparing a biobased block polymer of any one of claims 4-11 in flame retardants.
13. A flame retardant composite, which is characterized by comprising a flame retardant A, a matrix and an antioxidant;
wherein the flame retardant A is at least one selected from the group consisting of the biobased block polymer described in claims 1 to 3 and the biobased block polymer produced by the method for producing a biobased block polymer described in any one of claims 4 to 11.
14. The flame retardant composite of claim 13, wherein the matrix is polypropylene and/or polyethylene; and/or
The antioxidant is at least one selected from pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), N-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tri (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and triphenyl phosphite.
15. The flame retardant composite of claim 13 or 14, wherein the flame retardant composite further comprises a flame retardant B.
16. The flame retardant composite of claim 15, wherein the flame retardant B is ammonium polyphosphate and/or melamine polyphosphate.
17. The flame retardant composite of claim 15, wherein the flame retardant composite further comprises a synergist.
18. The flame retardant composite of claim 17, wherein the synergist is selected from at least one of diethyl 1-ethyl-3-methylimidazole phosphate, 1-benzyl-3-alkylbenzimidazole, diethyl 1-ethyl-3-methylimidazole phosphate, guanidine sulfamate, heteropolyacid, ionic liquid a, ionic liquid b, ionic liquid c, montmorillonite, silica, molecular sieve, and hydrotalcite.
19. The flame retardant composite of claim 13, wherein the matrix is present in an amount of 70-90 wt%, the flame retardant a is present in an amount of 3-15 wt%, the flame retardant B is present in an amount of 0-25 wt%, the synergist is present in an amount of 0-5 wt%, and the antioxidant is present in an amount of 0.03-1 wt%, based on the total amount of the flame retardant composite.
20. A method of preparing a flame retardant composite according to any of claims 13 to 19, comprising melt blending flame retardant a, a matrix, an antioxidant, optionally flame retardant B and optionally a synergist to obtain the flame retardant composite.
21. The method of claim 20, wherein the components are used in an amount such that the matrix is 70-90 wt%, the flame retardant a is 3-15 wt%, the flame retardant B is 0-25 wt%, the synergist is 0-5 wt% and the antioxidant is 0.03-1 wt% of the flame retardant composite.
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| CN1705705A (en) * | 2002-10-17 | 2005-12-07 | 西巴特殊化学品控股有限公司 | Flame retardant compositions |
| CN1950436A (en) * | 2004-05-13 | 2007-04-18 | 西巴特殊化学品控股有限公司 | Flame retardants |
| CN106243385A (en) * | 2016-07-27 | 2016-12-21 | 华南理工大学 | A kind of DOPO based flameproofing and preparation method thereof |
| CN108948424A (en) * | 2017-05-19 | 2018-12-07 | 四川大学 | A kind of response type phosphonium flame retardant and its preparation method and application |
| CN109280219A (en) * | 2018-07-19 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of efficiently based flameproofing of biology containing furan nucleus and its synthetic method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1705705A (en) * | 2002-10-17 | 2005-12-07 | 西巴特殊化学品控股有限公司 | Flame retardant compositions |
| CN1950436A (en) * | 2004-05-13 | 2007-04-18 | 西巴特殊化学品控股有限公司 | Flame retardants |
| CN106243385A (en) * | 2016-07-27 | 2016-12-21 | 华南理工大学 | A kind of DOPO based flameproofing and preparation method thereof |
| CN108948424A (en) * | 2017-05-19 | 2018-12-07 | 四川大学 | A kind of response type phosphonium flame retardant and its preparation method and application |
| CN109280219A (en) * | 2018-07-19 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of efficiently based flameproofing of biology containing furan nucleus and its synthetic method and application |
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