CN110003268A - A kind of preparation method of dialkylphosphinic salts - Google Patents
A kind of preparation method of dialkylphosphinic salts Download PDFInfo
- Publication number
- CN110003268A CN110003268A CN201910170113.9A CN201910170113A CN110003268A CN 110003268 A CN110003268 A CN 110003268A CN 201910170113 A CN201910170113 A CN 201910170113A CN 110003268 A CN110003268 A CN 110003268A
- Authority
- CN
- China
- Prior art keywords
- preparation
- dialkylphosphinic salts
- reaction
- initiator
- ionic liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 150000003839 salts Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- -1 azo compound Chemical class 0.000 claims description 33
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 150000001768 cations Chemical group 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 150000003233 pyrroles Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 31
- 239000005977 Ethylene Substances 0.000 description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- 239000003063 flame retardant Substances 0.000 description 15
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000011734 sodium Substances 0.000 description 12
- 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 10
- 239000004952 Polyamide Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical class CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000002459 sustained effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 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 description 5
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical class N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MNYOKDIIUJDYBM-UHFFFAOYSA-N 1-benzyl-3-methyl-2h-imidazole Chemical compound C1=CN(C)CN1CC1=CC=CC=C1 MNYOKDIIUJDYBM-UHFFFAOYSA-N 0.000 description 1
- FQTUOJOWQBMFTM-UHFFFAOYSA-N 1-butyl-3-ethenyl-2h-imidazole Chemical compound CCCCN1CN(C=C)C=C1 FQTUOJOWQBMFTM-UHFFFAOYSA-N 0.000 description 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- QQAJQOSQIHCXPL-UHFFFAOYSA-N 1-butyl-3-methyl-2h-pyridine Chemical compound CCCCN1CC(C)=CC=C1 QQAJQOSQIHCXPL-UHFFFAOYSA-N 0.000 description 1
- CDXLWOUTFCMPDM-UHFFFAOYSA-N 1-butyl-4-methyl-2h-pyridine Chemical compound CCCCN1CC=C(C)C=C1 CDXLWOUTFCMPDM-UHFFFAOYSA-N 0.000 description 1
- AXWLKJWVMMAXBD-UHFFFAOYSA-N 1-butylpiperidine Chemical compound CCCCN1CCCCC1 AXWLKJWVMMAXBD-UHFFFAOYSA-N 0.000 description 1
- JSHASCFKOSDFHY-UHFFFAOYSA-N 1-butylpyrrolidine Chemical compound CCCCN1CCCC1 JSHASCFKOSDFHY-UHFFFAOYSA-N 0.000 description 1
- RBBLMDJCDCGZOT-UHFFFAOYSA-N 1-decyl-2,3-dimethyl-2h-imidazole Chemical class CCCCCCCCCCN1C=CN(C)C1C RBBLMDJCDCGZOT-UHFFFAOYSA-N 0.000 description 1
- NUUDMTGMAZJCBY-UHFFFAOYSA-N 1-decyl-3-methyl-2h-imidazole Chemical compound CCCCCCCCCCN1CN(C)C=C1 NUUDMTGMAZJCBY-UHFFFAOYSA-N 0.000 description 1
- DVNFMHWKXQEEAH-UHFFFAOYSA-N 1-dodecyl-3-methyl-2h-imidazole Chemical compound CCCCCCCCCCCCN1CN(C)C=C1 DVNFMHWKXQEEAH-UHFFFAOYSA-N 0.000 description 1
- UVQPDGXQIPNYNU-UHFFFAOYSA-N 1-ethenyl-3-ethyl-2h-imidazole Chemical compound CCN1CN(C=C)C=C1 UVQPDGXQIPNYNU-UHFFFAOYSA-N 0.000 description 1
- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical compound CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 description 1
- GMDSSNPVDDOCII-UHFFFAOYSA-N 1-ethenyl-3-propyl-2H-imidazole Chemical compound C(=C)N1CN(C=C1)CCC GMDSSNPVDDOCII-UHFFFAOYSA-N 0.000 description 1
- ANTRPGYRFWBOCY-UHFFFAOYSA-N 1-ethoxy-3-methyl-2h-imidazole Chemical compound CCON1CN(C)C=C1 ANTRPGYRFWBOCY-UHFFFAOYSA-N 0.000 description 1
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical compound CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 description 1
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 1
- JWGNRZBHPGAAOQ-UHFFFAOYSA-N 1-hexyl-3-methyl-2H-pyridine Chemical compound C(CCCCC)N1CC(=CC=C1)C JWGNRZBHPGAAOQ-UHFFFAOYSA-N 0.000 description 1
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 description 1
- UFRSDCCXHKWLKT-UHFFFAOYSA-N 1-hexyl-4-methyl-2H-pyridine Chemical compound C(CCCCC)N1CC=C(C=C1)C UFRSDCCXHKWLKT-UHFFFAOYSA-N 0.000 description 1
- KTUWFYALZIAAGE-UHFFFAOYSA-N 1-methyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C=C1 KTUWFYALZIAAGE-UHFFFAOYSA-N 0.000 description 1
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 description 1
- JFYZBXKLRPWSGV-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole Chemical compound CCCN1CN(C)C=C1 JFYZBXKLRPWSGV-UHFFFAOYSA-N 0.000 description 1
- FIOYZGZRZWNKTB-UHFFFAOYSA-N 1-methyl-3-tetradecyl-2h-imidazole Chemical compound CCCCCCCCCCCCCCN1CN(C)C=C1 FIOYZGZRZWNKTB-UHFFFAOYSA-N 0.000 description 1
- XDEQOBPALZZTCA-UHFFFAOYSA-N 1-octylpyridin-1-ium Chemical compound CCCCCCCC[N+]1=CC=CC=C1 XDEQOBPALZZTCA-UHFFFAOYSA-N 0.000 description 1
- NGODQOAMHQTQTQ-UHFFFAOYSA-N 1-octylpyridin-1-ium;nitrate Chemical compound [O-][N+]([O-])=O.CCCCCCCC[N+]1=CC=CC=C1 NGODQOAMHQTQTQ-UHFFFAOYSA-N 0.000 description 1
- HGGLDADJQQPKKC-UHFFFAOYSA-N 2-butyl-1-methylimidazole Chemical compound CCCCC1=NC=CN1C HGGLDADJQQPKKC-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- IGAUTZDJQQBQRU-UHFFFAOYSA-N 3-methyl-1-octyl-2H-pyridine Chemical compound CC=1CN(C=CC=1)CCCCCCCC IGAUTZDJQQBQRU-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- NHQMOOZIVSRONZ-UHFFFAOYSA-N 4-methyl-1-octyl-2H-pyridine Chemical compound C(CCCCCCC)N1CC=C(C=C1)C NHQMOOZIVSRONZ-UHFFFAOYSA-N 0.000 description 1
- NMILGIZTAZXMTM-UHFFFAOYSA-N 4-propylmorpholine Chemical compound CCCN1CCOCC1 NMILGIZTAZXMTM-UHFFFAOYSA-N 0.000 description 1
- MTWVYGIIHVUGNL-UHFFFAOYSA-N CCCCP(O)=O Chemical class CCCCP(O)=O MTWVYGIIHVUGNL-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
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- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- BFBBORWYMUBDMS-UHFFFAOYSA-N [Na].C(C)P(O)=O Chemical compound [Na].C(C)P(O)=O BFBBORWYMUBDMS-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XHIHMDHAPXMAQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XHIHMDHAPXMAQK-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SPWAXFLJYHRRJL-UHFFFAOYSA-N butyl(ethyl)phosphinic acid Chemical class CCCCP(O)(=O)CC SPWAXFLJYHRRJL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- MJUJXFBTEFXVKU-UHFFFAOYSA-N diethyl phosphonate Chemical class CCOP(=O)OCC MJUJXFBTEFXVKU-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CAIZIGKCPQJNCW-UHFFFAOYSA-N nitric acid;pyridine Chemical compound O[N+]([O-])=O.C1=CC=NC=C1 CAIZIGKCPQJNCW-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Chemical class 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- RJFSDTDWWBECIL-UHFFFAOYSA-N trifluoro(methyl)-$l^{4}-sulfane Chemical compound CS(F)(F)F RJFSDTDWWBECIL-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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)]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a kind of preparation methods of dialkylphosphinic salts.The preparation method of this dialkylphosphinic salts, comprising the following steps: 1) hypophosphorous acid source and water are added in the reactor；2) alkene is added into reactor；3) it heats, the mixed liquor of initiator and ionic liquid is added, is reacted, obtains dialkylphosphinic salts.The present invention is by introducing ionic liquid as secondary solvent, increase alkene in the solubility property of solvent, and ionic liquid is to be gradually introduced into reaction system, while being stepped up dissolubility, the disposable a large amount of generations for introducing and leading to long-chain telomer are reduced, reaction pressure is reduced.
Description
Technical field
The invention belongs to technical field of flame retardant, in particular to a kind of preparation method of dialkylphosphinic salts.
Background technique
Flameproof polyamide and polyester are widely used two classes fire-resistant engineering plastics, they are mainly used for electronics, electrical, instrument
Table, automobile and other industries have the applicating history of decades.The polyamide and polyester industrially produced is divided into enhanced and non-increasing
Strong type two major classes, flame retardant products generally require UL94V0 fire-retardant rank.For some special applications, other performance is for example scorching hot
Silk, creepage trace index (CTI), heat ageing etc. have corresponding requirement.
Applying the flame-retardant system of Flameproof polyamide and polyester plastics on the market at present includes bromide fire retardant, generally there is bromo
Polystyrene (BPS), decabromodiphenylethane, brominated epoxy resin (BER) etc., compound a certain amount of antimony oxide (ATO), can
To stably reach UL94V0 fire-retardant rank.But bromide fire retardant is not enough environmentally friendly in addition to using, when burning, releases a large amount of toxic dense
Except cigarette, for playing fire-retardant polyamide or polyester plastics, ageing-resistant performance is poor, easily causes product flavescence.Secondly, fire-retardant
The creepage trace index of material is lower, not applicable for some demanding application systems of products C TI.
Another is halogen-free flame-retardant system, includes red phosphorus (RP), hypophosphites (AHP or ZHP), dialkyl phosphinic acid
Salt (OP), melamine cyanurate (MCA) etc..Wherein, although red phosphorus excellent fireproof performance, there is color requirement to product,
Red phosphorus is easy to be precipitated, and has corrosion to machine；Melamine cyanurate is for the fire-retardant unstable of polyamide；Hypophosphites decomposes
Temperature is lower, and bad control when processing, and is easy to decomposite hydrogen phosphide equipment and material is caused to be caught fire.
Dialkylphosphinic salts have good flame retardant property to Flameproof polyamide and polyester plastics, and hinder without bromine system
Combustion system bring environmental problem does not need additionally to add antimony oxide, at the same can be very good solve Flameproof polyamide and
The ageing-resistant problem of polyester plastics, and the creepage trace index of Flameproof polyamide product is improved, it is taken as bromine system to hinder on the market
Fire the favorable substitutes of agent.
The synthesis of dialkylphosphinic salts, earliest documents see the beauty of Shell Development Company in 1948
The United States Patent (USP) US2957931 of state patent US2724718 and Socony Mobil Oil Company in 1949, the two are adopted
The alkene addition of compound and unsaturation C=C with hypophosphorous acid and/or salt etc. containing P-H key, obtains the dioxane with P-C key
Base phosphinates.Although also there is document to carry out reacting obtained dialkyl hypophosphorous acid as raw material and yellow phosphorus etc. using alkyl halide backward
Salt, but have no that it has extensive industrialization.
After 2000, German Clariant company improves method on the basis of forefathers, uses hypophosphites and second
Aluminum diethylphosphinate fire retardant is made in alkene reaction, and has carried out extensive industrialization, and carry out a large amount of derivatives in this approach
Synthesis, it is domestic that also this fire retardant is conducted in-depth research there are many research institution.
Current dialkylphosphinic salts synthetic method is broadly divided into substantially using alkene and hypophosphorous acid and/or reactant salt
Two kinds of systems.One is use organic solvent system, most common solvent be acetic acid, due to ethylene acetic acid solubility compared with
Greatly, thus alkyl be combined to using pressure it is lower, generally in 0.5MPa or so.But there are two disadvantages for this method: first is that closing
At dialkylphosphinic salts fire retardant have acetate residual, subsequent use can corrode screw rod, while can also cause polyamide
It decomposes, acetic acid taste is heavier in processing.Patent document CN1660857A is pointed out: the residual solvent (acetic acid) with special low content
It is brought especially low with the diethyl phosphinates of telomerization product (ethyl-butyl hypophosphites) when they are introduced into plastics
The horizontal damage (the especially degradation of telomer) to surrounding plastic；Second is that using organic solvent (acetic acid) can bring it is some not
Desired telomer --- long-chain dialkylphosphinic salts, general content can contain too many long-chain dialkyl group between 6-12%
Phosphinates can have an impact Flameproof polyamide and polyester mechanical property, while the thermal decomposition temperature of long-chain dialkylphosphinic salts
Degree is usually less than diethyl phosphinates, so can reduce product decomposition temperature containing too many long-chain dialkylphosphinic salts.Separately
A kind of outer system is to be alkylated using water as solvent, since the dissolubility of ethylene in water is excessively poor, so can only mention
High pressure increases the solubility property of ethylene in water, generally requires 2MPa or more, just available more applicable yield, if
Hypotony, conversion rate of products can be very low, and mono-substituted alkyl phosphinate can also increase.But condition of high voltage is in industry
Upper industrialization can all bring certain risk.
Summary of the invention
Of the existing technology in order to overcome the problems, such as, the purpose of the present invention is to provide a kind of systems of dialkylphosphinic salts
Preparation Method.
In order to achieve the above purpose, the technical solution used in the present invention is:
A kind of preparation method of dialkylphosphinic salts, comprising the following steps:
1) hypophosphorous acid source and water are added in the reactor；The hypophosphorous acid source be hypophosphites or hypophosphites and
Hypophosphorous acid mixture；
2) alkene is added into reactor；
3) it heats, the mixed liquor of initiator and ionic liquid is added, is reacted, obtains dialkylphosphinic salts.
Preferably, in the preparation method step 1) of this dialkylphosphinic salts, hypophosphites Li, Na, K, Mg, Ca,
The hypophosphites of at least one of Ba, Al, Zr, Sn, Sr, Sb, Ge, Ti, Zn, Ce metal；It is further preferred that hypophosphites is
At least one of sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, hypo-aluminum orthophosphate, zinc hypophosphite.
Preferably, in the preparation method step 1) of this dialkylphosphinic salts, the mass ratio of hypophosphorous acid source and water is 1:
(2~10)；It is further preferred that the mass ratio of hypophosphorous acid source and water is 1:(5~8).
Preferably, in the preparation method step 2) of this dialkylphosphinic salts, shown in the structure of alkene such as formula (I):
In formula (I), R1、R2、R3、R4Independently indicate hydrogen, the alkyl or cycloalkyl of the linear chain or branched chain of C1-C18, benzene
Base, alkyl-substituted phenyl.
It is further preferred that alkene is the alkene of C2~C18 in the preparation method step 2) of this dialkylphosphinic salts
Hydrocarbon；Still further preferably, alkene is at least one of ethylene, propylene, butylene.
Preferably, in the preparation method step 2) of this dialkylphosphinic salts, after specially reactor is vacuumized, then
Alkene is added, and reactor pressure is made to remain 0.2MPa~0.4MPa.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, in step 3), initiator and ionic liquid
Mixed liquor be at the uniform velocity to be added, addition speed be 0.5L/h~1.5L/h；It is further preferred that initiator and ionic liquid is mixed
Closing liquid is added in reactor with the flow velocity of 0.8L/h~1.2L/h.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, initiator and ionic liquid is at the uniform velocity added
Mixed liquor be to be added by using metering pump.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, the mixed liquor of initiator and ionic liquid
In, the mass concentration of initiator is 0.5%~5%；It is further preferred that causing in the mixed liquor of initiator and ionic liquid
The mass concentration of agent is 1%~3%.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, the mixed liquor of initiator and ionic liquid
In, the solvent of mixed liquor is water.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, the mass ratio of initiator and ionic liquid
For 1:(0.01~100)；It is further preferred that the mass ratio of initiator and ionic liquid is 1:(0.1~10)；It is further excellent
The mass ratio of the volume of choosing, initiator and ionic liquid is 1:(0.5~2).
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, initiator is azo compound initiation
At least one of agent, peroxide initiator；It is further preferred that initiator be 4,4 '-azos bis- (4- cyanopentanoic acids), 2,
Bis- (2- amidine propane) dihydrochlorides of 2 '-azos bis- (2- methylbutyronitriles), 2,2 '-azos, 2,2 '-azo diisobutyl amidines two
Hydrochloride, hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, SODIUM PERCARBONATE, tert-butyl hydroperoxide, two uncle of peroxidating
At least one of butyl；Still further preferably, initiator 4,4 '-azos bis- (4- cyanopentanoic acids), 2,2 '-azos two are different
At least one of butyl amidine dihydrochloride, ammonium persulfate.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, ionic liquid be by cation group and
Anionic group composition, the cation group are selected from alkyl imidazolium cation, pyridine cationoid, piperidines cationoid, pyrrole
Cough up at least one of cationoid, morpholine cationoid, quaternaries cation, quaternary phosphonium salt cationoid, the yin from
Subbase group is selected from sulfuric ester root, phosphate root, tetrafluoroborate, hexafluoro-phosphate radical, hexafluoroantimonic anion, nitrate anion, trifluoro methylsulphur
Acid group, perchlorate, thiocyanate radical, methanesulfonate, p-methyl benzenesulfonic acid root, acetate, trifluoroacetic acid root, bisulfate ion, halogen
At least one of anion；It is further preferred that cation group is selected from 1,3- methylimidazole, 1- second in ionic liquid
Base -3- methylimidazole, 1- propyl -3- methylimidazole, 1- butyl -3- methylimidazole, 1- hexyl -3- methylimidazole, 1- octyl -3-
Methylimidazole, 1- decyl -3- methylimidazole, 1- dodecyl -3- methylimidazole, 1- myristyl -3- methylimidazole, 1- 16
Alkyl -3- methylimidazole, 1- benzyl -3- methylimidazole, 1- allyl -3- methylimidazole, 1- vinyl -3- methylimidazole, 1-
Ethyl -3- vinyl imidazole, 1- propyl -3- vinyl imidazole, 1- butyl -3- vinyl imidazole, 1- benzyl -3- vinyl miaow
Azoles, 1- allyl -3- vinyl imidazole, 1- ethyl -2,3- methylimidazole, 1- propyl -2,3- methylimidazole, 1- butyl -
2,3- methylimidazole, 1- hexyl -2,3- methylimidazole, 1- octyl -2,3- methylimidazole, 1- decyl -2,3- dimethyl
Imidazoles, 1- dodecyl -2,3- methylimidazole, 1- cetyl -2,3- methylimidazole, 1- benzyl -2,3- methylimidazole,
1- allyl -2,3- methylimidazole, N- ethylpyridine, N- butyl-pyridinium, N- octylpyridinium, N- butyl -3- picoline, N-
Hexyl -3- picoline, N- octyl -3- picoline, N- butyl -4- picoline, N- hexyl -4- picoline, N- octyl -
4- picoline, N- methyl, ethyl piperidine, N- methyl, propylpiperdine, N- methyl, butyl piperidine, N- methyl, ethyl pyrrolidine,
N- methyl, propyl pyrrole alkane, N- methyl, butyl pyrrolidine, N- methyl, ethyl morpholine, N- methyl, propylmorpholin, N- methyl, fourth
Base morpholine, 1- ethoxy -3- methylimidazole, 2- hydroxy-n, N, N,-trimethyl ethamine, N- sulfonic acid butyl -3- methylimidazole, 1-
At least one of ethylacrylate methyl -3- methylimidazole, 1- acetonitrile-base -3- methylimidazole, anionic group be selected from Methylsulfate base,
Ethyl-sulfate base, dimethyl phosphate base, p diethylaminobenzoic acid ester group, tetrafluoroborate, hexafluoro-phosphate radical, hexafluoroantimonic anion, nitrate anion,
Trifluoromethanesulfonic acid root, perchlorate, thiocyanate radical, methanesulfonate, p-methyl benzenesulfonic acid root, acetate, trifluoroacetic acid root, hydrogen sulfate
At least one of root；Still further preferably, ionic liquid 1,3- methylimidazole mesylate, N- octylpyridinium nitric acid
At least one of salt, 1- butyl -2,3- methylimidazole disulfate.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, the temperature of reaction is 60 DEG C~120 DEG C；
It is further preferred that the temperature of reaction is 80 DEG C~110 DEG C.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, the pressure of reaction is 0.1MPa~1MPa；
It is further preferred that the pressure of reaction is 0.3MPa~0.5MPa.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, the time of reaction is 2h~10h；Into one
Step is preferred, and the time of reaction is 4h~8h.
Preferably, in the preparation method step 3) of this dialkylphosphinic salts, cool down after reaction, reactor is discharged
In remaining alkene, obtain the aqueous solution of dialkylphosphinic salts；It is further preferred that be cooled to after reaction 50 DEG C with
Under, remaining alkene is discharged by the relief pipeline of reactor, obtains the aqueous solution of dialkylphosphinic salts.
Preferably, in the preparation method of this dialkylphosphinic salts, the mass ratio of hypophosphorous acid source and initiator is 1:
(0.01~0.05)；It is further preferred that the mass ratio of hypophosphorous acid source and initiator is 1:(0.02~0.04).
Further, in the preparation method of this dialkylphosphinic salts, obtained dialkylphosphinic salts structural formula is such as
Shown in formula (II):
In formula (II), R5、R6Independently indicate hydrogen, the alkyl or cycloalkyl of the linear chain or branched chain of C1-C18, phenyl, alkane
The phenyl that base replaces；N=1~4；M is at least one in Li, Na, K, Mg, Ca, Ba, Al, Zr, Sn, Sr, Sb, Ge, Ti, Zn, Ce
Kind.
The beneficial effects of the present invention are:
1) dialkylphosphinic salts preparation method of the invention uses water, as solvent, to reduce side reaction without the use of acetic acid
Generation, while reducing alkylation synthesis pressure, reduce equipment pressure requirements.
2) present invention is used as secondary solvent, solubility property of the increase alkene in solvent, and ion by introducing ionic liquid
Liquid is to be gradually introduced into reaction system, while being stepped up dissolubility, and reducing disposable introduce leads to long-chain telomer
It is a large amount of to generate, reduce reaction pressure.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained or be prepared by a conventional method to obtain from routine business approach.
Embodiment 1
One hydration sodium hypophosphite 3kg and water 20kg is added in 50L stainless steel cauldron, it is closed, it is set under stirring with nitrogen
It changes twice, vacuum is evacuated in kettle, ethylene is slowly introducing in reaction kettle by being set to the pressure reducer of 0.3MPa, until reaction
Pressure gauge is shown as 0.3MPa on kettle, opens heating device, is heated by oil bath to reaction kettle.When kettle reaction mixture
When being heated to 95 DEG C, continues logical ethylene to reacting kettle inner pressure and reach 0.5MPa, the ionic liquid 1 that will be stirred in advance, 3- bis-
Methylimidazole mesylate 100g, bis- (4- cyanopentanoic acid) 100g of 4,4 '-azos, water 5kg mixed liquor are at the uniform velocity squeezed into metering pump
In reaction kettle (metering pump flow rate set is 1.0L/h), with the progress of reaction, reacting kettle inner pressure is begun to decline, whenever pressure
When table numerical value drops to 0.3MPa, then logical ethylene makes it go up to 0.5MPa, under this condition sustained response 6h, and reaction was completed.It opens
Begin to cool down, when reactor temperature is down to 50 DEG C or less, be let out by relief pipeline except residual ethylene in kettle, obtains diethyl
Phosphonic acids sodium water solution.
Embodiment 2
One hydration sodium hypophosphite 3kg and water 20kg is added in 50L stainless steel cauldron, it is closed, it is set under stirring with nitrogen
It changes twice, vacuum is evacuated in kettle, ethylene is slowly introducing in reaction kettle by being set to the pressure reducer of 0.3MPa, until reaction
Pressure gauge is shown as 0.3MPa on kettle, opens heating device, is heated by oil bath to reaction kettle.When kettle reaction mixture
When being heated to 90 DEG C, continues logical ethylene to reacting kettle inner pressure and reach 0.5MPa, the ionic liquid N-octyl that will be stirred in advance
Pyridine nitrate 100g, ammonium persulfate 100g, water 5kg mixed liquor at the uniform velocity squeeze into reaction kettle that (metering flow rate pump is set with metering pump
It is set to 1.0L/h), with the progress of reaction, reacting kettle inner pressure is begun to decline, when pressure gauge numerical value drops to 0.3MPa,
Leading to ethylene again makes it go up to 0.5MPa, under this condition sustained response 6h.Reaction was completed, starts to cool down, works as reactor temperature
It when being down to 50 DEG C or less, is let out by relief pipeline except residual ethylene in kettle, obtains diethyl phosphinic acids sodium water solution.
Embodiment 3
One hydration sodium hypophosphite 3kg and water 20kg is added in 50L stainless steel cauldron, it is closed, it is set under stirring with nitrogen
It changes twice, vacuum is evacuated in kettle, ethylene is slowly introducing in reaction kettle by being set to the pressure reducer of 0.3MPa, until reaction
Pressure gauge is shown as 0.3MPa on kettle, opens heating device, is heated by oil bath to reaction kettle.When kettle reaction mixture
When being heated to 90 DEG C, continues logical ethylene to reacting kettle inner pressure and reach 0.5MPa, the ionic liquid 1- butyl-that will be stirred in advance
2,3- methylimidazole disulfate 100g, 2,2 '-azo diisobutyl amidine dihydrochloride 100g, water 5kg mixed liquor, with metering
Pump at the uniform velocity squeezes into reaction kettle (metering pump flow rate set is 1.0L/h), with the progress of reaction, under reacting kettle inner pressure starts
Drop, when pressure gauge numerical value drops to 0.3MPa, then logical ethylene makes it go up to 0.5MPa, under this condition sustained response 6h.
Reaction was completed, starts to cool down, and when reactor temperature is down to 50 DEG C or less, is let out by relief pipeline except residual ethylene in kettle,
Obtain diethyl phosphinic acids sodium water solution.
Comparative example 1
One hydration sodium hypophosphite 3kg and acetic acid 20kg is added in 50L enamel reaction still, it is closed, it is set under stirring with nitrogen
It changes twice, vacuum is evacuated in kettle, ethylene is slowly introducing in reaction kettle by being set to the pressure reducer of 0.3MPa, until reaction
Pressure gauge is shown as 0.3MPa on kettle, opens heating device, is heated by oil bath to reaction kettle.When kettle reaction mixture
When being heated to 100 DEG C, continues logical ethylene to reacting kettle inner pressure and reach 0.5MPa, 2 will stirred in advance, the bis- (2- of 2 '-azos
Amidine propane) two hydrogen chloride 100g, water 5kg mixed liquor at the uniform velocity squeezes into reaction kettle that (metering pump flow rate set is with metering pump
1.0L/h), with the progress of reaction, reacting kettle inner pressure is begun to decline, and when pressure gauge numerical value drops to 0.3MPa, then is led to
Ethylene makes it go up to 0.5MPa, under this condition sustained response 6h.Reaction was completed, starts to cool down, when reactor temperature is down to
It at 50 DEG C or less, is let out by relief pipeline except residual ethylene in kettle, obtains diethyl phosphinic acids sodium water solution.
Comparative example 2
One hydration sodium hypophosphite 3kg and water 20kg is added in 50L stainless steel cauldron, it is closed, it is set under stirring with nitrogen
It changes twice, vacuum is evacuated in kettle, ethylene is slowly introducing in reaction kettle by being set to the pressure reducer of 0.3MPa, until reaction
Pressure gauge is shown as 0.3MPa on kettle, opens heating device, is heated by oil bath to reaction kettle.When kettle reaction mixture
When being heated to 100 DEG C, continues logical ethylene to reacting kettle inner pressure and reach 0.5MPa, 2 will stirred in advance, the bis- (2- of 2 '-azos
Amidine propane) dihydrochloride 100g, water 5kg mixed liquor at the uniform velocity squeezes into reaction kettle that (metering pump flow rate set is with metering pump
1.0L/h), with the progress of reaction, reacting kettle inner pressure is begun to decline, and when pressure gauge numerical value drops to 0.3MPa, then is led to
Ethylene makes it go up to 0.5MPa, under this condition sustained response 6h.Reaction was completed, starts to cool down, when reactor temperature is down to
It at 50 DEG C or less, is let out by relief pipeline except residual ethylene in kettle, obtains diethyl phosphinic acids sodium water solution.
Comparative example 3
One hydration sodium hypophosphite 3kg and water 20kg is added in 50L stainless steel cauldron, it is closed, it is set under stirring with nitrogen
It changes twice, vacuum is evacuated in kettle, ethylene is slowly introducing in reaction kettle by being set to the pressure reducer of 0.3MPa, until reaction
Pressure gauge is shown as 0.3MPa on kettle, opens heating device, is heated by oil bath to reaction kettle.When kettle reaction mixture
When being heated to 100 DEG C, continues logical ethylene to reacting kettle inner pressure up to 2MPa, bis- (the 2- amidino groups of 2,2 '-azos will be stirred in advance
Propane) dihydrochloride 100g, water 5kg mixed liquor at the uniform velocity squeezes into reaction kettle that (metering pump flow rate set is with metering pump
0.5L/h), with the progress of reaction, reacting kettle inner pressure is begun to decline, when pressure gauge numerical value drops to 1MPa, then logical second
Alkene makes it go up to 2MPa, under this condition sustained response 11h.Reaction was completed, starts to cool down, when reactor temperature is down to 50 DEG C
It when following, is let out by relief pipeline except residual ethylene in kettle, obtains diethyl phosphinic acids sodium water solution.
Comparative example 4
Sodium hypophosphite 3kg, water 20kg and ionic liquid 1,3- methylimidazole mesylate 100g are hydrated by one, and 50L is added
It is closed in stainless steel cauldron, under stirring twice with nitrogen displacement, vacuum is evacuated in kettle, by ethylene by being set to
The pressure reducer of 0.3MPa is slowly introducing in reaction kettle, until pressure gauge is shown as 0.3MPa on reaction kettle, is opened heating device, is led to
Oil bath is crossed to heat reaction kettle.When kettle reaction mixture is heated to 95 DEG C, continue logical ethylene to reacting kettle inner pressure
Up to 0.5MPa, 4 will stirred in advance, bis- (4- cyanopentanoic acid) 100g of 4 '-azos, water 5kg mixed liquor, at the uniform velocity with metering pump
(metering pump flow rate set is 1.0L/h) is squeezed into reaction kettle, with the progress of reaction, reacting kettle inner pressure is begun to decline, whenever
When pressure gauge numerical value drops to 0.3MPa, then logical ethylene makes it go up to 0.5MPa, under this condition sustained response 6h.Terminate anti-
It answers, starts to cool down, when reactor temperature is down to 50 DEG C or less, is let out by relief pipeline except residual ethylene in kettle, obtain two
Ethylphosphinic acid sodium water solution.
The product of Examples 1 to 3 and comparative example 1~4 is carried out31PNMR analysis, molar content (mol%) knot of each substance
Fruit is as shown in table 1.
1 embodiment and comparative example product of table31PNMR analyzes result
By the result of table 1: relative to comparative example 1, using acetic acid as solvent, the telomer second of product of the present invention
Base butyl phosphinic acids sodium is less；Under same reaction pressure, it is molten not add secondary solvent using water as solvent for relative contrast's example 2
Ethylene is solved, product of the present invention has significantly higher diethyl phosphinic acids sodium yield；Relative contrast's example 3, using water as solvent, no
It adds secondary solvent and dissolves ethylene, in order to obtain same levels purity product, need to improve reaction pressure to 2MPa, present invention tool
There is more apparent low pressure advantage；Relative contrast's example 4 under equivalent assay conditions, is added at one time secondary solvent ionic liquid, leads
Product telomer ethyl-butyl phosphinic acids sodium ratio is caused to increase significantly, the purity of major product diethyl phosphinic acids sodium reduces.To sum up
Described, the dialkylphosphinic salts product purity that preparation method of the embodiment of the present invention obtains is high, and by-product is few.
Claims (10)
1. a kind of preparation method of dialkylphosphinic salts, it is characterised in that: the following steps are included:
1) hypophosphorous acid source and water are added in the reactor；The hypophosphorous acid source is hypophosphites or hypophosphites and time phosphorus
Acid blend；
2) alkene is added into reactor；
3) it heats, the mixed liquor of initiator and ionic liquid is added, is reacted, obtains dialkylphosphinic salts.
2. a kind of preparation method of dialkylphosphinic salts according to claim 1, it is characterised in that: secondary in step 1)
Phosphate is the hypophosphites of at least one of Li, Na, K, Mg, Ca, Ba, Al, Zr, Sn, Sr, Sb, Ge, Ti, Zn, Ce metal.
3. a kind of preparation method of dialkylphosphinic salts according to claim 1, it is characterised in that: secondary in step 1)
The mass ratio of source of phosphoric acid and water is 1:(2~10).
4. a kind of preparation method of dialkylphosphinic salts according to claim 1, it is characterised in that: in step 2), alkene
Shown in the structure of hydrocarbon such as formula (I):
In formula (I), R1、R2、R3、R4Independently indicate hydrogen, the alkyl or cycloalkyl of the linear chain or branched chain of C1-C18, phenyl, alkane
The phenyl that base replaces.
5. a kind of preparation method of dialkylphosphinic salts according to claim 1, it is characterised in that: in step 3), draw
The mixed liquor for sending out agent and ionic liquid is at the uniform velocity to be added, and addition speed is 0.5L/h~1.5L/h.
6. a kind of preparation method of dialkylphosphinic salts according to claim 5, it is characterised in that: in step 3), draw
In the mixed liquor for sending out agent and ionic liquid, the mass concentration of initiator is 0.5%~5%, the quality of initiator and ionic liquid
Than for 1:(0.01~100).
7. a kind of preparation method of dialkylphosphinic salts according to claim 6, it is characterised in that: in step 3), draw
Sending out agent is at least one of azo compound initiator, peroxide initiator.
8. a kind of preparation method of dialkylphosphinic salts according to claim 6, it is characterised in that: in step 3), from
Sub- liquid is made of cation group and anionic group, and the cation group is selected from alkyl imidazolium cation, pyridines
In cation, piperidines cationoid, pyrroles's cationoid, morpholine cationoid, quaternaries cation, quaternary phosphonium salt cationoid
At least one, the anionic group be selected from sulfuric ester root, phosphate root, tetrafluoroborate, hexafluoro-phosphate radical, hexafluoro antimony
Acid group, nitrate anion, trifluoromethanesulfonic acid root, perchlorate, thiocyanate radical, methanesulfonate, p-methyl benzenesulfonic acid root, acetate, trifluoro
At least one of acetate, bisulfate ion, halide anion.
9. according to a kind of described in any item preparation methods of dialkylphosphinic salts of claim 5~8, it is characterised in that: step
It is rapid 3) in, the temperature of reaction is 60 DEG C~120 DEG C, and the pressure of reaction is 0.1MPa~1MPa, and the time of reaction is 2h~10h.
10. a kind of preparation method of dialkylphosphinic salts according to claim 1, it is characterised in that: hypophosphorous acid source with
The mass ratio of initiator is 1:(0.01~0.05).
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