CN114292299A - Phosphorus-containing, nitrogen-containing and sulfonate-containing compound, and preparation method and application thereof - Google Patents
Phosphorus-containing, nitrogen-containing and sulfonate-containing compound, and preparation method and application thereof Download PDFInfo
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- CN114292299A CN114292299A CN202111627325.9A CN202111627325A CN114292299A CN 114292299 A CN114292299 A CN 114292299A CN 202111627325 A CN202111627325 A CN 202111627325A CN 114292299 A CN114292299 A CN 114292299A
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- Prior art keywords
- compound
- nitrogen
- phosphorus
- formula
- equal
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 179
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 125
- 239000011574 phosphorus Substances 0.000 title claims abstract description 125
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 165
- 239000003063 flame retardant Substances 0.000 claims abstract description 112
- 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 95
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 83
- 229920000642 polymer Polymers 0.000 claims abstract description 80
- 239000004417 polycarbonate Substances 0.000 claims abstract description 26
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 80
- -1 amine compound Chemical class 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 238000007259 addition reaction Methods 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 229910021529 ammonia Inorganic materials 0.000 claims description 37
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 35
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 31
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 150000002736 metal compounds Chemical class 0.000 claims description 31
- 238000006277 sulfonation reaction Methods 0.000 claims description 31
- 239000012948 isocyanate Substances 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
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- 238000001556 precipitation Methods 0.000 claims description 21
- 238000006386 neutralization reaction Methods 0.000 claims description 20
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000004122 cyclic group Chemical group 0.000 claims description 14
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- 150000002367 halogens Chemical class 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims description 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 10
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 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 8
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- 239000002904 solvent Substances 0.000 claims description 8
- 150000003460 sulfonic acids Chemical class 0.000 claims description 8
- 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 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 6
- MCLXOMWIZZCOCA-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propan-1-amine Chemical compound CO[Si](C)(C)CCCN MCLXOMWIZZCOCA-UHFFFAOYSA-N 0.000 claims description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 5
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 5
- 239000004970 Chain extender Substances 0.000 claims description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
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- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 5
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
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- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
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- 229910052703 rhodium Inorganic materials 0.000 claims description 5
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
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- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 35
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- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- LYLDIIUFTYRPPK-UHFFFAOYSA-N 1h-imidazole-2-sulfonic acid Chemical compound OS(=O)(=O)C1=NC=CN1 LYLDIIUFTYRPPK-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- UFHBHNRBFWFTSP-UHFFFAOYSA-L disodium hydrogen peroxide sulfite Chemical compound [Na+].[Na+].OO.[O-]S([O-])=O UFHBHNRBFWFTSP-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-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
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
The invention provides a compound containing phosphorus, nitrogen and sulfonate, which has a structure shown in a formula (I). The compound has good water resistance and flame retardance, does not obviously cause the reduction of the mechanical property of the polymer composition when being added into the polymer composition as an additive, can obtain transparent or non-transparent flame-retardant polymer composition products according to the structure of a compound containing phosphorus, nitrogen and sulfonate groups and the change of preparation raw materials, and has lower addition amount. The phosphorus-containing, nitrogen-containing and sulfonate-containing compounds provided by the present invention have been proven to have excellent effects of increasing the flame retardancy of polymer compositions, particularly flame-retardant polymer compositions, and are particularly suitable for use inThe flame retardant is used for flame retardance of polycarbonate and alloy materials thereof, and has extremely high industrial application value in the field of polycarbonate flame retardance. The preparation route provided by the invention has the advantages of simple process, strong controllability, easily obtained raw materials and easy suitability for industrial production.
Description
Technical Field
The invention belongs to the field of polymer flame retardants, and relates to a phosphorus-containing, nitrogen-containing and sulfonate-containing compound, a preparation method thereof, and a flame-retardant polymer composition, in particular to a phosphorus-containing, nitrogen-containing and sulfonate-containing compound, a preparation method thereof, and application thereof in the field of polymer processing.
Background
Epoxy resin, engineering plastics, polyester and other high polymer materials have wide application, but most high polymer materials are not flame-retardant, and halogen-containing (such as bromine and chlorine) flame retardants are required to be added to enable the high polymer materials to have the functions of fire prevention and flame retardance. The high molecular material added with the halogen-containing flame retardant can release a large amount of harmful and toxic substances during combustion. In the years, the green and environment-friendly phosphorus-containing flame retardant and the nitrogen-containing flame retardant become the research direction of scientific workers, and in the phosphorus-containing flame retardant, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a hot research direction as a reactive phosphorus-containing flame retardant intermediate due to the P-H chemical bond. Triallyl cyanurate (TAC) is often used as a crosslinking agent for thermosetting resins or synthetic rubbers to improve heat resistance, hydrolysis resistance, and mechanical properties.
In recent years, environmental-friendly flame retardants containing phosphorus, nitrogen and sulfonate have been researched and reported. For example, US4962168 discloses that the addition reaction of DOPO with triallyl isocyanate (TAIC) and triallyl cyanurate (TAC) respectively can obtain a phosphorus-and nitrogen-containing flame retardant, which can be widely applied to thermosetting and thermoplastic resins, but when applied to Polycarbonate (PC) and its alloys, a satisfactory flame retardant effect can be obtained only with an addition amount of up to 8% by weight. Patent CN1156539C discloses a flame-retardant epoxy resin, which contains DOPO group in the resin structure, although the resin structure may contain sulfonic acid group, the sulfonic acid group is not described and explained in detail, and the application of the flame-retardant resin is limited to the field of flame retardation of epoxy resin. The research on synthesis of intumescent sulfonate flame retardant and flame retardant polycarbonate thereof (2014) and the research on preparation of nitrogen-phosphorus-sulfur compound flame retardant system and the application thereof in polycarbonate (2015) of the university Master thesis in China are realized by taking cyanuric chloride, sulfanilic acid or aminoethanesulfonic acid, potassium hydroxide and DOPO as raw materials to prepare the flame retardant containing phosphorus, nitrogen and sulfonate and P-H bonds, but the preparation process is complex, the obtained product is light yellow and has limitation in application, and in addition, the product is very easy to dissolve in water and poor in water resistance and is difficult to realize industrial application in the polycarbonate flame retardant material. Patent CN107652468B discloses an imidazole sulfonate ionic liquid flame retardant containing a DOPO structure, wherein the flame retardant is prepared by reacting DOPO and paraformaldehyde to obtain an intermediate I, then reacting with substituted sulfonyl chloride to obtain an intermediate II, and finally reacting with substituted imidazole to obtain a target product, but one reaction period of the preparation process at least needs 31 hours, the production efficiency is low due to long time consumption, the product yield is low, the flame retardant has a satisfactory flame retardant effect only by adding more than 7 wt% of flame retardant, and the combustion char formation property is poor. Patent CN108440598B discloses a preparation method and application of a sulfur-nitrogen-phosphorus composite flame retardant, which adopts maleic anhydride to react with 2, 2-thiobis (5-aminobenzenesulfonic acid), and then reacts with DOPO to produce a sulfur-nitrogen-phosphorus composite flame retardant containing DOPO and sulfonic acid structural units, but the 2, 2-thiobis (5-aminobenzenesulfonic acid) raw material used in the invention is difficult to buy in the market, and the price of the raw material 4, 4' -diaminodiphenyl sulfide required for synthesis is very expensive, so the sulfur-nitrogen-phosphorus composite flame retardant prepared by the method is only suitable for scientific research and difficult to be applied industrially. Patent CN110945066A discloses a flame retardant and plasticizers-sulfonate and sulfinate for plastics, the flame retardant or plasticizer is halogen-free nitrogen sulfonate alcohol and halogen-free nitrogen sulfinate alcohol ester, which react with imidazole ring-containing compound to obtain sulfonic acid ester-containing and nitrogen-containing flame retardant products, but when used as a flame retardant, the flame retardant cannot be used alone, and needs to be compounded with phosphorus-containing flame retardants such as phosphazenes and phosphates, and still needs to be added with more phosphorus-containing flame retardants to achieve satisfactory flame retardant effect.
Therefore, how to find a suitable compound containing phosphorus, nitrogen and sulfonate to make up for the deficiencies of water resistance and flame retardant property, and further widen the depth and width of the application thereof has become one of the focuses of many prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem solved by the present invention is to provide a phosphorus, nitrogen and sulfonate containing compound, a preparation method thereof and a flame retardant polymer composition, wherein the phosphorus, nitrogen and sulfonate containing compound provided by the present invention is used as a flame retardant for a polymer material, and has the advantages of good water resistance, excellent flame retardant property, and especially high industrial application value in the field of polycarbonate flame retardation.
The invention provides a compound containing phosphorus, nitrogen and sulfonate, which has a structure shown in a formula (I);
the R is2Each independently selected from-CH2-CH2＝CH-、-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-、-CH2-C(CH3) Is CH-or-CH2-CH2-O-c (O) -CH ═ CH-, and at least comprises-CH2-CH2-CH2-、CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-or-CH2-CH2-O-C(O)-CH2-CH2-；
The R is1Each independently is selected from H, a structure shown in a formula (II) or a formula (III), and at least one structure is selected from the structures shown in the formula (II) or the formula (III);
wherein a, b and c are the number of substituents and are selected from integers, and 8 is more than or equal to b and more than or equal to 1, 4 is more than or equal to a and more than or equal to 0, 4 is more than or equal to c and more than or equal to 7 is more than or equal to a + c and more than or equal to 0, and a + b + c is less than or equal to 8;
said M comprises a metal and/or, ammonia/amine compound;
the R is3、R4Each independently selected from one or more of halogen, nitryl, C1-C15 alkyl and C1-C15 alkoxy.
Preferably, the compound comprises a flame retardant;
the compound is a solid;
the M comprises one or more of alkali metal, alkaline earth metal and amino-containing silicon compound.
Preferably, said R is3And R4Can form a saturated or unsaturated cyclic ring;
the cyclic ring comprises an unsubstituted cyclic ring or a cyclic ring substituted by C1-C6 alkyl;
the mass percentage content of the S element in the compound is 0.0001-10%;
and b is 1.
The invention provides a preparation method of a compound containing phosphorus, nitrogen and sulfonate, which comprises the following steps:
1) carrying out sulfonation reaction on DOPO or a derivative thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown in a formula (IV) and/or a formula (V);
2) carrying out addition reaction on the compound containing phosphorus and sulfonic acid group obtained in the step and the compound containing carbon-carbon unsaturated group and nitrogen, and then carrying out neutralization or precipitation reaction on the compound and a metal compound and/or an ammonia/amine compound to obtain a compound containing phosphorus, nitrogen and sulfonic acid salt with a structure shown in a formula (I);
or:
1') carrying out sulfonation reaction on DOPO or derivatives thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown as a formula (IV) and/or a formula (V);
2') carrying out neutralization or precipitation reaction on the phosphorus-containing and sulfonic acid group-containing compound obtained in the step and a metal compound and/or an ammonia/amine compound, and then carrying out addition reaction on the phosphorus-containing and sulfonic acid group-containing compound and a nitrogen-containing compound containing a carbon-carbon unsaturated group to obtain a phosphorus-containing, nitrogen-containing and sulfonic acid salt-containing compound with a structure shown in a formula (I);
or:
1'), carrying out addition reaction on DOPO or derivatives thereof and a compound containing carbon-carbon unsaturated groups and nitrogen to obtain a phosphorus-containing and nitrogen-containing compound intermediate;
2'), carrying out sulfonation reaction on the intermediate containing phosphorus and nitrogen obtained in the step and a sulfonating agent, and then carrying out neutralization or precipitation reaction on the intermediate and a metal compound and/or an ammonia/amine compound to obtain a compound containing phosphorus, nitrogen and sulfonate and having a structure shown in a formula (I);
the R is2Each independently selected from-CH2-CH2＝CH-、-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-、-CH2-C(CH3) Is CH-or-CH2-CH2-O-c (O) -CH ═ CH-, and at least comprises-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-or-CH2-CH2-O-C(O)-CH2-CH2-；
The R is1Each independently is selected from H, a structure shown in a formula (II) or a formula (III), and at least one structure is selected from the structures shown in the formula (II) or the formula (III);
wherein a, b and c are the number of substituents and are selected from integers, and 8 is more than or equal to b and more than or equal to 1, 4 is more than or equal to a and more than or equal to 0, 4 is more than or equal to c and more than or equal to 7 is more than or equal to a + c and more than or equal to 0, and a + b + c is less than or equal to 8;
said M comprises a metal and/or, ammonia/amine compound;
the R is3、R4Each independently selected from one or more of halogen, nitryl, C1-C15 alkyl and C1-C15 alkoxy.
Preferably, the sulfonating agent comprises one or more of concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid and sulfur trioxide;
the temperature of the sulfonation reaction is 0-150 ℃;
the sulfonation reaction time is 0.5-10 h.
Preferably, the nitrogen-containing compound containing carbon-carbon unsaturated groups comprises one or more of triallyl isocyanate, trimethyolyl isocyanate, ethyl triacrylate isocyanate, diallyl isocyanate and monoallyl isocyanate;
the addition reaction comprises the addition reaction under the condition of an initiator and/or a catalyst;
the catalyst comprises one or more of a platinum catalyst, a rhodium catalyst, an iridium catalyst, a palladium catalyst and a ruthenium catalyst;
the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide and methyl ethyl ketone peroxide.
Preferably, the temperature of the addition reaction is 20-160 ℃;
the time of the addition reaction is 0.5-25 h;
the raw materials of the addition reaction also comprise an addition reaction solvent;
the addition reaction solvent comprises one or more of benzene, toluene, xylene, dichloromethane, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide.
Preferably, the metal compound includes a metal compound that ionizes a metal ion in a solvent;
the metal compound comprises one or more of alkali metal compound, alkaline earth metal compound, aluminum sulfate and aluminum nitrate;
the ammonia/amine compound comprises one or more of ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine and amino-silicon-containing compound;
the amino-containing silicon compound comprises one or more of aminopropyl dimethyl methoxysilane, aminopropyl methyl dimethoxysilane, aminopropyl triethoxysilane, aminopropyl methyl polysiloxane and aminopropyl methyl phenyl polysiloxane.
The invention also provides a flame-retardant polymer composition which comprises the phosphorus-containing, nitrogen-containing and sulfonate-containing compound in any one of the technical schemes or the phosphorus-containing, nitrogen-containing and sulfonate-containing compound prepared by the preparation method in any one of the technical schemes.
Preferably, the polymer matrix of the flame retardant polymer composition comprises one or more of polycarbonate, epoxy resin, polyphenylene oxide, polyalkylene terephthalate, vinyl polymer, polyalkylene, polyacrylate, polymethacrylate, polysulfone, polyamide, polyimide, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and silicone rubber;
the weight content of the phosphorus-containing, nitrogen-containing and sulfonate-containing compound in the polymer composition is 0.01-30%;
additives are also included in the polymer composition;
the additive comprises one or more of pigment, UV stabilizer, antioxidant, anti-dripping agent, heat stabilizer, reinforcing filler, chain extender, colorant and flexibilizer;
the phosphorus-containing, nitrogen-containing and sulfonate-containing compounds are used as flame retardants of polymer compositions, and other flame retardants or flame retardant systems are also included in the polymer compositions.
The invention provides a compound containing phosphorus, nitrogen and sulfonate, which has a structure shown in a formula (I). Compared with the prior art, the invention aims at solving the problems of narrow applicability, large addition amount, poor water resistance, insufficient flame retardant property and the like of the existing flame retardant for processing polymers. The compound containing phosphorus, nitrogen and sulfonate groups not only has good water resistance and flame retardance, but also can not obviously cause the reduction of the mechanical property of the polymer composition when being added into the polymer composition as an additive, and can obtain a transparent or non-transparent flame-retardant polymer composition product according to the structure of the compound containing phosphorus, nitrogen and sulfonate groups and the change of preparation raw materials. The phosphorus-, nitrogen-and sulfonate-containing compounds of the present invention have proven to have excellent effects on increasing the flame retardancy of polymer compositions, in particular flame retardant polymer compositions.
In the scientific research process, the research of the invention considers that 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof and a sulfonating agent are subjected to sulfonation reaction, then are subjected to addition reaction with a compound containing carbon-carbon unsaturated groups and nitrogen, and are subjected to neutralization or precipitation reaction with a metal compound and an ammonia/amine compound to obtain a compound containing phosphorus, nitrogen and sulfonate. The novel compound containing phosphorus, nitrogen and sulfonate is obtained by utilizing the characteristics that benzene ring in 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof can be sulfonated and P-H bond can be subjected to addition reaction with a compound containing carbon-carbon unsaturated group and nitrogen. The preparation route provided by the invention has the advantages of simple process, strong controllability, easily obtained raw materials and easy industrial production and application. The compound containing phosphorus, nitrogen and sulfonate provided by the invention not only has good water resistance, but also has excellent flame retardant property, not only can improve the flame retardant property of the polymer composition, but also can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, has lower addition amount, is proved to be particularly suitable for the flame retardant of polycarbonate and alloy materials thereof, and has extremely high industrial application value in the field of polycarbonate flame retardant.
Experimental results show that the phosphorus-containing, nitrogen-containing and sulfonate-containing compound provided by the invention not only has good water resistance, but also has excellent flame retardant property, not only can improve the flame retardant property of the polymer composition, but also can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, and the addition amount is lower.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs the purity of the conventional one used in the field of analytical purification or preparation of polymer flame retardants.
All noun expressions, acronyms and designations of the invention belong to the general noun expressions, acronyms and designations in the field, each noun expression, acronyms and designation is clear and definite in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expression, acronyms and designations.
The invention provides a compound containing phosphorus, nitrogen and sulfonate, which has a structure shown in a formula (I);
the R is2Each independently selected from-CH2-CH2＝CH-、-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-、-CH2-C(CH3) Is CH-or-CH2-CH2-O-c (O) -CH ═ CH-, and at least comprises-CH2-CH2-CH2-、CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-or-CH2-CH2-O-C(O)-CH2-CH2-；
The R is1Each independently is selected from H, a structure shown in a formula (II) or a formula (III), and at least one structure is selected from the structures shown in the formula (II) or the formula (III);
wherein a, b and c are the number of substituents and are selected from integers, and 8 is more than or equal to b and more than or equal to 1, 4 is more than or equal to a and more than or equal to 0, 4 is more than or equal to c and more than or equal to 7 is more than or equal to a + c and more than or equal to 0, and a + b + c is less than or equal to 8;
said M comprises a metal and/or, ammonia/amine compound;
the R is3、R4Each independently selected from one or more of halogen, nitryl, C1-C15 alkyl and C1-C15 alkoxy.
In the present invention, said R2Each independently selected from-CH2-CH2＝CH-、-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-、-CH2-C(CH3) Is CH-or-CH2-CH2-O-c (O) -CH ═ CH-, and at least one R2comprising-CH2-CH2-CH2-、CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-or-CH2-CH2-O-C(O)-CH2-CH2-one of the above.
In the present invention, the number of the substituents a, b and c is preferably an integer. Specifically, b is more than or equal to 8 and more than or equal to 1, and specifically can be 1, 2, 3, 4, 5, 6, 7 or 8. A is more than or equal to 4 and is more than or equal to 0, and specifically can be 0, 1, 2, 3 or 4. C is more than or equal to 4 and is more than or equal to 0, and can be 0, 1, 2, 3 or 4. The sum of a and c is more than or equal to 7 and more than or equal to 0, and can be specifically 0, 1, 2, 3, 4, 5, 6 or 7. The sum of a, b and c is less than or equal to 8, and can be 1, 2, 3, 4, 5, 6, 7 or 8. Among them, b is more preferably 1 or 2, and most preferably 1.
In the present invention, said M comprises a metal and/or an ammonia/amine compound, more preferably a metal or ammonia/amine compound group. In the present invention, the ammonia/amine compound represents an independent material name.
In the present invention, the M preferably includes one or more of an alkali metal, an alkaline earth metal and an amino-containing silicon compound, more preferably an alkali metal, an alkaline earth metal or an amino-containing silicon compound group, further preferably sodium and potassium, and most preferably potassium.
In the present invention, said R3、R4Each independently is preferably one or more selected from halogen, nitro, C1-C15 alkyl and C1-C15 alkoxy, more preferably halogen, nitro, C1-C15 alkyl or C1-C15 alkoxy. Specifically, the alkyl group of C1-C15 may be an alkyl group of C3-C12, an alkyl group of C5-C10, or an alkyl group of C7-C9. The alkoxy of C1-C15 can be C3-C12, or C5-C10, or C7-C9.
In the present invention, said R3And R4Preferably, a saturated or unsaturated cyclic ring can be formed. Namely R3And R4Preferably, a saturated ring structure or an unsaturated ring structure may be formed.
In the present invention, the cyclic ring preferably includes an unsubstituted cyclic ring or a cyclic ring substituted with an alkyl group having from C1 to C6. Specifically, the alkyl group having 1 to 6 may be an alkyl group having 2 to 5 carbon atoms or an alkyl group having 3 to 4 carbon atoms.
In the present invention, the content of the S element in the compound is preferably 0.0001% to 10%, more preferably 0.001% to 8%, more preferably 0.01% to 7%, more preferably 0.1% to 6%, and more preferably 1% to 5% by mass.
In the present invention, the state of the compound is preferably a solid.
In the present invention, the compound preferably includes a flame retardant.
The steps of the invention provide a compound containing phosphorus, nitrogen and sulfonate with a specific structure.
In the present invention, each of R is2Are independently of each other bound to the N atom.
In the present invention, H may be included in the definition of the monovalent form group.
Wherein each R is1Are independently of each other with R2A linked monovalent group. The R is1Selected from H and at least one structure represented by formula (II) or formula (III) through P atom and R2Are connected. Specifically, the R is1At least one R1Selected from the structures shown in formula (II) or formula (III), the structures are formed by P atoms and R2The structure of the formula (II) is more preferably contained.
In the present invention, the sulfonate (-SO) in the formula (II), the formula (III)3M) the S elements of the radical are independently linked to the carbon of the benzene ring. Wherein, the content of the sulfonate group cannot be too high, otherwise, the hydrophilicity or water solubility of the product of the invention can be greatly increased, the water resistance of the product is deteriorated, if the content is too low, the flame retardant property of the product is affected, and preferably, the S element accounts for 0.0001-10 percent, and more preferably 2-6 percent of the compound of the formula (I).
In the present invention, each of R is3，R4Are each, independently of one another, a monovalent radical which is bonded to a carbon atom on the phenyl ring and comprises H, halogen (F, Cl, Br, I), nitro, C1-C15 alkyl, C1-C15 alkoxy. And said R is3And R4Taken together, may form a saturated or unsaturated cyclic ring, wherein the saturated or unsaturated cyclic ring may be optionally substituted with a C1-C6 alkyl group.
The invention provides a preparation method of a compound containing phosphorus, nitrogen and sulfonate, which comprises the following steps:
1) carrying out sulfonation reaction on DOPO or a derivative thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown in a formula (IV) and/or a formula (V);
2) carrying out addition reaction on the compound containing phosphorus and sulfonic acid group obtained in the step and the compound containing carbon-carbon unsaturated group and nitrogen, and then carrying out neutralization or precipitation reaction on the compound and a metal compound and/or an ammonia/amine compound to obtain a compound containing phosphorus, nitrogen and sulfonic acid salt with a structure shown in a formula (I);
or:
1') carrying out sulfonation reaction on DOPO or derivatives thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown as a formula (IV) and/or a formula (V);
2') carrying out neutralization or precipitation reaction on the phosphorus-containing and sulfonic acid group-containing compound obtained in the step and a metal compound and/or an ammonia/amine compound, and then carrying out addition reaction on the phosphorus-containing and sulfonic acid group-containing compound and a nitrogen-containing compound containing a carbon-carbon unsaturated group to obtain a phosphorus-containing, nitrogen-containing and sulfonic acid salt-containing compound with a structure shown in a formula (I);
or:
1'), carrying out addition reaction on DOPO or derivatives thereof and a compound containing carbon-carbon unsaturated groups and nitrogen to obtain a phosphorus-containing and nitrogen-containing compound intermediate;
2'), carrying out sulfonation reaction on the intermediate containing phosphorus and nitrogen obtained in the step and a sulfonating agent, and then carrying out neutralization or precipitation reaction on the intermediate and a metal compound and/or an ammonia/amine compound to obtain a compound containing phosphorus, nitrogen and sulfonate and having a structure shown in a formula (I);
the R is2Each independently selected from-CH2-CH2＝CH-、-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-、-CH2-C(CH3) Is CH-or-CH2-CH2-O-c (O) -CH ═ CH-, and at least comprises-CH2-CH2-CH2-、CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-or-CH2-CH2-O-C(O)-CH2-CH2-；
The R is1Each independently is selected from H, a structure shown in a formula (II) or a formula (III), and at least one structure is selected from the structures shown in the formula (II) or the formula (III);
wherein a, b and c are the number of substituents and are selected from integers, and 8 is more than or equal to b and more than or equal to 1, 4 is more than or equal to a and more than or equal to 0, 4 is more than or equal to c and more than or equal to 7 is more than or equal to a + c and more than or equal to 0, and a + b + c is less than or equal to 8;
said M comprises a metal and/or, ammonia/amine compound;
the R is3、R4Each independently selected from one or more of halogen, nitryl, C1-C15 alkyl and C1-C15 alkoxy.
The invention provides a preparation method of a compound containing phosphorus, nitrogen and sulfonate, which comprises the following steps:
1) carrying out sulfonation reaction on DOPO or a derivative thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown in a formula (IV) and/or a formula (V);
2) and (2) carrying out addition reaction on the compound containing phosphorus and sulfonic acid group obtained in the step and the compound containing carbon-carbon unsaturated group and nitrogen, and then carrying out neutralization or precipitation reaction on the compound and a metal compound and/or an ammonia/amine compound to obtain the compound containing phosphorus, nitrogen and sulfonic acid with the structure shown in the formula (I).
Note that, in the present invention, DOPO or a derivative thereof represents an independent material name; the phosphorus-and sulfonic acid group-containing compounds represent independent material names; the nitrogen-containing compound containing a carbon-carbon unsaturated group represents an independent material name; metal compounds represent independent material names; ammonia/amine compounds represent independent material names; the phosphorus-, nitrogen-and sulfonate-containing compounds represent independent material names.
According to the invention, DOPO or a derivative thereof and a sulfonating agent are subjected to sulfonation reaction to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown in a formula (IV) and/or a formula (V).
In the present invention, the sulfonating agent preferably includes one or more of concentrated sulfuric acid, oleum, chlorosulfonic acid, and sulfur trioxide, more preferably concentrated sulfuric acid, oleum, chlorosulfonic acid, or sulfur trioxide.
In the invention, the temperature of the sulfonation reaction is preferably 0-150 ℃, more preferably 30-120 ℃, and more preferably 60-90 ℃.
In the invention, the sulfonation reaction time is preferably 0.5-10 h, more preferably 2-8 h, and more preferably 4-6 h. In the present invention, the time of the sulfonation reaction differs depending on the kind of the sulfonating agent and the reaction solvent.
The phosphorus-containing and sulfonic acid group-containing compound obtained in the step is subjected to addition reaction with a nitrogen-containing compound containing a carbon-carbon unsaturated group, and then subjected to neutralization or precipitation reaction with a metal compound and/or an ammonia/amine compound to obtain the phosphorus-containing, nitrogen-containing and sulfonic acid salt-containing compound with the structure shown in the formula (I).
In the present invention, the nitrogen-containing compound containing a carbon-carbon unsaturated group preferably includes one or more of triallyl isocyanate, trimethacrylic isocyanate, ethyl triacrylate isocyanate, diallyl isocyanate and monoallyl isocyanate, more preferably triallyl isocyanate (triallyl isocyanurate, TAIC), trimethacrylic isocyanate (TMAIC), ethyl triacrylate isocyanate (THEIAC), diallyl isocyanate (DAIC) or monoallyl isocyanate (MAIC), and most preferably triallyl isocyanate (TAIC).
In the present invention, the addition reaction preferably includes performing the addition reaction under the condition of an initiator and/or a catalyst, and more preferably, performing the addition reaction under the condition of an initiator or a catalyst.
In the present invention, the catalyst preferably includes one or more of a platinum-based catalyst, a rhodium-based catalyst, an iridium-based catalyst, a palladium-based catalyst, and a ruthenium-based catalyst, more preferably a platinum-based catalyst, a rhodium-based catalyst, an iridium-based catalyst, a palladium-based catalyst, or a ruthenium-based catalyst, and more preferably a platinum-based catalyst.
In the present invention, the initiator preferably includes one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide, and methyl ethyl ketone peroxide, and more preferably azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide, or methyl ethyl ketone peroxide.
In the invention, the temperature of the addition reaction is preferably 20-160 ℃, more preferably 50-130 ℃, and more preferably 80-100 ℃.
In the invention, the time of the addition reaction is preferably 0.5-25 h, more preferably 5-20 h, and more preferably 10-15 h.
In the present invention, the raw materials for the addition reaction preferably include an addition reaction solvent.
In the present invention, the addition reaction solvent preferably includes one or more of benzene, toluene, xylene, dichloromethane, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, and N, N-dimethylformamide, and more preferably benzene, toluene, xylene, dichloromethane, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, or N, N-dimethylformamide.
In the present invention, the metal compound preferably includes a metal compound that ionizes a metal ion in a solvent.
In the present invention, the metal compound preferably includes one or more of an alkali metal compound, an alkaline earth metal compound, aluminum sulfate, and aluminum nitrate, and more preferably an alkali metal compound, an alkaline earth metal compound, aluminum sulfate, or aluminum nitrate.
In the present invention, the ammonia/amine-based compound preferably includes one or more of ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine, and amino-containing silicon-based compound, and more preferably ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine, or amino-containing silicon-based compound.
In the present invention, the amino-containing silicon compound preferably includes one or more of aminopropyldimethylmethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethylpolysiloxane and aminopropylmethylphenylpolysiloxane, and more preferably aminopropyldimethylmethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethylpolysiloxane or aminopropylmethylphenylpolysiloxane.
The invention also provides a preparation method of the compound containing phosphorus, nitrogen and sulfonate, and the other two preparation routes comprise:
1') carrying out sulfonation reaction on DOPO or derivatives thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown as a formula (IV) and/or a formula (V);
2') carrying out neutralization or precipitation reaction on the phosphorus-containing and sulfonic acid group-containing compound obtained in the step and a metal compound and/or an ammonia/amine compound, and then carrying out addition reaction on the phosphorus-containing and sulfonic acid group-containing compound and a nitrogen-containing compound containing a carbon-carbon unsaturated group to obtain the phosphorus-containing, nitrogen-containing and sulfonic acid salt-containing compound with the structure shown in the formula (I).
Or:
1'), carrying out addition reaction on DOPO or derivatives thereof and a compound containing carbon-carbon unsaturated groups and nitrogen to obtain a phosphorus-containing and nitrogen-containing compound intermediate;
2'), carrying out sulfonation reaction on the intermediate containing phosphorus and nitrogen obtained in the step and a sulfonating agent, and then carrying out neutralization or precipitation reaction on the intermediate and a metal compound and/or an ammonia/amine compound to obtain the compound containing phosphorus, nitrogen and sulfonate and having the structure shown in the formula (I).
In the present invention, the raw material selection, the specific reaction process and the process parameters in the two preparation routes, and the corresponding preferred principles thereof, may correspond to the raw material selection, the specific reaction process and the process parameters in the first preparation route, and the corresponding preferred principles thereof one by one, and are not described in detail herein.
The invention is a complete and detailed integral technical scheme, better ensures the structure and performance of the compound containing phosphorus, nitrogen and sulfonate, further improves the comprehensive performance of the compound containing phosphorus, nitrogen and sulfonate, such as flame retardance, and the like, and the preparation method of the compound containing phosphorus, nitrogen and sulfonate can specifically comprise the following steps:
the compound of formula (I) of the present invention comprises the following preparation method:
(1) the compound is prepared by carrying out sulfonation reaction on 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof and a sulfonating agent to generate a compound containing phosphorus and sulfonic acid groups shown in a formula (IV) and/or a formula (V), then carrying out addition reaction on the compound containing carbon-carbon unsaturated groups and nitrogen, and finally carrying out neutralization or precipitation reaction on the compound and a metal compound and an ammonia/amine compound.
(2) The compound is prepared by carrying out sulfonation reaction on 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof and a sulfonating agent to generate a compound containing phosphorus and sulfonic acid groups shown in a formula (IV) and/or a formula (V), then carrying out neutralization or precipitation reaction on the compound and a metal compound and an ammonia/amine compound, and finally carrying out addition reaction on the compound and a compound containing carbon-carbon unsaturated groups and nitrogen.
(3) The compound is prepared by performing addition reaction on 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof and a compound containing carbon-carbon unsaturated groups and nitrogen to obtain a phosphorus-nitrogen compound intermediate, performing sulfonation reaction on the phosphorus-nitrogen compound intermediate and a sulfonating agent, and finally performing neutralization or precipitation reaction on the phosphorus-nitrogen compound intermediate and a metal compound and an ammonia/amine compound.
In the formula (IV) and the formula (V), each R3，R4And a, b, c are the same as described above.
In the present invention, the production methods (1) and (2) are preferred, and the production method (1) is more preferred.
The 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and the derivatives thereof, preferably DOPO, are disclosed.
The compounds of formula (IV) and formula (V) can be mutually transformed under certain conditions, and the structural transformation condition of the compounds is similar to that of DOPO and hydrolysis products thereof. For example, the compound of formula (IV) can be hydrolyzed into the compound of formula (V) under certain temperature and certain temperature, and the compound of formula (V) is dehydrated under certain temperature and pressure to be converted into the compound of formula (IV). Further preferred according to the invention are compounds of formula (IV).
The carbon-carbon unsaturated group-containing and nitrogen-containing compound is selected from the following compounds: triallyl isocyanate (TAIC), trimethyolyl isocyanate (TMAIC), ethyl triacrylate isocyanate (theac), diallyl isocyanate (DAIC), monoallyl isocyanate (MAIC), and TAIC is more preferable.
In the present invention, the sulfonation is one of the reaction means commonly used in industrial production, and reference is made to the technical manual of synthesis of fine organic unit reaction, which is compiled by Zhang kingdom.
In the present invention, there is no particular requirement for the selection of the sulfonating agent, such as sulfuric acid (concentrated) at a concentration of 93% or more, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, preferably concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, further preferably concentrated sulfuric acid, chlorosulfonic acid, and most preferably chlorosulfonic acid. In the present invention, there is no particular requirement on the sulfonation temperature, and the sulfonation temperature may be carried out at a temperature lower than 60 ℃ or higher than 120 ℃, and the temperature cannot be too low, otherwise the sulfonation reaction rate is affected, and too high a temperature may cause excessive sulfonation, oxidation, sulfone and resin formation and other side reactions, but allows the presence of partial oxidation, sulfone and resin in the phosphorus-, nitrogen-and sulfonate-containing compounds of the present invention. In the present invention, when concentrated sulfuric acid or fuming sulfuric acid is used as the sulfonating agent, water is also generated during the sulfonation reaction due to the water contained in the sulfonating agent, and the presence of water can hydrolyze part of DOPO and its derivatives completely or partially to produce the compounds represented by the formulae (IV) and (V), and mixtures thereof. The amount of sulfonating agent used is not particularly limited, and is preferably such that at least one sulfonic acid group is generated in one molecule of DOPO and its derivatives.
In the present invention, when the compounds represented by the above formulas (iv) and (v), and mixtures thereof are used as raw materials to perform addition reaction with the carbon-carbon containing unsaturated group and the nitrogen-containing compound, the reaction solvent is not particularly required, and may be optionally added or not added depending on the reaction system, for example, the reaction solvent is added: benzene, toluene, xylene, dichloromethane, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, and the like. It should be noted that, the compound containing both carbon-carbon unsaturated group and nitrogen has high solubility in general organic solvent, and no special organic solvent is needed, while the intermediate compound obtained by sulfonating and salifying DOPO and its derivative has low solubility in organic solvent, and the corresponding suitable reaction solvent can be selected according to the different compounds. In addition, if the reaction system has no water, the finally obtained flame retardant product is mainly the compound of the formula (I) containing the structure shown in the formula (II), and if the reaction system contains water, the proportion of the compounds of the formula (II) and the formula (III) in the obtained flame retardant product is adjusted according to the amount of the water and specific reaction conditions, generally, the compound containing the structure shown in the formula (III) has higher hydrophilicity or water solubility than the compound containing the structure shown in the formula (II), and the product containing the structure shown in the formula (II) is preferably contained in the invention.
In the present invention, there is no particular requirement for a catalyst or initiator for the addition reaction, such as: a platinum-based catalyst, a rhodium-based catalyst, an iridium-based catalyst, a palladium-based catalyst, or a ruthenium-based catalyst, preferably a platinum-based catalyst such as: fine platinum powder, platinum black, platinum chloride, chloroplatinic acid and chloroplatinic acid salts, alcohol-modified chloroplatinic acid, platinum-olefin complexes, platinum-alkenylsiloxane complexes, platinum-carbonyl complexes, etc., such initiators as azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, etc., preferably azobisisobutyronitrile, dibenzoyl peroxide, cumene hydroperoxide, potassium persulfate, sodium persulfate, ammonium persulfate, further preferably azobisisobutyronitrile, dibenzoyl peroxide, potassium persulfate, sodium persulfate, such as oxidation-reduction initiation systems, for example: hydrogen peroxide-sodium sulfite, cyclohexanone peroxide-cobalt naphthenate, and the like. Further, the reaction temperature is not particularly limited so as to catalyze or initiate the addition reaction of the P-H bond with the carbon-carbon unsaturated group in the present invention.
In the invention, compounds shown in the formulas (IV) and (V) and a mixture thereof are used as raw materials to perform addition reaction with a compound containing carbon-carbon unsaturated groups and nitrogen at the same time and a mixture thereof to obtain a compound intermediate containing phosphorus, nitrogen and sulfonic acid groups, the intermediate can be further separated, or the intermediate can not be extracted.
The metal compound, preferably a metal compound capable of ionizing a metal ion in a solvent, is selected from the group consisting of: alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium chloride and potassium chloride, alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, calcium chloride, barium chloride, magnesium chloride and magnesium nitrate, and divalent or higher metal ion compounds such as: aluminum sulfate, aluminum nitrate, and the like. The ammonia or amine compound may be, for example, ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine, or the like, or an amino-containing silicon compound such as aminopropyldimethylmethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethylpolysiloxane, aminopropylmethylphenylpolysiloxane, or the like. In the present invention, alkaline compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, aminopropyltriethoxysilane and the like are more preferable, and potassium hydroxide is more preferable.
In the present invention, the neutralization reaction refers to an acid-base neutralization reaction between a basic compound and a compound represented by formula (iv) or formula (v) of the present invention.
In the present invention, the precipitation reaction is specifically defined, and due to the differences of the metal compounds, ammonia or amine compounds, the compounds represented by formula (iv) and formula (v), and the content of S element in the sulfonate in the product, the physicochemical properties (such as thermal stability, water resistance, and whether the mechanical properties and transparency of the flame retardant material are affected) of the compound represented by formula (i) of the present invention and the solubility thereof in the reaction system are different, some products can be directly separated from the reaction system in a precipitation manner, sometimes the product needs to be separated from the reaction system in a crystallization or recrystallization manner, which is a method well known in the chemical industry.
According to the invention, the structure of the compound containing phosphorus, nitrogen and sulfonate shown in the formula (I) can be different according to the proportion of the raw materials which simultaneously contain carbon-carbon unsaturated groups and nitrogen-containing compounds, so as to obtain the reactive flame retardant product containing carbon-carbon unsaturated groups, phosphorus, nitrogen and sulfonate. The structure of the compound of formula (i) is not a single structure, any deletion of the structure or different combinations of synthetic raw materials, variations in the contents of metal elements and S elements (herein, generally referring to S element in sulfonate structure), etc., and the properties of the resulting compound of formula (i) in flame retardancy, water solubility, melting temperature, and mechanical properties and transparency of the resulting flame retardant material may also vary, and the present inventors describe and explain in detail in the following examples as much as possible, and it should be understood by those skilled in the art that the scope of the present invention is not limited to the examples of the present invention.
The invention provides a flame-retardant polymer composition, which comprises a phosphorus-containing, nitrogen-containing and sulfonate-containing compound in any one of the technical schemes or a phosphorus-containing, nitrogen-containing and sulfonate-containing compound prepared by the preparation method in any one of the technical schemes.
In the present invention, the polymer matrix of the flame retardant polymer composition preferably comprises one or more of polycarbonate, epoxy resin, polyphenylene oxide, polyalkylene terephthalate, vinyl polymer, polyolefin, polyacrylate, polymethacrylate, polysulfone, polyamide, polyimide, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer and silicone rubber, more preferably polycarbonate, epoxy resin, polyphenylene oxide, polyalkylene terephthalate, vinyl polymer, polyolefin, polyacrylate, polymethacrylate, polysulfone, polyamide, polyimide, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer or silicone rubber.
In the present invention, the content by weight of the phosphorus-containing, nitrogen-containing and sulfonate-containing compound in the polymer composition is preferably 0.01% to 30%, more preferably 0.1% to 10%, and still more preferably 0.1% to 6%.
In the present invention, additives are preferably included in the polymer composition.
In the present invention, the additive preferably includes one or more of a pigment, a UV stabilizer, an antioxidant, an anti-dripping agent, a heat stabilizer, a reinforcing filler, a chain extender, a colorant, and a toughening agent, and more preferably a pigment, a UV stabilizer, an antioxidant, an anti-dripping agent, a heat stabilizer, a reinforcing filler, a chain extender, a colorant, or a toughening agent.
In the present invention, the phosphorus-containing, nitrogen-containing and sulfonate-containing compounds are used as flame retardants for polymer compositions, which preferably include other flame retardants or flame retarding systems.
The present invention provides the above polymer composition comprising at least one polymer matrix in which the phosphorus-containing, nitrogen-containing, and sulfonate-containing compounds of the present invention are dispersed.
In the present invention, the polymer matrix is exemplified by, but not limited to: vinyl polymers such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyalkenes such as polyethylene, polypropylene, polyalkylene terephthalates such as polybutylene terephthalate, polyethylene terephthalate, polyacrylates such as polymethyl acrylate, polymethacrylates such as polymethyl methacrylate, polyphenylene ethers, polysulfones, polycarbonates, polystyrenes, in particular high-impact polystyrenes, polyamides such as nylon 6, nylon 66, polyimides, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, acrylonitrile-butadiene-styrene copolymer/polycarbonate blends, polystyrene/polyphenylene ether blends, thermoplastic polyester/polycarbonate blends such as butylene terephthalate/polycarbonate blends, silicone rubber, epoxy resin and mixtures thereof.
According to the invention, any conventional additive may be added to the polymer composition, such as: pigment, UV stabilizer, antioxidant, anti-dripping agent, heat stabilizer, reinforcing filler, chain extender, colorant, toughening agent and the like.
The polymer composition according to the invention preferably also contains a flame retardant, i.e. a polymer composition which is preferably flame retardant. The flame retardant polymer composition has improved processability, dispersibility, flame retardancy and mechanical properties. There is no particular limitation on the flame retardant, and any known flame retardant system for polymer compositions may be used. The flame retardants used in the polymer compositions can be used singly or in combination, for example, halogenated aromatic compounds, especially brominated compounds, and antimony oxide, which have a synergistic flame retardant effect.
Specifically, the polymer composition is extruded, injection molded, blow molded, vulcanized, etc. to obtain an article.
The polymer composition may be prepared by any known method of mixing the components. Generally, there are two distinct mixing steps: premixing and melt mixing. The premixing is to mix the dry components, and generally adopt a tumbler mixer or a ribbon blender for premixing, if necessary, a high shear mixer can be used for preparing the premix; after premixing, it is usually melt mixed. The components of the raw materials may also be added directly to the feed section of the melt mixing device without a premixing step. In melt mixing, the polymer composition components are typically melt blended in a single or twin screw extruder, extruded and cut into moldings, such as conventional pellets, granules, and the like, using standard techniques. The composition is then molded in any equipment conventionally used for molding, such as in an injection molding machine.
The compound containing phosphorus, nitrogen and sulfonate groups provided by the invention not only has good water resistance and flame retardance, but also can not obviously cause the reduction of the mechanical property of the polymer composition when being added into the polymer composition as an additive, and can obtain transparent or non-transparent flame-retardant polymer composition products according to the structure of the compound containing phosphorus, nitrogen and sulfonate groups and the change of preparation raw materials.
The phosphorus-, nitrogen-and sulfonate-containing compounds provided by the present invention have proven to be particularly useful for increasing the flame retardancy of polymer compositions, in particular flame retardant polymer compositions. The compound can improve the flame retardant property of the polymer composition, can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, has lower addition amount, and is proved to be particularly suitable for the flame retardant of polycarbonate and alloy materials thereof.
The invention provides a compound containing phosphorus, nitrogen and sulfonate, a preparation method thereof and application thereof in the field of polymer processing. The compound containing phosphorus, nitrogen and sulfonate groups has good water resistance and flame retardance, does not obviously cause the reduction of the mechanical property of a polymer composition when being added into the polymer composition as an additive, and can obtain a transparent or non-transparent flame-retardant polymer composition product according to the structure of the compound containing phosphorus, nitrogen and sulfonate groups and the change of preparation raw materials. The phosphorus-, nitrogen-and sulfonate-containing compounds of the present invention have proven to have excellent effects on increasing the flame retardancy of polymer compositions, in particular flame retardant polymer compositions.
The invention carries out sulfonation reaction on 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof and a sulfonating agent, then carries out addition reaction on the sulfonated DOPO and compounds containing carbon-carbon unsaturated groups and nitrogen, and then carries out neutralization or precipitation reaction on the sulfonated DOPO and compounds containing metal compounds and ammonia/amines to obtain compounds containing phosphorus, nitrogen and sulfonate. The novel compound containing phosphorus, nitrogen and sulfonate is obtained by utilizing the characteristics that benzene ring in 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof can be sulfonated and P-H bond can be subjected to addition reaction with a compound containing carbon-carbon unsaturated group and nitrogen. The preparation route provided by the invention has the advantages of simple process, strong controllability, easily obtained raw materials and easy industrial production and application. The compound containing phosphorus, nitrogen and sulfonate provided by the invention not only has good water resistance, but also has excellent flame retardant property, not only can improve the flame retardant property of the polymer composition, but also can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, has lower addition amount, is proved to be particularly suitable for the flame retardant of polycarbonate and alloy materials thereof, and has extremely high industrial application value in the field of polycarbonate flame retardant.
Experimental results show that the phosphorus-containing, nitrogen-containing and sulfonate-containing compound provided by the invention not only has good water resistance, but also has excellent flame retardant property, not only can improve the flame retardant property of the polymer composition, but also can prepare transparent or non-transparent polymer composition products according to different application occasions of the polymer composition, and the addition amount is lower.
In order to further illustrate the present invention, a phosphorus-containing, nitrogen-containing and sulfonate-containing compound, a method for preparing the same, and a flame retardant polymer composition according to the present invention are described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, the detailed embodiments and the specific procedures are given only for further illustrating the features and advantages of the present invention, and not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
In the invention, the content of the S element in the phosphorus, nitrogen and sulfonate-containing compound is measured by adopting an ultraviolet fluorescence sulfur detector (model WMTS-5000), the notch impact strength of the simply supported beam of the polymer composition is measured according to the ISO179 standard, the combustion test is carried out according to the method specified by the UL 94 standard, and the light transmittance is measured according to the ASTM D1003 standard.
Preparation of intermediate of phosphorus-containing and sulfonic acid group-containing compound shown in formula (IV)
Adding 21.62g of DOPO and 20.81g of chloroform into a reaction vessel with nitrogen protection, a thermometer, a reflux condenser tube, a constant pressure dropping funnel and mechanical stirring, stirring at room temperature for full dissolution, slowly dropping 12.82g of chlorosulfonic acid and 15g of chloroform mixture into the reaction vessel through the constant pressure dropping funnel at 5 ℃, controlling the reaction temperature not to exceed 60 ℃, after dropping is finished, reacting for 1h at 35 ℃, and finally removing chloroform and hydrogen chloride through reduced pressure extraction to obtain 35.68g of a phosphorus and sulfonic acid group-containing compound intermediate crystal, wherein the yield is 97%, and the weight ratio of DOPO: chlorosulfonic acid: the molar ratio of chloroform is 1: 1.1: 3.
example 1
Adding 7.41g (about 0.025mol) of the intermediate of the compound containing phosphorus and sulfonic acid groups and 20g of ethanol into a reaction vessel provided with nitrogen protection, a thermometer, a reflux condenser tube, a constant pressure dropping funnel and mechanical stirring, slowly dropping 2.28g (1: 1.1) of TAIC, 5g of ethanol and 0.1g of azodiisobutyronitrile mixture into the reaction vessel through the constant pressure dropping funnel at the reflux temperature, continuing to react for 5 hours after dropping, cooling to room temperature, slowly adding a mixed solution of potassium hydroxide and ethanol through the constant pressure dropping funnel, adjusting the pH of the reaction system to be neutral, reacting for 2.5 hours at 50 ℃, finally removing ethanol and water under reduced pressure to obtain 10.06g (theoretical 10.64g) of the solid of the compound containing phosphorus, nitrogen and sulfonic acid groups, wherein the yield is 95%, and the mass content of the S element is 6.9% by an element analyzer.
Example 2
Adding 7.41g (about 0.025mol) of intermediate of a compound containing phosphorus and sulfonic acid groups and 20g of ethanol into a reaction vessel provided with nitrogen protection, a thermometer, a reflux condenser tube, a constant pressure dropping funnel and mechanical stirring, slowly dropping 2.28g (1: 1.1) of TAIC, 20g of ethanol and 0.1g of azodiisobutyronitrile mixture into the reaction vessel through the constant pressure dropping funnel at the reflux temperature, continuing to react for 5 hours after dropping, cooling to room temperature, adding 3.75g (3.68g, 1: 1.02) of aminopropyl dimethylmethoxysilane, reacting for 2.5 hours at 50 ℃, and finally decompressing and removing the solvent to obtain 13.18g (theoretical 13.37g) of solid of the compound containing phosphorus, nitrogen and sulfonic acid groups, wherein the yield is 99%, and the mass content of the S element is 5.6% by an element analyzer.
Example 3
Adding 7.41g (about 0.025mol) of the intermediate of the compound containing the phosphorus and the sulfonic acid group and 20g of ethanol into a reaction vessel provided with nitrogen protection, a thermometer, a reflux condenser tube, a constant pressure dropping funnel and mechanical stirring, slowly dropping 2.28g (1: 1.1) of TAIC, 20g of ethanol and 0.1g of azodiisobutyronitrile mixture into the reaction vessel through the constant pressure dropping funnel at the reflux temperature, continuing to react for 5 hours after dropping, cooling to room temperature, adding an ethanol solution containing about 1.39g of calcium chloride, reacting for 2 hours at 50 ℃, and finally removing the solvent and low-boiling substances under reduced pressure to obtain 9.98g (theoretical 10.17g) of the compound containing the phosphorus, the nitrogen and the sulfonic acid group, wherein the yield is 98%, and the mass content of the S element is 7.6% by an element analyzer.
Comparative example 1
Adding 108 g DOPO and 30 g dimethylacetamide into a 500ml three-necked bottle provided with a sample adding pipe, a thermometer, a condenser and a nitrogen protection device, introducing nitrogen, stirring and heating to 150 ℃, uniformly mixing 42.5 g TAIC and 1.8g benzoyl peroxide through the sample adding pipe, slowly adding into the three-necked bottle for 6 hours, and after the reaction is finished, evaporating the solvent to obtain 143.26 with the yield of 95%.
Comparative example 2
18.40g (0.1mol) of cyanuric chloride was charged into a four-necked flask containing 100mL of acetone, and the system was maintained at 0 to 3 ℃ and stirred to be sufficiently dissolved. 13.78g (0.11mol) of aminoethanesulfonic acid, 6.16g (0.11mol) of potassium hydroxide were dissolved in 100mL of water, and then added slowly to a solution of cyanuric chloride in acetone. In the reaction process, the pH value of the reaction system is adjusted by using a potassium hydroxide aqueous solution with the concentration of 1mol/L, so that the pH value of the system is maintained at 8-9, and the reaction is carried out for 3 hours. After the reaction, the reaction mixture was filtered, and the filter cake was washed with acetone (50 mL. times.3) and ice water (50 mL. times.2), and dried at room temperature to obtain TCT-S as a white solid.
Adding 10.83g (0.05mol) of DOPO into a four-neck flask filled with 50mL of deionized water, heating to 75 ℃, reacting for 4 hours to fully hydrolyze the DOPO, adding 6.00g (0.06mol) of potassium bicarbonate, adding 1mol/L hydrochloric acid to neutralize to be neutral after the solution is clarified. The solvent was removed by rotary evaporator and dried at 80 ℃ for 6h to give HAPP-K as a white powder.
Adding 5.45g (0.02mol) of HAPP-K into a four-neck flask filled with 100mL of deionized water, dissolving 3.11g (0.01mol) of TCT-S in 100mL of deionized water, slowly dripping an aqueous solution of TCT-S into the aqueous solution of HAPP-K by using a constant-pressure dropping funnel, maintaining the temperature of the system at about 45 ℃, and adjusting the pH value of the reaction system to 9-10 by using a 1mol/L KOH aqueous solution in the reaction process. When the pH value of the reaction system is not changed any more, gradually raising the temperature of the system to 90 ℃, and adjusting the pH value of the reaction system to 9-10 by using a KOH aqueous solution with the concentration of 1mol/L in the reaction process. When the temperature of the system is not changed any more, the reaction is stopped, the hot reaction solution is filtered by suction, and the filtrate is concentrated and dried in a vacuum drying oven to obtain light yellow solid. The obtained pale yellow solid was dissolved in anhydrous methanol, insoluble matter was removed by filtration, ethyl acetate of 4 times the volume of the methanol solution was slowly added to the methanol solution while stirring, the mixture was left to stand for 15 minutes, then, suction filtration was carried out under reduced pressure, the cake was washed with ethyl acetate (50 mL. times.3), and the cake was dried and crushed to obtain 5.90g of NPS-K as a white solid powder.
Example 4
5g of each of examples 1, 2 and 3 was put into 10g of water at room temperature and 100 ℃ and stirred for 1 minute, whereby example 1 was partially dissolved and examples 2 and 3 were almost not dissolved.
5g of samples of comparative examples 1 and 2 in the background art are respectively put into 10g of water at room temperature and 100 ℃ and stirred for 1 minute, and the samples of comparative example 1 are not dissolved, and the samples of comparative example 2 are all dissolved.
5g of KSS and FR-2025 sulfonate flame retardants widely used in the market are respectively put into 10g of water at room temperature and 100 ℃, stirred for 1 minute and completely dissolved.
Therefore, compared with KSS and FR-2025 flame retardants widely used in the market and phosphorus-containing, nitrogen-containing and sulfonate compounds under the comparative technology, the phosphorus-containing, nitrogen-containing and sulfonate compounds provided by the invention have better water solubility resistance.
Examples 5 to 7 and comparative examples 3 to 7
The phosphorus-containing, nitrogen-containing and sulfonate compound prepared in the embodiment 1-3 of the invention and the compound prepared in the comparative example 1-2 are used as flame retardants, and then are compared and detected with common flame retardants and flame-retardant matrixes.
Mixing the corresponding components by a mixer, confirming the uniform mixing, extruding and granulating by using a double-screw extruder, injecting the obtained granules into a required standard sample strip by an injection molding machine, and finally carrying out relevant standard tests. The PC was dried at 120 ℃ for 4h before use. The length-diameter ratio of the used double-screw extruder is 40, and the double-screw extruder is provided with accurate temperature control and vacuum exhaust equipment, the rotating speed of the screw is 100-700 r/min, and the extrusion working temperature is as follows: the first zone is 230-260 ℃, the second zone is 230-270 ℃, the third zone is 230-270 ℃, the fourth zone is 240-280 ℃, and the retention time is 1-2 minutes. The light transmittance (80 mm by 40mm by 3.2mm thick plaques were formed according to ASTM D1003), the flame retardant properties of the prepared polymer compositions and the flame retardant properties of the polymer composition plaques after boiling water for 1 hour.
Referring to Table 1, Table 1 shows the formulations and performance data for the polymer compositions prepared in examples 5-7 of the present invention and comparative examples 3-7.
TABLE 1
In examples 5 to 7 and comparative examples 3 to 7, polymer compositions of Polycarbonate (PC) (from SABIC), ABS (from Qimei), phosphorus-containing, nitrogen-containing, and sulfonate compound of the present invention, KSS, phosphorus-containing, nitrogen-containing, and sulfonate compound of the comparative examples, and phosphorus-containing and nitrogen-containing compound, as shown in Table 1, were prepared.
According to the test results in table 1, the flame retardant containing phosphorus, nitrogen and sulfonate compounds of the present invention can prepare V0 flame retardant suitable for transparent PC or natural color non-transparent PC according to the different kinds of sulfonate introduced, such as PC with high light transmittance for flame retardant of the products of examples 1 and 2, and example 3 is more suitable for flame retardant of natural color non-transparent PC. Due to the synergistic flame retardant effect of phosphorus, nitrogen and sulfonate, the product of the invention has better flame retardant effect under the condition of the same addition amount, and due to the introduction of different sulfonate structures, the prepared flame retardant polymer composition has better water precipitation resistance and flame retardant durability.
The foregoing detailed description of a phosphorus, nitrogen and sulfonate containing compound of the present invention, and the preparation and use thereof in the polymer processing field, and the specific examples used herein to describe the principles and embodiments of the present invention, are presented solely to aid in the understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A compound containing phosphorus, nitrogen and sulfonate is characterized by having a structure shown in a formula (I);
the R is2Each independently selected from-CH2-CH2＝CH-、-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-、-CH2-C(CH3) Is CH-or-CH2-CH2-O-c (O) -CH ═ CH-, and at least comprises-CH2-CH2-CH2-、CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-or-CH2-CH2-O-C(O)-CH2-CH2-；
The R is1Each independently is selected from H, a structure shown in a formula (II) or a structure shown in a formula (III), and at least one structure is selected from the structures shown in the formula (II) or the formula (III);
wherein a, b and c are the number of substituents and are selected from integers, and 8 is more than or equal to b and more than or equal to 1, 4 is more than or equal to a and more than or equal to 0, 4 is more than or equal to c and more than or equal to 7 is more than or equal to a + c and more than or equal to 0, and a + b + c is less than or equal to 8;
said M comprises a metal and/or, ammonia/amine compound;
the R is3、R4Each independently selected from one or more of halogen, nitryl, C1-C15 alkyl and C1-C15 alkoxy.
2. The compound of claim 1, wherein the compound comprises a flame retardant;
the compound is a solid;
the M comprises one or more of alkali metal, alkaline earth metal and amino-containing silicon compound.
3. A compound of claim 1, wherein R is3And R4Can form a saturated or unsaturated cyclic ring;
the cyclic ring comprises an unsubstituted cyclic ring or a cyclic ring substituted by C1-C6 alkyl;
the mass percentage content of the S element in the compound is 0.0001-10%;
and b is 1.
4. A method for preparing a compound containing phosphorus, nitrogen and sulfonate is characterized by comprising the following steps:
1) carrying out sulfonation reaction on DOPO or a derivative thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown in a formula (IV) and/or a formula (V);
2) carrying out addition reaction on the compound containing phosphorus and sulfonic acid group obtained in the step and the compound containing carbon-carbon unsaturated group and nitrogen, and then carrying out neutralization or precipitation reaction on the compound and a metal compound and/or an ammonia/amine compound to obtain a compound containing phosphorus, nitrogen and sulfonic acid salt with a structure shown in a formula (I);
or:
1') carrying out sulfonation reaction on DOPO or derivatives thereof and a sulfonating agent to obtain a phosphorus-containing and sulfonic acid group-containing compound with a structure shown as a formula (IV) and/or a formula (V);
2') carrying out neutralization or precipitation reaction on the phosphorus-containing and sulfonic acid group-containing compound obtained in the step and a metal compound and/or an ammonia/amine compound, and then carrying out addition reaction on the phosphorus-containing and sulfonic acid group-containing compound and a nitrogen-containing compound containing a carbon-carbon unsaturated group to obtain a phosphorus-containing, nitrogen-containing and sulfonic acid salt-containing compound with a structure shown in a formula (I);
or:
1'), carrying out addition reaction on DOPO or derivatives thereof and a compound containing carbon-carbon unsaturated groups and nitrogen to obtain a phosphorus-containing and nitrogen-containing compound intermediate;
2'), carrying out sulfonation reaction on the intermediate containing phosphorus and nitrogen obtained in the step and a sulfonating agent, and then carrying out neutralization or precipitation reaction on the intermediate and a metal compound and/or an ammonia/amine compound to obtain a compound containing phosphorus, nitrogen and sulfonate and having a structure shown in a formula (I);
the R is2Each independently selected from-CH2-CH2＝CH-、-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-、-CH2-C(CH3) Is CH-or-CH2-CH2-O-c (O) -CH ═ CH-, and at least comprises-CH2-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH(CH3)-CH2-or-CH2-CH2-O-C(O)-CH2-CH2-；
The R is1Each independently is selected from H, a structure shown in a formula (II) or a structure shown in a formula (III), and at least one structure is selected from the structures shown in the formula (II) or the formula (III);
wherein a, b and c are the number of substituents and are selected from integers, and 8 is more than or equal to b and more than or equal to 1, 4 is more than or equal to a and more than or equal to 0, 4 is more than or equal to c and more than or equal to 7 is more than or equal to a + c and more than or equal to 0, and a + b + c is less than or equal to 8;
said M comprises a metal and/or, ammonia/amine compound;
the R is3、R4Each independently selected from one or more of halogen, nitryl, C1-C15 alkyl and C1-C15 alkoxy.
5. The method of claim 4, wherein the sulfonating agent comprises one or more of concentrated sulfuric acid, oleum, chlorosulfonic acid, and sulfur trioxide;
the temperature of the sulfonation reaction is 0-150 ℃;
the sulfonation reaction time is 0.5-10 h.
6. The method according to claim 4, wherein the compound containing carbon-carbon unsaturated group and nitrogen includes one or more of triallyl isocyanate, trimethallyl isocyanate, ethyl triacrylate isocyanate, diallyl isocyanate and monoallyl isocyanate;
the addition reaction comprises the addition reaction under the condition of an initiator and/or a catalyst;
the catalyst comprises one or more of a platinum catalyst, a rhodium catalyst, an iridium catalyst, a palladium catalyst and a ruthenium catalyst;
the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide and methyl ethyl ketone peroxide.
7. The preparation method according to claim 4, wherein the temperature of the addition reaction is 20-160 ℃;
the time of the addition reaction is 0.5-25 h;
the raw materials of the addition reaction also comprise an addition reaction solvent;
the addition reaction solvent comprises one or more of benzene, toluene, xylene, dichloromethane, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide.
8. The production method according to claim 4, wherein the metal compound comprises a metal compound that ionizes a metal ion in a solvent;
the metal compound comprises one or more of alkali metal compound, alkaline earth metal compound, aluminum sulfate and aluminum nitrate;
the ammonia/amine compound comprises one or more of ammonia, aliphatic ammonia, aromatic amine, substituted aliphatic amine, substituted aromatic amine and amino-silicon-containing compound;
the amino-containing silicon compound comprises one or more of aminopropyl dimethyl methoxysilane, aminopropyl methyl dimethoxysilane, aminopropyl triethoxysilane, aminopropyl methyl polysiloxane and aminopropyl methyl phenyl polysiloxane.
9. A flame retardant polymer composition comprising the phosphorus, nitrogen and sulfonate containing compound according to any one of claims 1 to 3 or the phosphorus, nitrogen and sulfonate containing compound prepared by the preparation method according to any one of claims 4 to 8.
10. The flame retardant polymer composition of claim 9 wherein the polymer matrix of the flame retardant polymer composition comprises one or more of polycarbonate, epoxy resin, polyphenylene ether, polyalkylene terephthalate, vinyl polymer, polyalkylene, polyacrylate, polymethacrylate, polysulfone, polyamide, polyimide, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and silicone rubber;
the weight content of the phosphorus-containing, nitrogen-containing and sulfonate-containing compound in the polymer composition is 0.01-30%;
additives are also included in the polymer composition;
the additive comprises one or more of pigment, UV stabilizer, antioxidant, anti-dripping agent, heat stabilizer, reinforcing filler, chain extender, colorant and flexibilizer;
the phosphorus-containing, nitrogen-containing and sulfonate-containing compounds are used as flame retardants of polymer compositions, and other flame retardants or flame retardant systems are also included in the polymer compositions.
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