WO2014008617A1 - 一种烷基次膦酸盐聚合物及其制备方法和应用 - Google Patents
一种烷基次膦酸盐聚合物及其制备方法和应用 Download PDFInfo
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- WO2014008617A1 WO2014008617A1 PCT/CN2012/000989 CN2012000989W WO2014008617A1 WO 2014008617 A1 WO2014008617 A1 WO 2014008617A1 CN 2012000989 W CN2012000989 W CN 2012000989W WO 2014008617 A1 WO2014008617 A1 WO 2014008617A1
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- Prior art keywords
- polymer
- acid
- flame retardant
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- compound
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- -1 Alkyl phosphinate Chemical compound 0.000 title claims abstract description 102
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 239000003063 flame retardant Substances 0.000 claims abstract description 71
- 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 67
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 21
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 15
- 239000002585 base Substances 0.000 claims abstract description 14
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 10
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- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 6
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims abstract description 6
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 6
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 6
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims abstract description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims abstract description 5
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- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 14
- 150000003254 radicals Chemical class 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 10
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- 230000000996 additive effect Effects 0.000 claims description 9
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 8
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- 125000003118 aryl group Chemical group 0.000 claims description 6
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- 229910052700 potassium Inorganic materials 0.000 claims description 6
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- 230000008018 melting Effects 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 claims description 4
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- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
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- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical group NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 claims description 4
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- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 4
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
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- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims description 3
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 claims description 3
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 229940043430 calcium compound Drugs 0.000 claims description 3
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- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001177 diphosphate Substances 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
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- AZCYBBHXCQYWTO-UHFFFAOYSA-N 2-[(2-chloro-6-fluorophenyl)methoxy]benzaldehyde Chemical compound FC1=CC=CC(Cl)=C1COC1=CC=CC=C1C=O AZCYBBHXCQYWTO-UHFFFAOYSA-N 0.000 claims description 2
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- BUZAHHWYIYJFDZ-UHFFFAOYSA-N NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(=O)OP(O)(O)=O Chemical compound NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(=O)OP(O)(O)=O BUZAHHWYIYJFDZ-UHFFFAOYSA-N 0.000 claims description 2
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- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 claims description 2
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- FDJZNXLKZOXHPN-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O FDJZNXLKZOXHPN-UHFFFAOYSA-N 0.000 claims description 2
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
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- YMAWOPBAYDPSLA-UHFFFAOYSA-N glycine anhydride Natural products [NH3+]CC(=O)NCC([O-])=O YMAWOPBAYDPSLA-UHFFFAOYSA-N 0.000 claims description 2
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
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- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
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- NFVUAUVSFDFOJT-UHFFFAOYSA-N octanediamide Chemical compound NC(=O)CCCCCCC(N)=O NFVUAUVSFDFOJT-UHFFFAOYSA-N 0.000 claims description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical group OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 2
- QVJYHZQHDMNONA-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 QVJYHZQHDMNONA-UHFFFAOYSA-N 0.000 claims description 2
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
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- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-M diphenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-M 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 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
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- IPOBMWQSKXACEW-UHFFFAOYSA-N tetradecylurea Chemical compound CCCCCCCCCCCCCCNC(N)=O IPOBMWQSKXACEW-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003582 thiophosphoric acids Chemical group 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
Definitions
- the present invention relates to an alkyl phosphinate polymer, and more particularly to an alkyl phosphinate polymer and a process for the preparation thereof and use thereof.
- Background Art The flame retardant properties of polyester or nylon can be obtained by incorporating various types of additives.
- halogenated compounds particularly polybrominated aromatic compounds, have been used as flame retardant additives in such polymers. It is generally believed that when these products are ignited, the product inhibits the free radical gas phase reaction that occurs in the flame. This makes halogenated flame retardants very commonly used as additives for different types of polymer materials including polyester and nylon.
- halogenated flame retardants have been monitored for ecological care.
- Phosphorus-containing products are a logical alternative to this type of halogenated flame retardant.
- phosphorus-containing additives exhibit as high activity as halogenated flame retardants, but monument-containing additives are often seldom used.
- Most of the phosphorus-containing flame retardants provide flame retardant activity by a combination of a condensed phase reaction, a polymerized carbonization promotion, and a char formation. These methods are clearly dependent on the polymer in which the additive is used. Therefore, specific phosphorus-containing structures need to be designed for a variety of polymer types.
- this polymeric phosphinate is extremely acidic and increases with increasing polymerization. If it is added as a flame retardant to other polymer materials, strong acidity will greatly damage the mechanical properties of the material. . It cannot be applied. Obviously, if applied as a flame retardant, it must be a polymeric phosphinate with a low degree of polymerization.
- alkyl hypophosphite polymer proposed by the invention has the following structural formula: Wherein: fluorenyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, hydroxydecyl or alkoxy Any of them;
- R 2 is decyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, hydroxydecyl or alkoxy Any of them;
- Re is any one of an alkali metal, an alkaline earth metal, a transition metal, a metal-poor, a metalloid, a lanthanide or a protonated nitrogen base.
- Re is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, La, Bi, Sr, Mn, Li, Na, K, preferably Re is Al, Ca, Ti, Any of Zn, Sn, Zr, and La.
- the protonated nitrogen base is a proton base containing a nitrogen atom of a lone pair of electrons, preferably ammonia, melamine, triethanolamine, especially ⁇ 4 ' melamine, urea, biuret, hydrazine, dodecyl Anthraquinone, allantoin, decylamine acetate, benzoguanamine, fluorenylphenyltriazole, benzotriazole, 2-amino-4-mercaptopyrimidine, benzyl urea, acetylene urea, hydantoin, propane Amide oxime, dimercaptourea, diphenyl hydrazine, 5,5-diphenylhydantoin, hydrazine, hydrazine, -diphenylurea, glycine anhydride, tetradecylurea, and corresponding polymers, for example A melamine condensate such as mele, mel
- u is the average degree of polymerization, u is 1.2-6, preferably u is 2-5. It is determined by the ratio of the molecular weight regulator to the hypophosphorous or alkali metal hypophosphite salt when preparing the polymer.
- the preparation method of the alkyl phosphinate polymer proposed by the invention has the following specific steps:
- hypophosphorous acid or an alkali metal hypophosphite a molecular weight regulator and a polar solvent into a reactor of adjustable pressure, heating the mixture to 90-110 under normal pressure, and introducing the alkyne at a pressure of 3 bar.
- Hydrocarbon is added to the reaction vessel to achieve gas saturation; wherein: the polar solvent and the Shield (ie, the sum of the weight of the hypophosphorous acid or alkali metal hypophosphite and the molecular weight regulator) have a weight OHPI ratio of 4.0 to 6.0, and the molecular weight regulator
- the molar ratio with hypophosphorous acid or alkali metal hypophosphite is 0.4 ⁇ 9.0;
- the radical initiator is 0.5 to 13% by weight of the hypophosphorous or hypophosphorous alkali metallate, and the amount of the metal compound or protonated nitrogen base added (molar number) is the number of moles of hypophosphorous acid or alkali metal hypophosphite divided by m.
- m is the valence of the cation in the metal cation or protonated nitrogen base in the compound.
- the metal compound is a compound of an alkali metal, an alkaline earth metal, a transition metal, a metal-poor, a metalloid, or a lanthanide.
- the radical initiator solution means that the radical initiator is dissolved by a polar solvent, and the amount of the polar solvent is not limited enough to completely dissolve the radical initiator.
- the polar solvent which dissolves the hypophosphorous acid or alkali metal hypophosphite, the molecular weight modifier, and the radical initiator is water, a carboxylic acid, or an alcohol. More preferably, the polar solvent is water or acetic acid.
- the alkali metal, alkaline earth metal, transition metal, metal-deficient, metalloid, lanthanide compound is an oxide, a hydroxide, a hydroxide oxide, a sulfate, an acetate, a nitrate, a chloride or an alcohol Any of them.
- the alkali metal is Li, Na, K
- the alkaline earth metal is Mg, Ca, Sr
- the transition metal is Ti, Fe, Zr, Zn, Mn
- the lean metal is Al.
- Sn, Bi the metalloid is Sb, Ge
- the lanthanoid element is Ce, La.
- Li, Na, K, Mg, Ca, Sr, Ti, Fe, Zr, Zn, Mn, Al, Sn, Bi, Sb, Ge, Ce, La compounds are oxides, hydroxides, hydroxides Any of oxides, sulfates, acetates, nitrates, chlorides or alcoholates.
- the alkyne in the step (1) is acetylene.
- the molecular weight regulator structure in the step (1) conforms to the following formula: among them:
- R 2 is a C r C 6 alkyl group, an aryl group, dC 6 alkoxy group, a phenoxy group, dC 6 hydroxyalkyl group, a hydroxyl group, a hydroxyl group, sodium;
- c r c 6 alkoxy group c r c 6 hydroxyalkyl group, hydroxyl group or sodium hydroxy group.
- it is an indenyl group and is a mercapto group, a hydroxyl group; an ethyl group and R 2 is an ethyl group or a hydroxyl group; a phenoxy group and a phenoxy group; a neopentyl glycol ester group and R 2 is neopentyl glycol Ester group; or one of them is a hydroxymethyl group.
- the radical initiator in the step (2) is an azo compound
- the azo compound is a cation, an azo compound, a non-cationic azo compound, an inorganic peroxide free radical initiator or an organic peroxidation. Any of the free radical initiators.
- the cationic azo compound is 2,2-azobis(2-mercaptopropyl fluorene) dihydrochloride (or V50), and the non-cationic azo compound is diisobutyl phthalate, 4 , 4-azobis(4-cyanovaleric acid) or 2,2,-azobis(2-mercaptobutylene), the inorganic peroxide free radical initiator using hydrogen peroxide, peroxodisulfuric acid Ammonium, sodium peroxodisulfate or potassium peroxydisulfate, the organic peroxide free radical initiator is dibenzoyl peroxide, di-tert-butyl peroxide or peracetic acid.
- the use of the alkyl phosphinate polymers proposed by the present invention as flame retardants, flame retardant compositions and flame retardant polymer molding compositions is as follows: adding an additive to an alkyl phosphinate polymer to obtain a flame retardant composition, wherein: The phosphonate polymer is added in an amount of 70 wt% to 95 wt%, and the additive is added in an amount of 5 wt% to 30 wt%.
- the resulting flame retardant composition has an average particle size of from 0.1 to 3000 ⁇ m, preferably from 0.1 to 1000 ⁇ m, further from 1 to 100 ⁇ m.
- the additive is melamine phosphate, dimelamine phosphate, penta-melamine triphosphate, trimelamine diphosphate, tetramelamine triphosphate, hexaamine pentaphosphate, melamine II Phosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate or melamine polyphosphate, zinc compound, magnesium compound, Any of a calcium compound, an aluminum compound, a manganese compound, a tin compound, or a carbodiimide or a (poly)isocyanate.
- it is an oligomeric ester of tris(hydroxyethyl)isocyanurate with an aromatic polycarboxylic acid, benzoguanamine, tris(hydroxyethyl)isourethane, urinary guanidine, glycoluril Any of melamine, melamine cyanurate, urea cyanurate, dicyandiamide or hydrazine.
- the carbodiimide such as carbonyl dicaprolactone; the magnesium compound such as magnesium oxide, magnesium hydroxide, hydrotalcite, dihydrate, magnesium carbonate or calcium magnesium carbonate; the hook compound such as calcium hydroxide, oxidation Calcium, hydrocalumite; the zinc compound such as zinc oxide (such as active zinc oxide), zinc hydroxide, hydrated zinc oxide, zinc carbonate (such as alkaline zinc carbonate, zinc-free acid), zinc stannate, hydroxystannic acid Zinc, alkaline zinc silicate, alkaline zinc phosphate, basic zinc borate, basic zinc molybdate, or basic zinc sulfide; the aluminum compound such as alumina, aluminum hydroxide, hydrous aluminum oxide, or aluminum phosphate; The manganese compound such as manganese oxide, manganese hydroxide; the tin compound such as tin oxide.
- the magnesium compound such as magnesium oxide, magnesium hydroxide, hydrotalcite, dihydrate, magnesium carbonate or calcium magnesium carbonate
- the hook compound such as calcium hydro
- the application of the flame-retardant polymer molding composition proposed by the invention is as follows: The alkyl phosphinate polymer, the polymer and the additive are mixed in a mixer and melted in a compounding device at a certain temperature. Uniformly, the resulting product is extruded and cooled to obtain the desired product.
- the polymer is a polyamide and a copolyamide derived from a diamine and a dicarboxylic acid, and/or an aminocarboxylic acid, or a corresponding lactam, such as polyamide 2,12, polyamide 4 (poly 4- Aminobutyric acid), polyamide 4,6 (poly(tetradecylene adipamide)), polyamide 6 (polycaprolactam, poly 6-aminocaproic acid), polyamide 6,6 (poly( ⁇ , ⁇ , -hexamethylene adipamide)), polyamide 6,9 (poly(hexamethylene decanoate)), polyamide 6,10 (poly(hexamethylene sebacamide)), poly Amide 6,12 (poly(hexamethylene decyldodecanamide)), polyamide 6/6,6 (poly(hexamethylene hexanoamide-co-caprolactam)), polyamide 7 (poly 7-J ⁇ ) Heptanoic acid), polyamide 7,7 (poly 4- Amin
- the polymer is a polyester derived from a dicarboxylic acid and a diol, and/or a hydroxycarboxylic acid, or a corresponding lactone, such as polyethylene terephthalate, polybutylene terephthalate Ester (Celanex 2500, Celanex 2002, Celanese; Ultradur, BASF), poly(1,4-dihydroxydecylcyclohexane terephthalate), polyhydroxybenzoate, and derived from hydroxyl end groups a polyether block polyetherester; and a polyester modified by polycarbonate or MBS.
- a dicarboxylic acid and a diol and/or a hydroxycarboxylic acid, or a corresponding lactone
- polyethylene terephthalate polybutylene terephthalate Ester (Celanex 2500, Celanex 2002, Celanese; Ultradur, BASF), poly(1,4-dihydroxydecylcyclohexane terephthalate
- the compounding device is a single screw extruder or a multi-zone screw extruder.
- the extruder (mixing combination device) having a screw diameter (D) multiple has an effective screw length (L) of 4 to 200 D, preferably 10 to 50 D, and D is a screw diameter.
- the melting temperature is: polyethylene terephthalate (PET) is 250-290 ⁇ , and polybutylene terephthalate (PBT) is 230-270 X:, polyamide 6 ( PA6) is 260-290", polyamide 6,6 (PA6,6) is 260-290 ⁇ .
- the flame retardant component is mixed with the polymer pellets and optionally with additives at a temperature of 230 ⁇
- the molding composition is in the injection molding machine at a melt temperature of 240 ⁇ Test specimens are obtained at 270 °C (GRPBT) or 260 ⁇ 290 (GRPA 66). For test specimens from each mixture, test specimens with a thickness of 1.6 mm are used to determine UL94 "Test for Flammabilit of Plastic Materials for Parts" In Devices and Appliances"("Combustible Performance Test for Materials for Appliances and Appliance Parts", Plastic Flammability Standards issued by Underwriters Laboratories, Inc.) (Insurance Laboratory) Combustion Rating. The following combustion ratings are given by UL94:
- V0 The burning time is never longer than 10 seconds.
- the total burning time of 10 times of ignition is less than 50 seconds. There is no fire and dripping.
- the sample is not completely burned.
- the afterglow of the sample after the ignition is not longer than the duration. 30 seconds
- V-1 The continuous burning time after the end of ignition is never longer than 30 seconds, the sum of the continued burning time of 10 times of ignition is not more than 250 seconds, and the afterglow duration of the sample after the ignition is never longer than 60 seconds, other Standard is like V-0
- V-2 Cotton indicator is fired. Ignite; other standards are like V-1
- Burning level V-2 is not met.
- the method of the present invention is measured in accordance with the method provided in U.S. Patent No. 7,129,320 B2.
- the flame retardant polymer molding composition of the present invention is suitable for use in the production of fibers, films, or molded articles, particularly in the electrical and electronic arts.
- the present invention preferably uses the flame-retardant polymer molding of the present invention as a lamp component such as a lamp holder and a lamp holder, a plug and a plug-in board, a bobbin, a case for a capacitor or a contactor, and a circuit switch, a relay case and a reflection Device.
- the invention has the beneficial effects of providing a high heat resistant compound, especially suitable as a flame retardant for glass fiber reinforced polyester and nylon.
- a mixture of 15 KG sodium hypophosphite, 130 KG molecular weight regulator diethyl phosphine oxide and 750 kg deionized water was charged to a 2000 L jacketed pressure reactor. Once the reaction mixture It has been heated to 100 and acetylene is added through a pressure reducing valve set to 3 bar until saturation is reached in the reactor. A solution containing 2.0 KG potassium persulfate in 200 KG of water was uniformly fed to the mixture under continuous stirring at a temperature of 100 to 105". A total of 20.5 KG of acetylene was consumed. The reaction was continued for 2 hours, the reactor was depressurized, and cooled to After 80"C.
- a mixture of 50 KG of sodium hypophosphite and 100 KG of mercaptophosphoric acid and 700 kg of acetic acid was charged to a 2000 L jacketed pressure reactor. Once the reaction mixture had been heated to 100X, acetylene was added through a pressure reducing valve set to 3 bar until saturation was reached in the reactor. An acetic acid solution containing 2.0KG 2,2-azobis(2-mercaptopropylhydrazine) diy acid salt (or V50) is added to the mixture under continuous stirring at a temperature of 100 to 105 ° C. A total of 30.1 KG was consumed. The reaction was continued for 2 hours. The reactor was depressurized, and after cooling to 80 Torr.
- a mixture of 80 KG of sodium hypophosphite and 50 KG of methyl phosphite and 700 kg of acetic acid was charged to a 2000 L jacketed pressure reactor. Once the reaction mixture had been heated to 100 Torr, acetylene was added through a pressure reducing valve set to 3 bar until saturation was reached in the reactor. An acetic acid solution containing 2.0KG 2,2-azobis(2-mercaptopropylhydrazine) dihydrochloride (or V50) is added to the mixture under continuous stirring at a temperature of 100 to 105*C. in. A total of 30.1 KG of acetylene was consumed. Continue to react for 2 hours. The reactor was depressurized and cooled to 80.
- a mixture of 80 KG of sodium hypophosphite and 50 KG of mercaptophosphoric acid and 700 kg of acetic acid was charged into a 2000 L jacketed pressure reactor. Once the reaction mixture had been heated to 100 C, acetylene was added through a pressure reducing valve set to 3 bar until saturation was reached in the reactor. An acetic acid solution containing 2.0 KG of 2,2-azobis(2-mercaptopropylhydrazine) dihydrochloride (or V50) was added to the mixture under continuous stirring at a temperature of 100 to 105. A total of 30.1 KG of acetylene was consumed. Continue to react for 2 hours. The reactor was depressurized and cooled to 80 Torr.
- a mixture of 80 KG of sodium hypophosphite, 25 KG methylphosphite and 35 KG diphenyl phosphinate and 600 kg of acetic acid was charged to a 2000 L jacketed pressure reactor. Once the reaction mixture has been heated to 90, acetylene is added through a pressure reducing valve set to 3 bar until saturation is reached in the reactor. An aqueous solution containing 2.2 KG of 2,2-azobis(2-mercaptopropylhydrazine) dihydrochloride (or V50) was uniformly fed to the mixture under continuous stirring at a temperature of 90 Torr, and acetylene was added until saturation. A total of 27.5KG of acetylene was consumed.
- a mixture of 80 KG of sodium hypophosphite and 70 KG of diphenyl phosphite and 700 kg of acetic acid was charged into a 2000 L jacketed pressure reactor. Once the reaction mixture has been heated to hydrazine, acetylene is added through a pressure reducing valve set to 3 bar until saturation is reached in the reactor. A solution of 2.0 KG of 2,2-azobis(2-methylpropylindole) dihydrochloride (or V50) in acetic acid was uniformly fed to the mixture under continuous stirring at a temperature of 100 to 105 Torr. A total of 30.1 KG of acetylene was consumed. The reaction was continued for 2 hours with ⁇ decompression, and after cooling to 80 Torr.
- a mixture of 80 KG sodium hypophosphite, 25 KG decylphosphite and 35 KG diphosphonate and 600 kg acetic acid was charged to a 2000 L jacketed pressure reactor. Once the reaction mixture had been heated to 100 ⁇ , acetylene was added through a pressure reducing valve set to 3 bar until saturation was reached in the reactor. A solution of 2.0 KG of 2,2-azobis(2-mercaptopropylhydrazine) dihydrochloride (or V50) in acetic acid was uniformly fed to the mixture under continuous stirring at a temperature of 100 to 105*C. A total of 27.1KG was consumed and the reaction was continued for 2 hours. The reactor was depressurized and cooled to 80.
- V0 V0 V0 VI V0 V0 VI class is obvious to those skilled in the art, various modifications and changes can be made thereto without departing from the scope and spirit of the invention. Other technical modifications made in light of the above are within the scope of the invention.
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Abstract
一种具有结构式（1）的烷基次膦酸盐聚合物，其中：R1为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、羟甲基或烷氧基中任一种；R2为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、异己基、羟甲基或烷氧基中任一种；Re为碱金属、碱土金属、过渡金属、贫金属、类金属、镧系金属或质子化氮碱中任一种，x=1/m，其中m为Re的化合价。还公开了烷基次膦酸盐聚合物的制备方法、烷基次膦酸盐聚合物的阻燃剂聚合物和阻燃剂组合物。本发明的聚合物具有高耐热性，适用于玻纤增强聚酯、尼龙和阻燃剂。
Description
一种烷基次膦酸盐聚合物及其制备方法和应用
技术领域 本发明涉及一种烷基次膦酸盐聚合物，具体涉及一种烷基次膦酸盐聚 合物及其制备方法和应用。 背景技术 聚酯或尼龙的阻燃性能可通过掺入各种类型的添加剂获得。通常， 卤 代化合物， 特别是多溴代芳香化合物已被用作这类聚合物中的阻燃添加 剂。通常认为当这些产品被点燃时，该产品抑制在火焰中发生的自由基气 相反应。这使得卤代阻燃剂非常普遍地用作包括聚酯和尼龙的不同类型聚 合物材料的添加剂。 然而， 在最近约十五年期间， 因为生态关怀， 卤代阻 燃剂已经受到监查。此时，阻燃剂工业在压力下将朝着认为更加环境友好 的阻燃添加剂的方向改变。含磷的产品是这类卤代阻燃剂合乎逻辑的替代 品。在一些应用中，含磷的添加剂显示出与卤代阻燃剂一样高的活性，但 是含碑的添加剂通常很少使用。大部分含磷的阻燃剂通过凝相反应、聚合 物碳化促进和成炭的组合提供阻燃活性。这些方法明显取决于其中使用这 种添加剂的聚合物。 因此，具体含磷的结构需要被设计成用于多种聚合物 类型。在 20世纪 70年代末和 80年代初， 制备了二芳基次膦酸、烷基 芳基次磷酸或二烷基次膦酸的各种盐，例如铝或锌盐，例如在美国专利文 献号为 4,180,495； 4,208,321和 4，208，322 中阐明的，这些次膦酸盐被添 加到 PET 中或与聚酯共聚合， 在 10- 20wt %的水平， 通过单位的氧指 数（LOI )测量， 观察到阻燃性改善。 中国专利 CN 1660875A公开了二烷 基次膦酸盐的制备方法及应用，将其应用在玻纤增强尼龙或聚酯上，添加 20%可满足阻燃要求。 为了提高阻燃效率， 需要提高阻燃剂中的磷含量。
炔烃和含有 P-H的次膦酸化合物在自由基引发下发生的加成反应是 已知的反应， 美国专利 US5647995A公开了利用该反应制备一系列的烷基 次膦酸化合物。美国专利 US6727335B2利用该反应制备了高聚合度的聚合 次膦酸， 聚合路线如下：
O H O H
[引发剂 1 11/
HO― P R-CSC-R, HO一 P.
H C R(=CHR
[31发剖 1
显然这种方法制备聚合物端基选择的范围较小， 只 H能是 2个碳原子以 上的烯烃或烷烃或 H原子。 当聚合度很大时， 端基对聚合物的性能的影响 可以忽略；但对低聚合度的高分子化合物，端基对聚合物性能的影响就很 大。
我们发现这种聚合次膦酸盐酸性极大，且随聚合度增加而增加，如果 作为阻燃剂而添加在其他高分子材料中，很强的酸性将对材料的机械性能 有极大的破坏。 而不能被应用。显然，如果作为阻燃剂应用必然只能是低 聚合度的聚合次膦酸盐。
因此，为提高磷含量，研发低聚合度的烷基次磷酸盐作为阻燃剂有其 现实的价值。 发明内容 本发明的目的在于提供一种烷基次膦酸盐聚合物及其制备方法和应 用。
本发明提出的烷基次磷酸盐聚合物， 其结构式如下：
其中： 为曱基、 乙基、 正丙基、 异丙基、 正丁基、 异丁基、 叔丁 基、 正戊基、 异戊基、 正己基、 异己基、 羟曱基或烷氧基中任一种；
R2为曱基、 乙基、 正丙基、 异丙基、 正丁基、 异丁基、 叔丁基、 正 戊基、 异戊基、 正己基、 异己基、 羟曱基或烷氧基中任一种；
Re为碱金属、 碱土金属、 过渡金属、 贫金属、 类金属、 镧系元素或 质子化氮碱中任一种，
X=l/m,其中 m为 Re的化合价。
优选地 Re为 Mg、 Ca、 Al、 Sb、 Sn、 Ge、 Ti、 Fe、 Zr、 Zn、 Ce、 La、 Bi、 Sr、 Mn、 Li、 Na、 K， 优选地 Re为 Al、 Ca、 Ti、 Zn、 Sn、 Zr、 La中任一种。
优选地所述质子化氮碱为含有孤对电子的氮原子的质子碱， 优选氨、 蜜胺、 三乙醇胺， 尤其是 ΝΗ4' ·蜜胺、 脲、 缩二脲、 胍、 十二烷基胍、 尿囊素、 乙酸胍胺、 苯并胍胺、 曱苯基三唑、 苯并三唑、 2-氨基 -4-曱基嘧 啶、苄基脲、 乙炔脲、 乙内酰脲、 丙二酰胺眯、二曱基脲、二苯基胍、 5,5- 二苯基乙内酰脲、 Ν，Ν，-二苯基脲、 甘氨酸酐、 四曱基脲，以及相应的聚合 物， 例如蜜胺缩合物， 如蜜勒胺、 蜜白胺、 三聚二氦胺、 或具有较高缩合 度的缩合物。
u是平均聚合度， u为 1.2-6， 优选地 u为 2-5。 它是由制备聚合物时 分子量调节剂与次磷酸或次磷酸碱金属盐的比例决定的。
制备的原理如下：
HO 1 P/、H ♦ ^~CSC— R2 + HO一 P
、R
H
( I ) ( Π ) 瞧荆 J
r金羼化合物 j R
F¾， C H K;
(1)将次磷酸或次磷酸碱金属盐、 分子量调节剂和极性溶剂混合， 装 入可调节压力的反应釜中， 常压下将混合物加热至 90~110 ， 以 3巴的 压力将炔烃加入所述的反应釜中达到气体饱和；其中：极性溶剂与溶盾（即 次磷酸或次磷酸碱金属盐与分子量调节剂重量的和）的重量 OHPI比为 4.0 ~ 6.0, 分子量调节剂与次磷酸或次磷酸碱金属盐的摩尔比为 0.4 ~ 9.0 ；
(2)连续搅拌游离基引发剂溶液， 在温度 90 110Ό下均匀加入到步骤 (1)所得混合物中， 继续加入炔烃直至饱和， 保温 2~4小时， 调整压力至 常压并冷却至 70 ~ 80* ， 再加入金属化合物或质子化氮碱进行反应， 保 温 2 ~ 2.5小时， 分离固体， 洗涤干燥， 即得到所需产物。
其中：
游离基引发剂为次磷酸或次磷碱金属酸盐重量的 0.5 ~ 13%， 金属化 合物或质子化氮碱加入量（摩尔数）为次磷酸或次磷酸碱金属盐的摩尔数 除以 m，其中 m为化合物中金属阳离子或质子化氮碱中阳离子的化合价。
所述的金属化合物为碱金属、碱土金属、过渡金属、贫金属、类金属、 镧系元素的化合物。
游离基引发剂溶液，指采用极性溶剂溶解游离基引发剂，极性溶剂的 用量不限， 足以完全溶解游离基引发剂即可。
优选地， 溶解次磷酸或次磷酸碱金属盐、分子量调节剂、 游离基引发 剂的极性溶剂为水、 羧酸、 醇。 更优选的， 极性溶剂为水或醋酸。
优选地， 碱金属、碱土金属、 过渡金属、 贫金属、 类金属、 镧系元素 化合物为氧化物、氢氧化物、氢氧化物氧化物、硫酸盐、 乙酸盐、硝酸盐、 氯化物或醇化物中任一种。
优选地， 所述的碱金属为 Li、 Na、 K， 所述的碱土金属为 Mg、 Ca、 Sr， 所述的过渡金属为 Ti、 Fe、 Zr、 Zn、 Mn, 所述的贫金属为 Al、 Sn、 Bi， 所述的类金属为 Sb、 Ge, 所述的镧系元素为 Ce、 La.
更优选地， Li、 Na、 K、 Mg、 Ca、 Sr、 Ti、 Fe、 Zr、 Zn、 Mn、 Al、 Sn、 Bi、 Sb、 Ge、 Ce、 La化合物为氧化物、 氢氧化物、 氢氧化物氧化物、 硫酸盐、 乙酸盐、 硝酸盐、 氯化物或醇化物中任一种。
本发明中， 步骤 (1)中所述炔烃为乙炔。
本发明中， 步驟 (1)中所述分子量调节剂结构符合下式：
其中：
为 d-C6烷基、 芳基、 CrC6烷氧基、 苯氧基、 d- 羟烷基、 羟 基、 羟钠基；
R2为 CrC6烷基、 芳基、 d-C6烷氧基、 苯氧基、 d-C6羟烷基、 羟 基、 羟钠基；
且 、 不能同为 crc6烷氧基、 crc6羟烷基、 羟基、 羟钠基。 优选地， 为曱基且 为曱基， 羟基； 为乙基且 R2为乙基或羟 基； 为苯氧基且 为苯氧基； 为新戊二醇酯基且 R2为新戊二醇酯 基； 或 之一为羟甲基。 本发明中， 步骤 (2)中所述游离基引发剂为偶氮化合物， 所述偶氮化 合物为阳离子、偶氮化合物、 非阳离子偶氮化合物、无机过氧化物游离基 引发剂或有机过氧化物游离基引发剂中任一种。
优选地， 所述阳离子偶氮化合物采用 2,2-偶氮二（2-曱基丙基脒）二 盐酸盐 (或称 V50 )， 所述非阳离子偶氮化合物采用二异丁睛、 4，4-偶氮二 ( 4-氰基戊酸）或 2，2，-偶氮二（2-曱基丁睛）， 所述无机过氧化物游离基 引发剂采用过氧化氢、过二硫酸铵、过二硫酸钠或过二硫酸钾，有机过氧 化物游离基引发剂采用氧化二苯甲酰、 二叔丁基过氧化物或过乙酸。
本发明提出的烷基次膦酸盐聚合物作为阻燃剂、阻燃剂组合物和阻燃 聚合物模塑组合物的应用。 本发明提出的烷基次膦酸盐聚合物作为阻燃剂组合物的应用，具体方 法如下：将烷基次膦酸盐聚合物中加入添加剂，得到阻燃剂组合物，其中： 烷基次膦酸盐聚合物的加入量为 70wt-95wt %，添加剂的加入量为 5wt-30wt%。 所得阻燃剂组合物的平均颗拉尺寸为 0.1-3000 μ ιη,较佳为 0.1-1000 μ ιη, 进一步为 1-100 μ ιη。
本发明中， 所述添加剂为蜜胺磷酸盐、二蜜胺磷酸盐、五蜜胺三磷酸 盐、三蜜胺二磷酸盐、四蜜胺三磷酸盐、六蜜胺五磷酸盐、蜜胺二磷酸盐、 蜜胺四磷酸盐、 蜜胺焦磷酸盐、 蜜胺多磷酸盐、 蜜白胺多磷酸盐、 蜜勒胺 多磷酸盐或三聚二氰胺多磷酸盐、锌化合物、镁化合物、钙化合物、铝化 合物、锰化合物、 锡化合物或碳二亚胺或（多）异氰酸酯中任一种。 优选 地， 为三（羟基乙基）异氰尿酸酯与芳族多羧酸的低聚物酯、 苯并胍胺、 三（羟基乙基）异氛尿酸酯、 尿嚢素、 甘脲、 蜜胺、 蜜胺氰尿酸酯、 脲氰 尿酸酯、双氰胺或或胍中任一种。所述碳二亚胺如羰基二己内酸胺； 所述 镁化合物如氧化镁、 氢氧化镁、 水滑石、 二水滑石、 碳酸镁或碳酸镁钙； 所述钩化合物如氢氧化钙、氧化钙、水铝钙石；所述锌化合物如氧化锌（如 活性氧化锌）、 氢氧化锌、 水合氧化锌、 碳酸锌（如碱性碳酸锌、 无 酸锌） 、 锡酸锌、 羟基锡酸锌、 碱性硅酸锌、 碱性磷酸锌、 碱性硼酸锌、 碱性钼酸锌、或碱性硫化锌；所述铝化合物如氧化铝、氢氧化铝、水铝氧、 或磷酸铝； 所述锰化合物如氧化锰， 氢氧化锰； 所述锡化合物如氧化锡。 本发明提出的阻燃聚合物模塑组合物的应用， 具体方法如下： 将烷基次膦酸盐聚合物、聚合物和添加剂在混合器中混合，在一定温 度下在配混组合装置中熔融均匀， 所得产物挤出， 冷却， 即得所需产品。
本发明中， 所述聚合物是衍生自二胺和二羧酸， 和 /或氨基羧酸，或 相应内酰胺的聚酰胺和共聚酰胺， 如聚酰胺 2,12， 聚酰胺 4 (聚 4-氨基丁 酸)， 聚酰胺 4,6 (聚 (四亚曱基己二酰胺）） ， 聚酰胺 6 (聚己内酰胺， 聚 6-氨基己酸）， 聚酰胺 6，6 (聚 (Ν，Ν，-六亚曱基己二酰胺))， 聚酰胺 6,9 (聚 (六亚曱基壬烷二酸胺）），聚酰胺 6，10 (聚 (六亚甲基癸二酰胺))， 聚酰胺
6,12 (聚 (六亚曱基十二烷二酰胺）） ， 聚酰胺 6/6,6 (聚 (六亚曱基己酰胺- 共-己内酰胺))， 聚酰胺 7 (聚 7- J^庚酸)， 聚酰胺 7，7 (聚七亚甲基庚二 酰胺)， 聚酰胺 8 (聚 8-氨基辛酸)， 聚酰胺 8，8 (聚八亚曱基辛二酰胺)， 聚酰胺 9 (聚 9-氨基壬酸)， 聚酰胺 9,9 (聚九亚曱基壬酰胺)， 聚酰胺 10 (聚 10-氨基癸酸)， 聚酰胺 10,9 (聚（十亚曱基壬酰胺 ) )， 聚酰胺 10,10 (聚十亚曱基葵酰胺)， 聚酰胺 11 (聚 11-氨基十一酸)， 聚酰胺 12 (聚月 桂基内酰胺)， 衍生自间-二曱苯， 二胺和己二酸的芳族聚酰胺； 由六亚甲 基二胺和间苯二甲酸和 /或对苯二曱酸制成的聚酰胺（聚六亚曱基间苯二 曱酰胺或聚六亚曱基对苯二甲酰胺）， 如果合适， 由弹性体作为改性剂而 制成，如聚 2，4，4-三曱基六亚曱基对苯二曱酰胺或聚间 -亚苯基间苯二曱酰 胺； 上述聚醜胺与聚烯烃， 与烯烃共聚物， 与离聚体， 或与化学健接或接 枝的弹性体； 或与聚醚， 如与聚乙二醇， 聚丙二醇， 或聚四亚曱基二醇的 嵌段共聚物； 或者被通过 EPDM或被 ABS改性的共聚酰胺或聚酰胺； 或 者在处理过程中缩合的聚酰胺（ "RIM聚酰胺体系" ）。
所述聚合物是衍生自二羧酸和二醇，和 /或羟基羧酸，或相应的内酯 的聚酯， 如聚对苯二甲酸乙二醇酯， 聚对苯二曱酸丁二醇酯 ( Celanex 2500， Celanex 2002， Celanese； Ultradur， BASF ) ，聚 (1,4-二羟曱基环己 烷对苯二甲酸酯)， 聚羟基苯曱酸酯， 以及衍生自具有羟基端基的聚醚的 嵌段聚醚酯； 以及被聚碳酸酯或被 MBS 改性的聚酯。
本发明中， 所述配混组合装置采用单螺杆挤出机或多区螺杆挤出机。 其螺杆直径（D )倍数的挤出机（配混组合装置）的有效螺杆长度 (L )为 4-200D, 较佳的为 10-50D, D为螺杆直径。
本发明中，熔融温度为：聚对苯二曱酸乙二醇酯（ PET )是 250-290Ό , 聚对苯二曱酸丁二醇酯（ PBT )是 230-270 X：，聚酰胺 6(PA6 )是 260-290 " , 聚酰胺 6，6(PA6，6 )是 260-290 Ό。 阻燃塑料模塑组合物和塑料模塑品的生产， 加工， 和测试
阻燃剂组分与聚合物粒料和视需要与添加剂混合， 并在温度 230 ~
260 V (制做增强阻燃 ΡΒΤ, 即 GRPBT )或 260 ~ 280 (制做增强 阻燃 ΡΑ66, 即 GRPA 66 )下加入双螺杆挤出机中。 将匀化的聚合物挤 出物引出， 在水浴中冷却， 并随后造粒.
在充分干燥之后， 将模塑组合物在注塑机中在熔体温度 240 ~
270 °C ( GRPBT )或 260 ~ 290 ( GRPA 66 )下加工得到试验试 样. 针对来自每种混合物的试验试样使用厚度 1 . 6mm 的试验试样测定 UL94 "Test for Flammabilit of Plastic Materials for Parts in Devices and Appliances" ( "设备和器具部件材料的可燃性能试验"，美国 Underwriters Laboratories公司发布的塑胶可燃性标准） （保险实验室）燃烧等级. 以 下燃烧等级由 UL94给出：
V0 ： 继续燃烧时间决不长于 10秒， 10次点燃时的继续燃烧时间 的总和不超过 50秒， 没有起火滴落，样品未完全烧完，试样在点燃结束 之后的余辉延续时间决不长于 30秒
V-1 ：在点燃结束之后的继续燃烧时间决不长于 30秒， 10次点燃 时的继续燃烧时间的总和不超过 250秒， 试样在点燃结束之后的余辉延 续时间决不长于 60秒， 其它标准如同 V-0
V-2 ： 棉指示物被火滴. 点燃； 其它标准如同 V-1
不可分类（n.d. ): 不满足燃烧等级 V-2 。
平均聚合度 u， 使用 31P潘按美国专利 US 7129320B2提供的方法 测量 本发明阻燃聚合物模塑组合物适用于生产纤维，膜，或模塑品， 尤其 用于电气和电子领域。本发明优选使用本发明阻燃聚合物模塑品作为灯部 件， 如灯座和灯架， 插头和插入线路板， 线圈架， 用于电容器或接触器的 外壳， 和电路开关， 继电器外壳和反射器。
本发明的有益效果在于：提供一种高耐热的化合物，尤其适用于作为 玻纤增强聚酯， 尼龙的阻燃剂。 具体实施方式 以下结合实施例对本发明进行详细说明。但应理解， 以下实施例仅是 对本发明实施方式的举例说明， 而非是对本发明的范围限定。
在实施例中， 原料来源如表一所示， 其余原料非特别说明均为市售。 表一
三聚氰胺焦磷酸盐 MPP Ciba M200
聚对苯二曱酸丁二醇 （简写 Celanex 2300GVl/30(含 30%玻纤）
PBT1 )
聚对苯二甲酸丁二醇 （简写 GE 307
PBT2 )
玻纤 HP3786 ( 3.2MM ) 台湾必成公司 曱基亚膦酸二乙酯 山东维天精细化工科技有限公司 尼龙 66 ( PA66 ) BASF A3
2,2, -偶氮二 ( 2-甲基丙基脒)
青岛柯信新材料科技有限公司
二盐酸盐 (或称 V50 )
硼酸锌 ZB 吉青化工
实施例 1 分子量调节剂二乙基氧化膦制备
在氩气保护下， 在 2000L反应釜中加入 22Kg镁粉和 250L干燥 THF ， 先加入 3L溴乙烷， 待反应引发后， 开动搅拌， 水浴冷却下滴加 106Kg溴乙烷和 400L干燥 THF的混合液，保持微沸状态，滴加完毕后， 室温下继续反应 1 h 。 冰水浴冷却， 向上述所制备的格氏试剂中滴加 41.5KG亚磷酸二乙酯和 150L干燥 THF 的混合液，温度控制 25 Ό以下， 25 Ό水浴中反应 4h左右。冰水浴冷却， 滴加冷却至 0 的碳酸钾溶液 ( 126 . 5Kg碳酸钾溶于 150L水中）水解。 过滤， 滤液真空脱除溶剂 ( 50 循环水泵真空度为 0 . 08MPa ) , 得淡黄色液体， 所得液体减 压蒸餾（真空度为 0 . 095MPa ) ， 收集 84 X左右的馏分， 收集到无色透 明液体二乙基氧化磚。 实施例 2 分子量调节剂曱基亚磷酸制备
将 100KG 10% 的盐酸装入 1000L的搪瓷反应釜中， 通入氮气， 升 温至 70-80 Ό连续滴加 200KG的曱基亚膦酸二乙酯， 滴加完毕温度维持 在 85 - 90 V ，l h .冷却至室温， 减压蒸馏， 除去 HC1, 乙醇和水分， 得 到无色的液体。 即为曱基亚磷酸。 实施例 3 二烷基次膦酸铝聚合物制备
将 15 KG的次磷酸钠， 130KG分子量调节剂二乙基氧化膦和 750kg 去离子水的混合物装入 2000L带夹套的压力反应器中。 一旦反应混合物
已被加热至 100 ，将乙炔通过被设定为 3巴的减压阀加入直至在反应器 中达到饱和。将含 2.0KG过硫酸钾在 200KG水中的溶液在连续搅拌下在 温度 100 ~ 105" 下均匀加料到该混合物中。共消耗乙炔 20.5KG。 继续反 应 2 小时， 减压该反应器， 和冷却至 80"C之后。 在 2小时内， 加入 29 KG50 %浓度的含 A1203 16.53wt%的 A12(S04)3水溶液。 将所得固体随后 离心， 用水洗涤两次， 然后在 130 下真空干燥。 得到产物： u为 1.2, 磷含量： 26.0%。 实施例 4 二烷基次膦酸铝聚合物
将 50KG的次磷酸钠和 100KG曱基亚磷酸及 700kg醋酸的混合物装 入 2000L带夹套的压力反应器中。一旦反应混合物已被加热至 100X，将 乙炔通过被设定为 3 巴的减压阀加入直至在反应器中达到饱和。 将含 2.0KG 2，2-偶氮二（2-曱基丙基脒）二益酸盐 (或称 V50 )的醋酸溶液在连 续搅拌下在温度 100 ~ 105"C下均勾加料到该混合物中。 共消耗乙块 30.1KG。 继续反应 2 小时。 减压该反应器， 和冷却至 80Ό之后。 在 2 小时内， 加入 350 KG50 %浓度的含 Al20316.53wt。/。的 A12(S04)3水溶液。 将所得固体随后离心， 用水洗涤两次， 然后在 130Ό下真空干燥。 得到产 物： u=1.7， 磷含量： 30.3%。 实施例 5 二烷基次膦酸铝聚合物制备
将 80KG的次磷酸钠和 50KG甲基亚磷酸及 700kg醋酸的混合物装 入 2000L带夹套的压力反应器中。一旦反应混合物已被加热至 100Ό ,将 乙炔通过被设定为 3 巴的减压阀加入直至在反应器中达到饱和。 将含 2.0KG 2，2-偶氮二（2-曱基丙基脒）二盐酸盐 (或称 V50 )的醋酸溶液在连 续搅拌下在温度 100 ~ 105*C下均勾加料到该混合物中。 共消耗乙炔 30.1KG。 继续反应 2 小时。 减压该反应器， 和冷却至 80 之后。 在 2 小时内，加入 285 KG 50 %浓度的含 120316.53 1%的 A12(S04)3水溶液。 将所得固体随后离心， 用水洗涤两次， 然后在 130 下真空干燥。 得到产 物： u=3.4, 磷含量： 30.3%。 实施例 6 二烷基次膦酸钙聚合物制备
将 80KG的次磷酸钠和 50KG曱基亚磷酸及 700kg醋酸的混合物装
入 2000L带夹套的压力反应器中。一旦反应混合物已被加热至 100" ，将 乙炔通过被设定为 3 巴的减压阀加入直至在反应器中达到饱和。 将含 2.0KG 2，2-偶氮二（2-曱基丙基脒）二盐酸盐 (或称 V50 )的醋酸溶液在连 续搅拌下在温度 100 ~ 105 "C下均匀加料到该混合物中。 共消耗乙炔 30.1KG。 继续反应 2 小时。 减压该反应器， 和冷却至 80 之后。 在 2 小时内， 加入191 10；40 %浓度的€3<：12水溶液。 将所得固体随后离心， 用水洗涤两次， 然后在 130 下真空干燥。 得到产物： u=3.0， 磷含量： 27.2%。 实施例 7 二烷基次膦酸镧聚合物制备
将 80KG的次磷酸钠和 50KG曱基亚磷酸及 700kg醋酸的混合物装 入 2000L带夹套的压力反应器中。一旦反应混合物已被加热至 lOOC将 乙炔通过被设定为 3 巴的减压阀加入直至在反应器中达到饱和。 将含 2.0KG 2，2-偶氮二（2-曱基丙基脒）二盐酸盐 (或称 V50 )的醋酸溶液在连 续搅拌下在温度 100 ~ 105 下均勾加料到该混合物中。 共消耗乙炔 30.1KG。 继续反应 2 小时。 减压该反应器， 和冷却至 80Ό之后。 在 2 小时内， 加入 325 KG 50 %浓度的含 LaCl3 . 6 0水溶液。 将所得固体 随后离心， 用水洗涤两次， 然后在 下真空干燥。 得到产物： u=3.1, 磷含量： 22.0% 实施例 8 二烷基次膦酸锌聚合物制备
将 80KG的次磷酸钠、 25KG甲基亚磷酸和 35 KG亚膦酸二苯酯及 600kg醋酸的混合物装入 2000L带夹套的压力反应器中。一旦反应混合物 已被加热至 90 将乙炔通过被设定为 3巴的减压阀加入直至在反应器 中达到饱和。将含 2.2KG 2，2-偶氮二（ 2-曱基丙基脒）二盐酸盐 (或称 V50 ) 水溶液在连续搅拌下在温度 90Ό下均匀加料到该混合物中， 继续加入乙 炔直至饱和， 共消耗乙炔 27.5KG。 保温 3 小时后， 减压该反应器， 冷却 至 80 ， 加入 310 KG 50 %浓度的 ZnS04.7H20水溶液。保温 2小时.将 所得固体随后离心，用水洗涤两次，然后在 130Ό下真空干燥。得到产物： u=3.9，碑含量： 22.0%.
实施例 9 二烷基次膦酸锦聚合物制备
将 80KG的次磷酸钠、 50KG曱基亚磷酸及 600kg去离子水的混合物 装入 2000L带夹套的压力反应器中。 一旦反应混合物已被加热至 90Ό , 将乙炔通过被设定为 3 巴的减压阀加入直至在反应器中达到饱和。 将含 3.0KG过二硫酸铵的水溶液在连续搅拌下在温度 90"C下均匀加料到该混 合物中。 共消耗乙炔 30.0KG。 继续反应 4 小时。 减压该反应器， 和冷却 至 70 "C之后。加入177 。浓度50%的€6( 13 7 溶液， 保温 2.5小时。将 所得固体随后离心，用水洗涤两次，然后在 130 下真空干燥。得到产物： u=3.3，碑含量： 22.6%。 实施例 10 二烷基次膦酸铝聚合物制备
将 80KG的次磷酸钠和 70KG亚磷酸二苯酯及 700kg醋酸的混合物 装入 2000L带夹套的压力反应器中。 一旦反应混合物已被加热至 ΙΟΟΌ , 将乙炔通过被设定为 3 巴的减压阀加入直至在反应器中达到饱和。 将 2.0KG 2，2-偶氮二（2-甲基丙基脒）二盐酸盐 (或称 V50 )的醋酸溶液在连 续搅拌下在温度 100~105 Ό下均匀加料到该混合物中。 共消耗乙炔 30.1KG。 继续反应 2 小时 β 减压该反应器， 和冷却至 80Ό之后。 在 2 小时内，加入 155 KG50 %浓度的含 A120316.53wt%的 A12(S04)3水溶液。 将所得固体随后离心， 用水洗涤两次， 然后在 下真空干燥。 得到产 物： u=6.0, 磷含量: 21.3%. 实施例 11 二烷基次膦酸铝聚合物制备
将 80KG的次磷酸钠、 25KG曱基亚磷酸和 35 KG亚膦酸二苯酯及 600kg醋酸的混合物装入 2000L带夹套的压力反应器中。一旦反应混合物 已被加热至 100η，将乙炔通过被设定为 3巴的减压阀加入直至在反应器 中达到饱和。 将 2.0KG 2，2-偶氮二（2-曱基丙基脒）二盐酸盐 (或称 V50 ) 的醋酸溶液在连续搅拌下在温度 100〜105*C下均匀加料到该混合物中。共 消耗乙块 27.1KG, 继续反应 2 小时。 减压该反应器， 和冷却至 80 之 后。在 2小时内，加入 220 KG 50 %浓度的含 Al20316.53wt%的 A12(S04)3 水溶液。将所得固体随后离心，用水洗涤两次，然后在 130 下真空干燥， 得到产物： u=4.2， 磷含量： 25.7%。
实施例 12 UL94阻燃测试
根据上文"阻燃塑料模塑组合物和塑料模塑品的生产，加工，和测试" 部分的一般说明， 将由 14 %重量的实施例 3的产物和 6 %重量的 MPP和 80 %重量聚对苯二甲酸丁二醇酯（PBT1)组成的混合物在双螺杆挤出机中 在 230至 260 下配混， 得到阻燃聚合物模塑组合物。 在干燥之后， 模塑 组合物在注塑机中在熔体温度 240至 270 X下加工得到阻燃聚合物模塑 品。 试验试样根据 UL94的分级是 V-0. 实施例 13 UL94阻燃测试
根据上文"阻燃塑料模塑组合物和塑料模塑品的生产，加工，和测试" 部分的一般说明， 将由 14 %重量的实施例 4的产物和 6 %重量的 MPP和 80 %重量聚对苯二曱酸丁二醇酯（ PBT1)组成的混合物在双螺杆挤出机中 在 230至 260 下配混， 得到阻燃聚合物模塑组合物。 在干燥之后， 模塑 组合物在注塑机中在熔体温度 240至 270 下加工得到阻燃聚合物模塑 品。 试验试样根据 UL94的分级是 V-0. 实施例 14 UL94阻燃测试
根据上文"阻燃塑料模塑组合物和塑料模塑品的生产，加工，和测试" 部分的一般说明， 将由 14 %重量的实施例 5的产物和 6 %重量的 MPP和 50 %重量聚对苯二曱酸丁二醇酯（ PBT2)和 30%重量玻纤组成的混合物在 双螺杆挤出机中在 230至 260*C下配混， 得到阻燃聚合物模塑组合物。 在 干燥之后，模塑组合物在注塑机中在熔体温度 240至 270 X：下加工得到阻 燃聚合物模塑品。 试验试样根据 UL94的分级是 V-0。 实施例 15 UL94阻燃测试
根据上文"阻燃塑料模塑组合物和塑料模塑品的生产，加工，和测试" 的一般说明，将由 14 %重量的实施例 10的产物和 6 %重量的 MPP和 50 % 重量聚对苯二曱酸丁二醇酯（ PBT2)和 30%重量玻纤组成的混合物在双螺 杆挤出机中在 230至 260Ό下配混， 得到阻燃聚合物模塑组合物。在干燥 之后，模塑组合物在注塑机中在熔体温度 240至 270 下加工得到阻燃聚 合物模塑品。 试猃试样根据 UL94的分级是 V-1。
实施例 16 UL94阻燃测试
根据上文"阻燃塑料模塑组合物和塑料模塑品的生产，加工，和测试" 的一般说明，将由 14 %重量的实施例 11的产物和 6 %重量的 MPP和 80 % 重量聚对苯二甲酸丁二醇酯（PBT2)组成的混合物在双螺杆挤出机中在 230至 260 "C下配混， 得到阻燃聚合物模塑组合物。 在干燥之后， 模塑组 合物在注塑机中在熔体温度 240至 270 下加工得到阻燃聚合物模塑品。 试验试样根据 UL94的分级是 V-0。 实施例 17 UL94阻燃测试
根据上文"阻燃塑料模塑组合物和塑料模塑品的生产，加工，和测试" 的一般说明， 将由 12 %重量的实施例 4的产物， 5 %重量蜜胺多磷酸盐， 1 %重量硼酸锌， 52 %重量聚酰胺 PA66和 30 %重量玻璃纤维组成的混合 物在双螺杆挤出机中在 260至 280 下配混，得到阻燃聚合物模塑组合物。 在干燥之后，模塑组合物在注塑机中在熔体温度 260至 300 X下加工得到 阻燃聚合物模塑品。 试验试样根据 UL94的分级是 V-0. 实施例 18 UL94阻燃测试
根据上文"阻燃塑料模塑组合物和塑料模塑品的生产，加工，和测试" 的一般说明， 将由 14 %重量的实施例 7的产物和 5 %重量的 MPP和 1 % 重量的磷酸铝和 80 %重量聚对苯二甲酸丁二醇酯（ PBT1)组成的混合物在 双螺杆挤出机中在 230至 260 下配混， 得到阻燃聚合物模塑组合物.在 干燥之后，模塑组合物在注塑机中在熔体温度 240至 270 "C下加工得到阻 燃聚合物模塑品。 试验试样根据 UL94的分级是 V-1。 实施例应用结果见表二。
表二实施例应用结果
实施例 12 13 14 15 16 17 18 实施例 3产物 14
实施例 4产物 14 12 实施例 5产物 14
实施例 7产物 14
实施例 10产物 14
实施例 11产物 14
ZB 1
MPP 6 6 6 6 6 5 5 磷酸铝 1
PBT1 80 80 80
PBT2 50 80 80
玻纤 30 30
PA6,6 52
对应的 UL94等
V0 V0 V0 VI V0 V0 VI 级 对于本领域技术人员显而易见的是， 在不背离本发明的范围和精神 的前提下， 可对其进行各种修改和变动， 上述各项技术特征之间的组合 及根据上述内容所完成的其它技术方案改变均属本发明范围。
Claims
1.一种烷基次膦酸盐聚合物， 其结构式如下
Re为碱金属、 碱土金属、 过渡金属、 贫金属、 类金属、 镧系元素或 质子化氮碱中任一种， x=l/m，其中 m为 Re的化^
平均聚合度 u=1.2 ~ 6。
2、 根据权利要求 1所述的烷基次膦酸盐聚合物， 其特征在于所述的 碱金属为 Li、 Na、 K, 所述的碱土金属为 Mg、 Ca、 Sr, 所述的过渡金属 为 Ti、 Fe、 Zr、 Zn、 Mn, 所述的贫金属为 Al、 Sn、 Bi, 所述的类金属为 Sb、 Ge, 所述的镧系元素为 Ce、 La, 优选地所述 Re为 Al、 Ca、 Ti、 Zn、 Sn、 Zr、 La中任一种， 所述质子化氮碱为氨、 蜜胺、三乙醇胺、 NH4， '蜜 胺、 脲、 缩二脲、 胍、 十二烷基胍、 尿嚢素、 乙酸胍胺、 苯并胍胺、 曱苯 基三唑、 苯并三唑、 2-氨基 -4-曱基嘧啶、 苄基脲、 乙炔脲、 乙内酰脲、 丙 二酰胺眯、 二曱基脲、 二苯基胍、 5，5-二苯基乙内酰脲、 N，N，-二苯基脲、 甘氨酸酐、 四甲基脲，以及相应的聚合物中任一种， 优选地所述廣子化氮 碱为蜜勒胺、 蜜白胺、 三聚二氟胺、 或具有较高缩合度的蜜胺缩合物。
3、 根据权利要求 1所述的烷基次膦酸盐聚合物， 其特征在于所述聚 合度 u=2 ~ 5。
4、 一种权利要求 1所述的烷基次膦酸盐聚合物的制备方法， 其特征 在于具体步骤如下：
(1)将次磷酸或次磷酸碱金属盐、 分子量调节剂和极性溶剂混合， 装 入可调节压力的反应釜中， 常压下将混合物加热至 90~110 ， 以 3巴的压 力将炔烃加入所述的反应釜中达到气体饱和；
其中， 极性溶剂与溶质的重量比为 4.0 ~ 6.0，分子量调节剂与次磷酸 或次磷酸碱金属盐的摩尔比为 0.4 ~ 9.0;
(2)连续搅拌游离基引发剂溶液， 在温度 90~110X下均匀加入到步 骤 (1)所得混合物中， 继续加入炔烃直至饱和， 保温 2~4小时， 调整压力至 常压并冷却至 70 ~ 80*C，再加入金属化合物或质子化氮碱进行反应，保温 2 ~ 2.5小时， 分离固体， 洗涤干燥， 即得到所需产物；
其中， 游离基引发剂为次磷酸或次磷碱金属酸盐重量的 0.5 ~ 13%; 所述的金属化合物或质子化氮碱加入摩尔量为次磷酸或次磷酸碱金 属盐的摩尔量除以 m，其中 m为所述的金属化合物中金属阳离子或质子 化氮碱中阳离子的化合价；
所述的金属化合物为碱金属、碱土金属、过渡金属、贫金属、类金属、 镧系元素的化合物。
5、 根据权利要求 4所述的制备方法， 其特征在于步骤 (1)中所述炔烃 为乙炔。
6、 根据权利要求 4所述的制备方法， 其特征在于步骤 (1)中所述分子 量调节剂结构符合下式：
0
II
R「P— H
R2 其中
为 CrC6烷基、 芳基、 d-C6烷氧基、 苯氧基、 crc6羟烷基、 羟 基、 羟钠基；
R2为 0(：6烷基、 芳基、 d-C6烷氧基、 苯氧基、 d- 羟烷基、 羟 基、 羟钠基；
且 、 R2不能同为 CrC6烷氧基、 d- 羟烷基、 羟基、 羟钠基， 优选地，
Ri为甲基且 R2为曱基， 羟基； 为乙基且 R2为乙基， 羟基； Ri为 苯氧基且 R2为苯氧基； 为新戊二醇酯基且 R2为新戊二醇酯基； 或 之一为羟甲基。
7、 根据权利要求 4所述的制备方法， 其特征在于溶解次磷酸或次磷 酸碱金属盐、 分子量调节剂、 游离基引发剂的极性溶剂为水、 羧酸、 醇， 优选地所述的极性溶剂为水或醋酸。
8、根据权利要求 4所述的制备方法， 其特征在于碱金属、碱土金属、 过渡金属、 贫金属、 类金属、镧系元素化合物为氧化物、 氢氧化物、 氢氧 化物氧化物、 硫酸盐、 乙酸盐、 硝酸盐、 氯化物或醇化物中任一种。
9、根据权利要求 4所述的制备方法，其特征在于所述的碱金属为 Li、 Na、 K， 所述的碱土金属为 Mg、 Ca、 Sr, 所述的过渡金属为 Ti、 Fe、 Zr> Zn、 Mn, 所述的贫金属为 Al、 Sn、 Bi， 所述的类金属为 Sb、 Ge， 所述的镧系元素为 Ce、 La, 优选地 Li、 Na、 K、 Mg、 Ca、 Sr、 Ti、 Fe、 Zr、 Zn、 Mn、 Ah Sn、 Bi、 Sb、 Ge、 Ce、 La化合物为氧化物、 氢氧化 物、 氢氧化物氧化物、硫酸盐、 乙酸盐、硝酸盐、 氯化物或醇化物中任一 种。
10、 根据权利要求 4所述的制备方法， 其特征在于步骤 (2)中所述游离 基引发剂为偶氮化合物， 所述偶氮化合物为阳离子、偶氮化合物、非阳离 子偶氮化合物、 无机过氧化物游离基引发剂或有机过氧化物游离基引发 剂， 优选地， 所述阳离子偶氮化合物采用 2，2-偶氮二（2-甲基丙基脒）二 盐酸盐 (或称 V50 ) , 所述非阳离子偶氮化合物采用二异丁睛、 4，4-偶氮二
( 4-氰基戊酸）或 2，2，-偶氮二（2-曱基丁睛） ， 所述无机过氧化物游离基 引发剂采用过氧化氢、过二硫酸铵、过二硫酸钠或过二硫酸钾，有机过氧 化物游离基引发剂采用氧化二苯曱酰、 二叔丁基过氧化物或过乙酸。
11、 一种阻燃剂组合物， 包括权利要求 1-3任一的烷基次膦酸盐聚合 物和添加剂 0
12、根据权利要求 11所述的阻燃剂组合物，所述的烷基次膦酸盐聚合 物的加入量为 70wt-95wt%， 所述的添加剂的加入量为 5wt-30wt%。
13、根据权利要求 11所述的阻燃剂组合物，其特征在于所述的阻燃剂 组合物的平均颗拉尺寸为 0.1-3000 μ ιη,优选地所述的阻燃剂组合物的平 均颗拉尺寸为 1-100 μ ιη。
14、 根据权利要求 11-13任一的阻燃剂组合物， 其特征在于所述添加 剂为蜜胺磷酸盐、二蜜胺磷酸盐、五蜜胺三磷酸盐、三蜜胺二磷酸盐、 四 蜜胺三磷酸盐、 六蜜胺五磷酸盐、 蜜胺二碑酸盐、 蜜胺四磷酸盐、 蜜胺焦 磷酸盐、 蜜胺多磷酸盐、 蜜白胺多磷酸盐、 蜜勒胺多磷酸盐、三聚二氛胺 多磷酸益、三（羟基乙基）异氰尿酸酯与芳族多羧酸的低聚物酯、苯并胍 胺、 三（羟基乙基）异氰尿酸酯、 尿囊素、 甘脲、 蜜胺、 蜜胺氰尿酸酯、 脲氰尿酸酯、双氰胺或、胍、锌化合物、镁化合物、钙化合物、铝化合物、
锰化合物、 锡化合物、 碳二亚胺、 （多）异氰酸酯中任一种， 优选地所述 添加剂为所述碳二亚胺如羰基二己内酸胺；所述镁化合物如氧化镁、氢氧 化镁、水滑石、二水滑石、碳酸镁或碳酸镁钙；所述钙化合物如氢氧化钙、 氧化钙、 水铝钙石； 所述锌化合物如氧化辞、 氢氧化锌、 水合氧化锌、碳 酸锌、 锡酸锌、 羟基锡酸锌、碱性硅酸锌、碱性磷酸锌、 碱性硼酸锌、碱 性钼酸锌、 或碱性硫化锌； 所述铝化合物如氧化铝、 氢氧化铝、 水铝氧、 或磷酸铝； 所述锰化合物如氧化锰， 氢氧化锰； 所述锡化合物如氧化锡。
15、 一种阻燃聚合物模塑组合物， 包括权利要求 1-3任一的烷基次膦 酸盐聚合物、 聚合物和添加剂。
16、根据权利要求 15所述的阻燃聚合物模塑组合物，其特征在于所述 的聚合物是衍生自二胺和二羧酸，和 /或氨基羧酸，或相应内酰胺的聚酰 胺和共聚酰胺，优选地所述的聚合物为聚酰胺 2,12， 聚 4-氨基丁酸， 聚 (四 亚曱基己二酰胺)， 聚 6-氨基己酸， 聚 (N，N，-六亚曱基己二酰胺)， 聚 (六亚 甲基壬烷二酸胺)，聚 (六亚曱基癸二酰胺)，聚 (六亚甲基十二烷二酰胺)，聚 (六亚曱基己酰胺 -共-己内酰胺)， 聚 7- J^庚酸， 聚七亚曱基庚二酰胺， 聚 8-氨基辛酸，聚八亚甲基辛二酰胺，聚 9-氨基壬酸，聚九亚甲基壬酰胺， 聚 10-氨基癸酸， 聚（十亚曱基壬酰胺）， 聚十亚甲基葵酰胺， 聚 11- J> 十一酸， 聚月桂基内酰胺， 衍生自间-二曱苯， 二胺和己二酸的芳族聚酰 胺； 聚六亚甲基对苯二曱酰胺， 聚 2，4，4-三曱基六亚曱基对苯二甲酰胺， 聚间-亚苯基间苯二曱酰胺； 上述聚酰胺与聚烯烃， 与烯烃共聚物， 与离 聚体， 或与化学健接或接枝的弹性体； 或与聚醚， 如与聚乙二醇， 聚丙二 醇，或聚四亚甲基二醇的嵌段共聚物； 或者被通过 EPDM或被 ABS改性的 共聚酰胺或聚酰胺； 或者在处理过程中缩合的聚酰胺中任一种。
17、根据权利要求 15所述的阻燃聚合物模塑组合物，其特征在于所述 的聚合物是衍生自二羧酸和二醇，和 /或羟基羧酸，或相应的内酯的聚酯， 优选地所述的聚合物是聚对苯二曱酸乙二醇酯， 聚对苯二曱酸丁二醇酯， 聚 (1,4-二羟曱基环己坑对苯二曱酸酯)， 聚羟基苯甲酸酯， 衍生自具有羟 基端基的聚醚的嵌段聚醚酯， 以及被聚碳酸酯或被 MBS 改性的聚酯。
18、 一种权利要求 15所述的阻燃聚合物模塑组合物的制备方法，
1 )将权利要求 1-3任一烷基次膦酸盐聚合物、聚合物和添加剂在混合 器中混合，
2 )在配混组合装置中将混合物熔融均匀， 挤出混合物， 冷却， 即得
所需产品。
19、根据权利要求 18所述的阻燃聚合物模塑组合物的制备方法，其特 征在于，所述配混组合装置采用单螺杆挤出机或多区螺杆挤出机，配混组 合装置的有效螺杆长度为 4-200D, 其中 D为螺杆直径。
20、 根据权利要求 18-19任一阻燃聚合物模塑组合物的制备方法， 其 特征在于， 所述的聚合物为聚对苯二曱酸乙二醇酯， 熔融温度为
250-290 ; 或者所述的聚合物为聚对苯二曱酸丁二醇酯， 熔融温度为 230-270 X：； 或者所述的聚合物为聚酰胺 6， 熔融温度为 260-290 * ; 或者 所述的聚合物为聚酰胺 6，6， 熔融温度为 260-290 "C。
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| JP2018090913A (ja) * | 2015-04-10 | 2018-06-14 | 株式会社カネカ | 難燃性ポリエステル人工毛髪用繊維 |
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| EP3543272A4 (en) * | 2016-11-17 | 2020-05-20 | Mitsui Chemicals, Inc. | METHOD FOR PRODUCING POLYURETHANE RESIN, POLYURETHANE RESIN AND MOLDED BODY |
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| US6569974B1 (en) * | 1999-03-22 | 2003-05-27 | Clariant Gmbh | Polymeric phosphinic acids and salts thereof |
| US7348396B2 (en) * | 2003-03-04 | 2008-03-25 | Clariant Produkte (Deutschland) Gmbh | Modified polyethylenephosphinic acids and their salts |
| CN101906117A (zh) * | 2010-07-01 | 2010-12-08 | 叶金标 | 一种烷基次膦酸盐聚合物及其制备方法和应用 |
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| US4208322A (en) | 1978-04-13 | 1980-06-17 | Pennwalt Corporation | Polyester-polyamide resins flame retarded by poly(metal phosphinate)s |
| US4180495A (en) | 1978-04-13 | 1979-12-25 | Pennwalt Corporation | Polyester resins flame retarded by poly(metal phosphinate)s |
| US5647995A (en) | 1994-04-29 | 1997-07-15 | Nalco Chemical Company | Method for the control of calcium carbonate scale using compounds prepared from acetylenic compounds and inorganic phosphite salts and their derivatives |
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| US6569974B1 (en) * | 1999-03-22 | 2003-05-27 | Clariant Gmbh | Polymeric phosphinic acids and salts thereof |
| US7348396B2 (en) * | 2003-03-04 | 2008-03-25 | Clariant Produkte (Deutschland) Gmbh | Modified polyethylenephosphinic acids and their salts |
| CN101906117A (zh) * | 2010-07-01 | 2010-12-08 | 叶金标 | 一种烷基次膦酸盐聚合物及其制备方法和应用 |
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