WO2022147941A1 - Dialkyl phosphinate preparation method - Google Patents
Dialkyl phosphinate preparation method Download PDFInfo
- Publication number
- WO2022147941A1 WO2022147941A1 PCT/CN2021/094487 CN2021094487W WO2022147941A1 WO 2022147941 A1 WO2022147941 A1 WO 2022147941A1 CN 2021094487 W CN2021094487 W CN 2021094487W WO 2022147941 A1 WO2022147941 A1 WO 2022147941A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- preparation
- dialkyl phosphinate
- reaction
- halogenated
- catalyst
- Prior art date
Links
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- -1 quaternary ammonium salt compound Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 150000008052 alkyl sulfonates Chemical class 0.000 claims abstract description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000004821 distillation Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 6
- 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 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 125000002009 alkene group Chemical group 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 8
- 125000005210 alkyl ammonium group Chemical group 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 7
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- LPFYDEANGXVAOA-UHFFFAOYSA-M sodium;diethylphosphinate Chemical compound [Na+].CCP([O-])(=O)CC LPFYDEANGXVAOA-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 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 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical class CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- BVTJGGGYKAMDBN-UHFFFAOYSA-N Dioxetane Chemical compound C1COO1 BVTJGGGYKAMDBN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- DRDKFCAHTAHYER-UHFFFAOYSA-N bis(2-methylpropyl)phosphinic acid Chemical compound CC(C)CP(O)(=O)CC(C)C DRDKFCAHTAHYER-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- DGZNEHPVXXRBIU-UHFFFAOYSA-N di(butan-2-yl)phosphinic acid Chemical compound CCC(C)P(O)(=O)C(C)CC DGZNEHPVXXRBIU-UHFFFAOYSA-N 0.000 description 1
- KSHDLNQYVGBYHZ-UHFFFAOYSA-N dibutylphosphinic acid Chemical compound CCCCP(O)(=O)CCCC KSHDLNQYVGBYHZ-UHFFFAOYSA-N 0.000 description 1
- UHUMDOUHVGSPDJ-UHFFFAOYSA-N diethylphosphane;hydrochloride Chemical compound [Cl-].CC[PH2+]CC UHUMDOUHVGSPDJ-UHFFFAOYSA-N 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-M dimethylphosphinate Chemical compound CP(C)([O-])=O GOJNABIZVJCYFL-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XNUIJAWJCXOJRK-UHFFFAOYSA-N ethyl(propyl)phosphinic acid Chemical compound CCCP(O)(=O)CC XNUIJAWJCXOJRK-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- SZTJCIYEOQYVED-UHFFFAOYSA-N methyl(propyl)phosphinic acid Chemical compound CCCP(C)(O)=O SZTJCIYEOQYVED-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- 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)]
- C07F9/32—Esters thereof
-
- 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
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the invention relates to the technical field of preparation of dialkyl phosphinates, in particular to a preparation method of dialkyl phosphinates.
- Phosphate ester is a multi-purpose chemical product, among which phosphite ester and alkyl phosphate ester are the main varieties of organophosphorus flame retardants, which have long-lasting flame retardant effect, good compatibility with polymer substrates, water resistance, It has the advantages of weather resistance, etc., so it is widely used in polymer materials such as polyurethane, epoxy resin, polycarbonate, and unsaturated resin.
- Phosphites include dimethyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc., which are mostly obtained by reacting phosphorus trichloride with corresponding alcohol or phenol.
- Phosphites with monoalkyl C-P structure including dimethyl methylphosphonate (DMMP), diethyl ethyl phosphate (DEEP), etc., mostly use trimethyl phosphite and triethyl phosphite as raw materials. rearrangement reaction.
- monoalkyl flame retardants are chemicals that are monitored by the International Organization for the Prohibition of Chemical Weapons, and their production, use and circulation are strictly controlled.
- Dialkylphosphinates also have good flame retardant properties due to the presence of hypophosphorous acid structures in their molecular structures. Hypophosphorous acid structures are contained in the molecular structures of currently widely used hypophosphite and organic derivative salt flame retardants. Moreover, because dialkyl phosphinates do not contain a monoalkyl structure, they are not controlled chemicals by the International OPCW, and have broad prospects in the follow-up development. However, the development and application of this type of compounds at home and abroad are late, and they have just started, and there are few chemical structures reported publicly.
- the present invention provides a method for preparing a dialkyl phosphinate, which uses a dialkyl phosphinate and a halogenated compound as raw materials to synthesize dialkyl by one-step method
- the phosphinate ester has higher yield, less by-products and easy separation, simple steps, short time-consuming, safe and environmentally friendly process, lower cost and easier implementation.
- the reaction process is as follows:
- R 1 and R 2 are independently selected from C 1 -C 24 alkyl groups (including alkane, cycloalkyl, etc.), aryl or alkenyl groups, and R 3 is selected from alkane groups, aromatic groups, alkenes group, epoxy group, alcohol group, phenol group or halogenated group, M is a metal element, X is a halogen, m is the valence number of the metal element M, and n is an integer of 1-3.
- the catalyst is one or more of phase transfer catalysts or amphoteric compounds, including cationic polyalkyl quaternary ammonium salt compounds, cationic halogenated polyalkyl quaternary ammonium salt compounds, alkyl ammonium chlorides, and alkyl ammonium bromides , at least one of anionic alkyl sulfate compounds, alkyl sulfonates, alkylbenzene sulfonates, nonionic surfactants, and quaternary phosphonium salts.
- phase transfer catalysts or amphoteric compounds including cationic polyalkyl quaternary ammonium salt compounds, cationic halogenated polyalkyl quaternary ammonium salt compounds, alkyl ammonium chlorides, and alkyl ammonium bromides , at least one of anionic alkyl sulfate compounds, alkyl sulfonates, alkylbenzene sulfonates, nonionic surfactants,
- the reactant dialkyl hypophosphite is solid, while the halogenated compound is usually liquid, which realizes the liquid-solid reaction under the action of the catalyst, and the one-step method realizes the preparation of the target product, the conversion rate is high, and the generation of
- the target compound by-produced inorganic halogenated metal salts, dialkyl hypophosphites are liquid, and these by-produced metal salts are insoluble in halogenated compounds and dialkyl hypophosphites, and exist in the reaction system in solid form It is easy to separate from the target product, and the halogenated metal salt is less harmful to the environment, will not burn and explode, the process is environmentally friendly and safe, and solves the defects of the traditional synthesis process.
- the halogenated compound can also be extracted from the product by simple means such as negative pressure evaporation. On the one hand, it can be recovered and recycled, and on the other hand, the purity of the target product dialkyl phosphinate is
- the dialkyl phosphinate can be specifically selected from: dimethyl phosphinate, diethyl phosphinate, methyl ethyl phosphinate, di-n-propyl phosphinate, diisopropyl phosphinate Phosphinate, methylpropylphosphinate, ethylpropylphosphinate, di-n-butylphosphinate, di-sec-butylphosphinate, diisobutylphosphinate, Di-tert-butyl phosphinate, methyl butyl hypophosphite, ethyl butyl hypophosphite, di-n-octyl hypophosphite, diisooctyl hypophosphite and other alkane groups up to 24 carbons of hypophosphite, etc.
- M is preferably selected from at least one of sodium, potassium, calcium, aluminum, magnesium, zinc, and barium.
- the halogenated compound can be specifically selected from: halogenated methane, halogenated ethane, halogenated propane, halogenated butane, halogenated ethylene oxide, halogenated propylene oxide, halogenated methyl propylene oxide, halogenated Butylene oxides, halomethanols, haloethanols, halobutanols, haloethylenes, halopropenes, halobenzenes, halotoluenes, halophenols, halomethylphenols, and other haloaromatics groups, olefins, epoxy groups, alcohols, phenolic groups, etc.
- X is preferably one or more selected from fluorine, chlorine, bromine and iodine.
- the catalyst includes polyalkyl ammonium chloride, polyalkyl ammonium bromide, alkyl sulfate, alkyl sulfonate, alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl phenol poly At least one of oxyethylene ether, alkyl phosphate, and polyol.
- the polyol includes ethylene glycol and the like.
- the temperature of the reaction is preferably 40-150°C, more preferably 100-150°C.
- the pressure of the reaction can be negative pressure, normal pressure, or pressure greater than one atmosphere, preferably 0-5 MPa, more preferably greater than one atmosphere and not greater than 5 MPa.
- reaction time can be selected according to actual needs.
- the length of the reaction time can be adjusted, depending on the catalyst, the reaction temperature, the desired degree of reaction, and the like.
- the reaction can be completed in 0.5-20 hours with a relatively fast reaction rate; optionally, the reaction time is 1-10 hours.
- the molar ratio of the dialkylphosphinate to the halogenated compound is preferably 1:0.1-10, more preferably 1:1.01-5.
- the amount of the catalyst used is 0.001wt% to 10wt% of the amount of the dialkylphosphinate. Further preferably, the dosage of the catalyst is 0.1wt%-5.0wt% of the dosage of the dialkylphosphinate.
- the preparation method can adopt batch or continuous reaction.
- a series of reaction devices such as pipeline reactors, can be used to carry out the reaction. After the reaction is completed, the product and raw materials are separated, and the excess halogenated compound is returned to the raw material tank to realize continuous reaction.
- the batch reaction can be carried out by using a series of reaction devices, such as a reaction kettle. After the reaction is completed, the product and raw materials are separated, and the excess halogenated compound is returned to the raw material tank to realize continuous reaction.
- a series of reaction devices such as a reaction kettle.
- C 1 -C 24 etc. refer to the number of carbon atoms contained in the group.
- alkyl is a group formed by the loss of any hydrogen atom on the molecule of an alkane compound.
- the alkane compounds include straight-chain alkanes, branched-chain alkanes, cycloalkanes, and the like.
- the finished product can be further purified.
- the purification includes methods such as reaction with additives, filtration or distillation.
- the product is filtered and distilled to obtain the product.
- the distillation described here can be distillation, evaporation; such as vacuum distillation, atmospheric distillation, falling film evaporation and other operating processes.
- the present invention Compared with the prior art, the present invention has the following main advantages: the present invention adopts dialkyl phosphinate and halogenated compounds as raw materials for one-step synthesis.
- the reaction process has the advantages of convenient operation, high reaction yield, little by-product pollution and low preparation cost.
- Fig. 1 is the schematic diagram of the phosphorus nuclear magnetic resonance spectrum ( 31 P NMR chart) of the product obtained in Example 1;
- Figure 2 is a schematic diagram of the hydrogen nuclear magnetic resonance spectrum ( 1 H NMR diagram) of the product obtained in Example 1;
- Fig. 3 is the nuclear magnetic resonance phosphorus spectrum schematic diagram of the product obtained therefrom in Example 2;
- Fig. 4 is the hydrogen nuclear magnetic resonance spectrum schematic diagram of the product obtained in Example 2.
- Fig. 5 is the nuclear magnetic resonance phosphorus spectrum schematic diagram of the product obtained in Example 3.
- FIG. 6 is a schematic diagram of the hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 3.
- FIG. 6 is a schematic diagram of the hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 3.
- the raw materials are purchased through commercial channels.
- NMR Nuclear Magnetic Resonance
- the molecular structure of the obtained target product can be determined by 31 P NMR and 1 H NMR.
- the calculation method of the yield is: (weight of product/theoretical weight of product) ⁇ 100%.
- Example 3 The only difference from Example 3 is that no catalyst is added, and the remaining steps and conditions are the same.
- the product is filtered and distilled to obtain 10 g of finished product with a conversion rate of 3%, and the product of formula (III) is obtained. It can be seen that if no catalyst is added, the conversion rate of this reaction is very low, and the conditions for industrial production are not met.
- the traditional technique for preparing ethyl diethyl hypophosphite takes sodium diethyl hypophosphite as a raw material, and the preparation technique comprises 3 steps:
- Example 1 Compared with Example 1, the same target product is prepared from the same raw material, the preparation steps of Comparative Example 2 are too long, and the yield is 67.5%, which is far lower than the one-step process of the present invention, and there are many by-products and side-products.
- the product is highly polluted and not environmentally friendly.
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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A dialkyl phosphinate preparation method, comprising: using dialkyl phosphinate and a halogenated compound as raw materials, and reacting under the action of a catalyst to obtain dialkyl phosphinate, the catalyst being one or more of a phase transfer catalyst or an amphoteric compound, and comprising at least one of a cationic polyalkyl quaternary ammonium salt compound, a cationic halogenated polyalkyl quaternary ammonium salt compound, alkyl ammonium chloride, alkyl ammonium bromide, an anionic alkyl sulfate compound, alkyl sulfonate, alkylbenzene sulfonate, a nonionic surfactant, and a quaternary phosphonium salt. The dialkyl phosphinate is synthesized by using the dialkyl phosphinate and the halogenated compound as raw materials by means of a one-step method, and compared with existing traditional synthesis methods, the present invention has the advantages that the yield is higher, byproducts are few, separation is easy, the steps are simple, consumed time is short, the process is safe and environmentally friendly, costs are low, and implementation is easier.
Description
本发明涉及二烷基次膦酸酯的制备技术领域,具体涉及一种二烷基次膦酸酯的制备方法。The invention relates to the technical field of preparation of dialkyl phosphinates, in particular to a preparation method of dialkyl phosphinates.
磷酸酯是一种多用途的化工品,其中亚磷酸酯和烷基磷酸酯是有机磷系阻燃剂的主要品种,它具有阻燃效果持久,与聚合物基材相容性好,耐水,耐候等优点,因而在聚氨酯,环氧树脂,聚碳酸酯,不饱和树脂等高分子材料中应用广泛。Phosphate ester is a multi-purpose chemical product, among which phosphite ester and alkyl phosphate ester are the main varieties of organophosphorus flame retardants, which have long-lasting flame retardant effect, good compatibility with polymer substrates, water resistance, It has the advantages of weather resistance, etc., so it is widely used in polymer materials such as polyurethane, epoxy resin, polycarbonate, and unsaturated resin.
亚磷酸酯包括亚磷酸二甲酯、亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三苯基酯等,多为使用三氯化磷和对应的醇或酚反应得到。Phosphites include dimethyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc., which are mostly obtained by reacting phosphorus trichloride with corresponding alcohol or phenol.
单烷基C-P结构的亚磷酸酯,包括甲基膦酸二甲酯(DMMP),乙基磷酸二乙酯(DEEP)等,多以亚磷酸三甲酯、亚磷酸三乙酯为原料,通过重排反应得到。同时单烷基类阻燃剂为国际禁化武组织重点监控的化学品,其生产、使用、流通均受到严格的管制。Phosphites with monoalkyl C-P structure, including dimethyl methylphosphonate (DMMP), diethyl ethyl phosphate (DEEP), etc., mostly use trimethyl phosphite and triethyl phosphite as raw materials. rearrangement reaction. At the same time, monoalkyl flame retardants are chemicals that are monitored by the International Organization for the Prohibition of Chemical Weapons, and their production, use and circulation are strictly controlled.
二烷基次膦酸酯,由于分子结构中存在次磷酸结构,同样具有良好的阻燃性能,目前广泛应用的次磷酸盐及有机衍生物盐类阻燃剂分子结构中就含有次磷酸结构。而且二烷基次膦酸酯因其不含有单烷基结构,不属于国际禁化武组织监控化学品,在后续的发展上具有广阔的前景。但该类化合物在国内外的开发和应用晚,刚起步,公开报道的化学结构很少,合成方法也主要为磷酰氯与醇或环氧化合物的反应(如公开号为CN112028932A的专利技术)或其他方法(如公开号为CN103965511A的专利技术)等,合成过程较长,工艺繁琐,反应压力高,对设备要求较高,所用单体昂贵,成本较高,而且副产大量的高污染的卤酸和易燃易爆的有机物,工艺不环保和不安全。因此,有必要开发新型的合成工艺,解决现有工艺面临的问题。Dialkylphosphinates also have good flame retardant properties due to the presence of hypophosphorous acid structures in their molecular structures. Hypophosphorous acid structures are contained in the molecular structures of currently widely used hypophosphite and organic derivative salt flame retardants. Moreover, because dialkyl phosphinates do not contain a monoalkyl structure, they are not controlled chemicals by the International OPCW, and have broad prospects in the follow-up development. However, the development and application of this type of compounds at home and abroad are late, and they have just started, and there are few chemical structures reported publicly. Other methods (such as the patented technology whose publication number is CN103965511A), etc., have long synthesis process, cumbersome process, high reaction pressure, high equipment requirements, expensive monomers, high cost, and by-produced a large amount of highly polluting halogens. Acids and flammable and explosive organics, the process is not environmentally friendly and unsafe. Therefore, it is necessary to develop a new synthesis process to solve the problems faced by the existing process.
发明内容SUMMARY OF THE INVENTION
针对上述技术问题以及本领域存在的不足之处,本发明提供了一种二烷基次膦酸酯的制备方法,采用二烷基次膦酸盐和卤代化合物为原料一步法合成二烷基次膦酸酯,相较于现有传统的合成方法,得率更高,副产物少且易分离,步骤简单,耗时短,工艺安全环保,成本较低,更容易实施。In view of the above-mentioned technical problems and deficiencies in the art, the present invention provides a method for preparing a dialkyl phosphinate, which uses a dialkyl phosphinate and a halogenated compound as raw materials to synthesize dialkyl by one-step method Compared with the existing traditional synthesis method, the phosphinate ester has higher yield, less by-products and easy separation, simple steps, short time-consuming, safe and environmentally friendly process, lower cost and easier implementation.
一种二烷基次膦酸酯的制备方法,以二烷基次膦酸盐和卤代化合物为原料,在催化剂作用下反应得到所述二烷基次膦酸酯;A preparation method of dialkyl phosphinate, using dialkyl phosphinate and halogenated compound as raw materials, and reacting under the action of a catalyst to obtain the dialkyl phosphinate;
反应过程如下:The reaction process is as follows:
其中,R
1、R
2分别独立选自C
1-C
24的烷基(包括链烷基、环烷基等)、芳基或烯基,R
3选自烷烃基团、芳香基团、烯烃基团、环氧基团、醇基团、酚基团或卤代基团,M为金属元素,X为卤素,m为金属元素M的价态数,n为1-3的整数。
Wherein, R 1 and R 2 are independently selected from C 1 -C 24 alkyl groups (including alkane, cycloalkyl, etc.), aryl or alkenyl groups, and R 3 is selected from alkane groups, aromatic groups, alkenes group, epoxy group, alcohol group, phenol group or halogenated group, M is a metal element, X is a halogen, m is the valence number of the metal element M, and n is an integer of 1-3.
所述催化剂为相转移催化剂或两性化合物中的一种或多种,包括阳离子多烷基季铵盐化合物、阳离子卤代多烷基季铵盐化合物、烷基氯化铵、烷基溴化铵、阴离子烷基硫酸盐化合物、烷基磺酸盐、烷基苯磺酸盐、非离子表面活性剂、季膦盐中的至少一种。The catalyst is one or more of phase transfer catalysts or amphoteric compounds, including cationic polyalkyl quaternary ammonium salt compounds, cationic halogenated polyalkyl quaternary ammonium salt compounds, alkyl ammonium chlorides, and alkyl ammonium bromides , at least one of anionic alkyl sulfate compounds, alkyl sulfonates, alkylbenzene sulfonates, nonionic surfactants, and quaternary phosphonium salts.
在本发明的制备方法中,反应物二烷基次磷酸盐为固体,而卤代化合物通常为液体,实现了在催化剂作用下的液固反应,一步法实现目标产物制备,转化率高,生成物除了目标化合物外,副产无机的卤化金属盐,二烷基次磷酸酯为液体,而副产的这些金属盐不溶于卤代化合物和二烷基次磷酸酯,以固体形式存在于反应体系中,很容易与目标产品分离,而且卤化金属盐对环境的危害较小,不会燃烧和爆炸,工艺环保和安全,解决了传统合成工艺的缺陷。此外,卤代化合物也可以通过负压蒸发等简单方式就从产物中抽离,一方面可回收循环利用,另一方面保证了目标产物二烷基次膦酸酯的纯度。In the preparation method of the present invention, the reactant dialkyl hypophosphite is solid, while the halogenated compound is usually liquid, which realizes the liquid-solid reaction under the action of the catalyst, and the one-step method realizes the preparation of the target product, the conversion rate is high, and the generation of In addition to the target compound, by-produced inorganic halogenated metal salts, dialkyl hypophosphites are liquid, and these by-produced metal salts are insoluble in halogenated compounds and dialkyl hypophosphites, and exist in the reaction system in solid form It is easy to separate from the target product, and the halogenated metal salt is less harmful to the environment, will not burn and explode, the process is environmentally friendly and safe, and solves the defects of the traditional synthesis process. In addition, the halogenated compound can also be extracted from the product by simple means such as negative pressure evaporation. On the one hand, it can be recovered and recycled, and on the other hand, the purity of the target product dialkyl phosphinate is guaranteed.
所述二烷基次膦酸盐具体可选自:二甲基次膦酸盐,二乙基次膦酸盐,甲基乙基次磷酸盐,二正丙基次膦酸盐,二异丙基次膦酸酸盐,甲基丙基 次磷酸盐,乙基丙基次磷酸盐,二正丁基次膦酸盐,二仲丁基次膦酸盐,二异丁基次膦酸盐,二叔丁基次膦酸盐,甲基丁基次磷酸盐,乙基丁基次磷酸盐、二正辛基次磷酸盐、二异辛基次磷酸盐以及24个碳以内的其他烷烃基团的次磷酸盐等。The dialkyl phosphinate can be specifically selected from: dimethyl phosphinate, diethyl phosphinate, methyl ethyl phosphinate, di-n-propyl phosphinate, diisopropyl phosphinate Phosphinate, methylpropylphosphinate, ethylpropylphosphinate, di-n-butylphosphinate, di-sec-butylphosphinate, diisobutylphosphinate, Di-tert-butyl phosphinate, methyl butyl hypophosphite, ethyl butyl hypophosphite, di-n-octyl hypophosphite, diisooctyl hypophosphite and other alkane groups up to 24 carbons of hypophosphite, etc.
M优选自钠、钾、钙、铝、镁、锌、钡中的至少一种。M is preferably selected from at least one of sodium, potassium, calcium, aluminum, magnesium, zinc, and barium.
所述卤代化合物具体可选自:卤代甲烷、卤代乙烷、卤代丙烷、卤代丁烷、卤代环氧乙烷、卤代环氧丙烷,卤代甲基环氧丙烷,卤代环氧丁烷、卤代甲醇、卤代乙醇、卤代丁醇、卤代乙烯、卤代丙烯、卤代苯、卤代甲苯、卤代苯酚、卤代甲基苯酚以及其他卤代芳香基团、烯烃、环氧基团、醇、酚基团等。The halogenated compound can be specifically selected from: halogenated methane, halogenated ethane, halogenated propane, halogenated butane, halogenated ethylene oxide, halogenated propylene oxide, halogenated methyl propylene oxide, halogenated Butylene oxides, halomethanols, haloethanols, halobutanols, haloethylenes, halopropenes, halobenzenes, halotoluenes, halophenols, halomethylphenols, and other haloaromatics groups, olefins, epoxy groups, alcohols, phenolic groups, etc.
X优选自氟、氯、溴、碘中的一种或多种。X is preferably one or more selected from fluorine, chlorine, bromine and iodine.
本发明的制备方法,当无催化剂加入时,转化率极低,不具备工业化生产条件。作为优选,所述催化剂包括多烷基氯化铵、多烷基溴化铵、烷基硫酸盐、烷基磺酸盐、烷基苯磺酸盐、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、烷基磷酸酯、聚多元醇中的至少一种。所述多元醇包括乙二醇等。In the preparation method of the present invention, when no catalyst is added, the conversion rate is extremely low, and the industrial production conditions are not met. Preferably, the catalyst includes polyalkyl ammonium chloride, polyalkyl ammonium bromide, alkyl sulfate, alkyl sulfonate, alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl phenol poly At least one of oxyethylene ether, alkyl phosphate, and polyol. The polyol includes ethylene glycol and the like.
所述反应的温度优选为40-150℃,进一步优选为100-150℃。The temperature of the reaction is preferably 40-150°C, more preferably 100-150°C.
所述反应的压力可以为负压、常压或者大于一个大气压的压力,优选为0-5MPa,进一步优选为大于一个大气压的压力且不大于5MPa。The pressure of the reaction can be negative pressure, normal pressure, or pressure greater than one atmosphere, preferably 0-5 MPa, more preferably greater than one atmosphere and not greater than 5 MPa.
本领域技术人员可以根据实际需要,选择反应时间。可选地,反应时间长短可调,决定于催化剂、反应温度、所需的反应程度等。通常情况下,反应速度较快在0.5-20小时就可完成反应;可选地,反应时间为1-10小时。Those skilled in the art can select the reaction time according to actual needs. Optionally, the length of the reaction time can be adjusted, depending on the catalyst, the reaction temperature, the desired degree of reaction, and the like. Usually, the reaction can be completed in 0.5-20 hours with a relatively fast reaction rate; optionally, the reaction time is 1-10 hours.
所述二烷基次膦酸盐和卤代化合物摩尔比优选为1:0.1-10,进一步优选为1:1.01-5。The molar ratio of the dialkylphosphinate to the halogenated compound is preferably 1:0.1-10, more preferably 1:1.01-5.
作为优选,所述催化剂的用量为所述二烷基次膦酸盐的用量的0.001wt%-10wt%。进一步优选,所述催化剂的用量为所述二烷基次膦酸盐的用量的0.1wt%-5.0wt%。Preferably, the amount of the catalyst used is 0.001wt% to 10wt% of the amount of the dialkylphosphinate. Further preferably, the dosage of the catalyst is 0.1wt%-5.0wt% of the dosage of the dialkylphosphinate.
所述的制备方法可采用间歇式或连续式反应。The preparation method can adopt batch or continuous reaction.
连续式工艺中可采用一系列的反应装置,如管道式反应器进行反应。反应结束后分离产物和原材料,将过量的卤代化合物返回到原料罐中实现连续反应。In the continuous process, a series of reaction devices, such as pipeline reactors, can be used to carry out the reaction. After the reaction is completed, the product and raw materials are separated, and the excess halogenated compound is returned to the raw material tank to realize continuous reaction.
间歇式反应可采用一系列的反应装置,如反应釜进行反应。反应结束后分离产物和原材料,将过量的卤代化合物返回到原料罐中实现连续反应。The batch reaction can be carried out by using a series of reaction devices, such as a reaction kettle. After the reaction is completed, the product and raw materials are separated, and the excess halogenated compound is returned to the raw material tank to realize continuous reaction.
本发明中,C
1-C
24等指基团中所包含的碳原子数。
In the present invention, C 1 -C 24 etc. refer to the number of carbon atoms contained in the group.
本发明中,“烷基”是由烷烃化合物分子上失去任意一个氢原子所形成的基团。所述烷烃化合物包括直链烷烃、支链烷烃、环烷烃等。In the present invention, "alkyl" is a group formed by the loss of any hydrogen atom on the molecule of an alkane compound. The alkane compounds include straight-chain alkanes, branched-chain alkanes, cycloalkanes, and the like.
本发明的制备方法,反应得到所述二烷基次膦酸酯后,可进一步提纯得到成品。In the preparation method of the present invention, after the dialkyl phosphinate is obtained by reaction, the finished product can be further purified.
所述提纯包括添加助剂反应、过滤或蒸馏等方法。可选地,反应结束后产品经过滤,蒸馏,得到产物。此处所述的蒸馏可以为蒸馏,蒸发;如减压蒸馏,常压蒸馏,降膜蒸发等操作工艺。The purification includes methods such as reaction with additives, filtration or distillation. Optionally, after the reaction, the product is filtered and distilled to obtain the product. The distillation described here can be distillation, evaporation; such as vacuum distillation, atmospheric distillation, falling film evaporation and other operating processes.
本发明与现有技术相比,主要优点包括:本发明采用二烷基次膦酸盐和卤代化合物为原料一步法合成。反应过程操作方便,反应收率高,副产污染小,制备成本低。Compared with the prior art, the present invention has the following main advantages: the present invention adopts dialkyl phosphinate and halogenated compounds as raw materials for one-step synthesis. The reaction process has the advantages of convenient operation, high reaction yield, little by-product pollution and low preparation cost.
图1为实施例1所得产物的核磁共振磷谱示意图(
31P NMR图);
Fig. 1 is the schematic diagram of the phosphorus nuclear magnetic resonance spectrum ( 31 P NMR chart) of the product obtained in Example 1;
图2为实施例1所得产物的核磁共振氢谱示意图(
1H NMR图);
Figure 2 is a schematic diagram of the hydrogen nuclear magnetic resonance spectrum ( 1 H NMR diagram) of the product obtained in Example 1;
图3为实施例2所得产物的核磁共振磷谱示意图;Fig. 3 is the nuclear magnetic resonance phosphorus spectrum schematic diagram of the product obtained therefrom in Example 2;
图4为实施例2所得产物的核磁共振氢谱示意图;Fig. 4 is the hydrogen nuclear magnetic resonance spectrum schematic diagram of the product obtained in Example 2;
图5为实施例3所得产物的核磁共振磷谱示意图;Fig. 5 is the nuclear magnetic resonance phosphorus spectrum schematic diagram of the product obtained in Example 3;
图6为实施例3所得产物的核磁共振氢谱示意图。FIG. 6 is a schematic diagram of the hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 3. FIG.
下面结合附图及具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法,通常按照常规条件,或按照制造厂商所建议的条件。The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. The operation method without specifying the specific conditions in the following examples is usually in accordance with the conventional conditions, or in accordance with the conditions suggested by the manufacturer.
如无特别说明,原料均通过商业途径购买。Unless otherwise specified, the raw materials are purchased through commercial channels.
核磁共振(NMR)测试:所用型号为AVANCE DMX 400MHz,瑞士Bruker公司;测试方法为:Nuclear Magnetic Resonance (NMR) test: The model used is AVANCE DMX 400MHz, from Bruker, Switzerland; the test method is:
1H NMR,以CDCl
3为溶剂,四甲基硅烷内标;
1 H NMR, with CDCl 3 as solvent, tetramethylsilane internal standard;
31P NMR,以氘代卤代仿为溶剂,85%磷酸外标,扫描次数为64次;
31 P NMR, using deuterated haloform as solvent, 85% phosphoric acid external standard, and the number of scans was 64 times;
通过
31P NMR和
1H NMR可以确定所获得的目标产物的分子结构。
The molecular structure of the obtained target product can be determined by 31 P NMR and 1 H NMR.
以下实施例、对比例中,产率的计算方法为:(产物重量/产物理论重量)×100%。In the following examples and comparative examples, the calculation method of the yield is: (weight of product/theoretical weight of product)×100%.
实施例1 制备具有式(I)结构的化合物Example 1 Preparation of compounds having the structure of formula (I)
向装有搅拌器、温度计的压力釜中加入288g(2mol)二乙基次膦酸酸钠,6.0g催化剂四丁基溴化铵,开启搅拌,通入氮气置换三次,通入500g氯乙烷,升温至110-140℃,保温搅拌10小时后降温、排空、开启真空,脱去未反应完的氯乙烷。产物经过滤,蒸馏,得成品270g,转化率90%,得到式(I)化合物产品。其
31P NMR和
1H NMR分别如图1、2所示,从谱图可以分析所制得的化合物具有式(I)所示的结构。
Add 288g (2mol) sodium diethyl phosphinate, 6.0g catalyst tetrabutylammonium bromide in the autoclave equipped with stirrer, thermometer, open stirring, feed nitrogen replacement three times, feed 500g ethyl chloride , heat up to 110-140 ℃, heat preservation and stirring for 10 hours, then cool down, empty, open the vacuum, and remove the unreacted ethyl chloride. The product was filtered and distilled to obtain 270 g of finished product, the conversion rate was 90%, and the compound product of formula (I) was obtained. Its 31 P NMR and 1 H NMR are shown in Figures 1 and 2, respectively, and it can be analyzed from the spectrum that the prepared compound has the structure shown in formula (I).
实施例2 制备具有式(II)结构的化合物Example 2 Preparation of compounds having the structure of formula (II)
向装有搅拌器、温度计的压力釜中加入288g(2mol)二乙基次膦酸酸钠,6.0g催化剂四丁基溴化铵,开启搅拌,通入氮气置换三次,通入550g氯乙醇,升温至110-140℃,保温搅拌10小时后开启真空,脱去未反应完的氯乙醇、降温。产物经过滤,蒸馏,得成品305g,转化率92%,得到式(II)化合物产品。其
31P NMR和
1H NMR分别如图3、4所示,从谱图可以分析所制得的化合物具有式(II)所示的结构。
Add 288g (2mol) sodium diethyl phosphinate, 6.0g catalyst tetrabutylammonium bromide in the autoclave equipped with stirrer, thermometer, open stirring, feed nitrogen replacement three times, feed 550g chloroethanol, The temperature was raised to 110-140° C., and the vacuum was turned on after stirring for 10 hours, and the unreacted chloroethanol was removed, and the temperature was lowered. The product was filtered and distilled to obtain 305 g of finished product, the conversion rate was 92%, and the compound product of formula (II) was obtained. Its 31 P NMR and 1 H NMR are shown in Figures 3 and 4, respectively, and it can be analyzed from the spectrum that the prepared compound has the structure represented by formula (II).
实施例3 制备具有式(III)结构的化合物Example 3 Preparation of compounds having the structure of formula (III)
向装有搅拌器、温度计的压力釜中加入288g(2mol)二乙基次膦酸酸钠,6.0g催化剂四丁基溴化铵,600g环氧氯丙烷,开启搅拌,通入氮气置换三次,升温至110-120℃,保温搅拌10小时后开启真空,脱去未反应完的环氧氯丙烷。产物经过滤,蒸馏提纯,得成品338g,转化率95%,得式(III)产品。其
31P NMR和
1H NMR分别如图5、6所示,从谱图可以分析所制得的化合物具有式(III)所示的结构。
Add 288g (2mol) sodium diethyl phosphinate, 6.0g catalyst tetrabutylammonium bromide, 600g epichlorohydrin in the autoclave equipped with stirrer, thermometer, open stirring, feed nitrogen and replace three times, The temperature was raised to 110-120° C., and the vacuum was turned on after stirring for 10 hours to remove the unreacted epichlorohydrin. The product was filtered and purified by distillation to obtain 338 g of finished product, the conversion rate was 95%, and the product of formula (III) was obtained. Its 31 P NMR and 1 H NMR are shown in Figures 5 and 6, respectively, and it can be analyzed from the spectrum that the prepared compound has the structure represented by formula (III).
对比例1Comparative Example 1
与实施例3的区别仅在于不加催化剂,其余步骤和条件均相同,产物经过滤,蒸馏,得成品10g,转化率3%,得式(III)产品。可见,如果不加入催化剂,该反应的转化率很低,不具备工业化生产的条件。The only difference from Example 3 is that no catalyst is added, and the remaining steps and conditions are the same. The product is filtered and distilled to obtain 10 g of finished product with a conversion rate of 3%, and the product of formula (III) is obtained. It can be seen that if no catalyst is added, the conversion rate of this reaction is very low, and the conditions for industrial production are not met.
对比例2Comparative Example 2
传统的制备二乙基次磷酸乙酯(结构式(I))的工艺,以二乙基次磷酸钠为原料,制备工艺包括3个步骤:The traditional technique for preparing ethyl diethyl hypophosphite (structural formula (I)) takes sodium diethyl hypophosphite as a raw material, and the preparation technique comprises 3 steps:
(1)二乙基次磷酸的制备(1) Preparation of diethyl hypophosphorous acid
600g的浓度30wt%的二乙基次磷酸钠溶液中,通过阳离子交换树脂,得到二乙基次磷酸溶液,静置分层,取油相液体,蒸发去除水分,得到140g二乙基次磷酸,得率为91.8%。600g of sodium diethyl hypophosphite solution with a concentration of 30wt% was passed through a cation exchange resin to obtain a diethyl hypophosphorous acid solution. The yield was 91.8%.
(2)二乙基次磷酸酰氯的制备(2) Preparation of diethyl hypophosphite acid chloride
122g二乙基次磷酸,升温至80-90℃,滴加入125g二氯亚砜,并用氢氧化钠溶液,吸收副产物二氧化硫和氯化氢,形成亚硫酸钠和氯化钠的混合副产物溶液。滴加5小时,保温1小时。减压蒸馏提纯,得到121g二乙基次磷酸酰氯,得率为86.1%。122g of diethyl hypophosphorous acid was heated to 80-90°C, 125g of thionyl chloride was added dropwise, and sodium hydroxide solution was used to absorb by-product sulfur dioxide and hydrogen chloride to form a mixed by-product solution of sodium sulfite and sodium chloride. Add dropwise for 5 hours and keep warm for 1 hour. Under reduced pressure distillation and purification, 121 g of diethyl hypophosphite acid chloride was obtained, and the yield was 86.1%.
(3)二乙基次磷酸乙基酯的制备(3) Preparation of ethyl diethyl hypophosphite
70克二乙基次磷酰氯升温至50-60℃,逐渐滴加入70g无水乙醇中加入45g吡啶滴加时间4小时,保温1小时。过滤出副产物吡啶盐酸盐,减压蒸馏提纯,得到成品二乙基次磷酸乙酯64g,得率为85.4%。70 g of diethylphosphine chloride was heated to 50-60° C., gradually added dropwise to 70 g of anhydrous ethanol, and 45 g of pyridine was added dropwise for 4 hours and kept for 1 hour. The by-product pyridine hydrochloride was filtered out and purified by distillation under reduced pressure to obtain 64 g of ethyl diethyl hypophosphite with a yield of 85.4%.
与实施例1相比,从同一个原料出发制备同一个目标产物,对比例2的制备步骤过长,得率为67.5%,得率远低于本发明的一步工艺,且副产多,副产物污染较大,不环保。Compared with Example 1, the same target product is prepared from the same raw material, the preparation steps of Comparative Example 2 are too long, and the yield is 67.5%, which is far lower than the one-step process of the present invention, and there are many by-products and side-products. The product is highly polluted and not environmentally friendly.
此外应理解,在阅读了本发明的上述描述内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。In addition, it should be understood that after reading the above description of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
Claims (8)
- 一种二烷基次膦酸酯的制备方法,其特征在于,以二烷基次膦酸盐和卤代化合物为原料,在催化剂作用下反应得到所述二烷基次膦酸酯;A method for preparing dialkyl phosphinate, characterized in that, using dialkyl phosphinate and a halogenated compound as raw materials, and reacting under the action of a catalyst to obtain the dialkyl phosphinate;反应过程如下:The reaction process is as follows:其中,R 1、R 2分别独立选自C 1-C 24的烷基、环烷基、芳基或烯基,R 3选自烷烃基团、芳香基团、烯烃基团、环氧基团、醇基团、酚基团或卤代基团,M为金属元素,X为卤素,m为金属元素M的价态数,n取1-3的整数; Wherein, R 1 and R 2 are independently selected from C 1 -C 24 alkyl, cycloalkyl, aryl or alkenyl groups, and R 3 is selected from alkane groups, aromatic groups, alkene groups, epoxy groups , an alcohol group, a phenol group or a halogenated group, M is a metal element, X is a halogen, m is the valence number of the metal element M, and n is an integer of 1-3;所述催化剂为相转移催化剂或两性化合物中的一种或多种,包括阳离子多烷基季铵盐化合物、阳离子卤代多烷基季铵盐化合物、多烷基氯化铵、多烷基溴化铵、阴离子烷基硫酸盐化合物、烷基磺酸盐、烷基苯磺酸盐、非离子表面活性剂、季膦盐中的至少一种。The catalyst is one or more of phase transfer catalysts or amphoteric compounds, including cationic polyalkyl quaternary ammonium salt compounds, cationic halogenated polyalkyl quaternary ammonium salt compounds, polyalkyl ammonium chloride, polyalkyl bromide At least one of ammonium chloride, anionic alkyl sulfate compounds, alkyl sulfonates, alkylbenzene sulfonates, nonionic surfactants, and quaternary phosphonium salts.
- 根据权利要求1所述的制备方法,其特征在于,M选自钠、钾、钙、铝、镁、锌、钡中的至少一种;preparation method according to claim 1, is characterized in that, M is selected from at least one in sodium, potassium, calcium, aluminum, magnesium, zinc, barium;X选自氟、氯、溴、碘中的一种或多种。X is selected from one or more of fluorine, chlorine, bromine and iodine.
- 根据权利要求1所述的制备方法,其特征在于,所述催化剂包括多烷基氯化铵、多烷基溴化铵、烷基硫酸盐、烷基磺酸盐、烷基苯磺酸盐、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、烷基磷酸酯、聚多元醇中的至少一种。The preparation method according to claim 1, wherein the catalyst comprises polyalkylammonium chloride, polyalkylammonium bromide, alkyl sulfate, alkylsulfonate, alkylbenzenesulfonate, At least one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkyl phosphate ester, and polyhydric alcohol.
- 根据权利要求1所述的制备方法,其特征在于,所述反应的温度为40-150℃,压力为0-5MPa,时间为0.5-20小时。The preparation method according to claim 1, wherein the temperature of the reaction is 40-150° C., the pressure is 0-5 MPa, and the time is 0.5-20 hours.
- 根据权利要求1所述的制备方法,其特征在于,所述二烷基次膦酸盐和卤代化合物摩尔比为1:0.1-10。The preparation method according to claim 1, wherein the molar ratio of the dialkyl phosphinate to the halogenated compound is 1:0.1-10.
- 根据权利要求1所述的制备方法,其特征在于,所述催化剂的用量为所述二烷基次膦酸盐的用量的0.001wt%-10wt%。The preparation method according to claim 1, wherein the amount of the catalyst is 0.001wt% to 10wt% of the amount of the dialkylphosphinate.
- 根据权利要求1所述的制备方法,其特征在于,采用间歇式或连续 式反应。The preparation method according to claim 1, is characterized in that, adopts batch type or continuous type reaction.
- 根据权利要求1所述的制备方法,其特征在于,反应得到所述二烷基次膦酸酯后,进一步提纯得到成品;The preparation method according to claim 1, characterized in that, after the reaction to obtain the dialkyl phosphinate, further purification is performed to obtain a finished product;所述提纯包括添加助剂反应、过滤或蒸馏。The purification includes additive reaction, filtration or distillation.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110008008.2A CN112661790B (en) | 2021-01-05 | 2021-01-05 | Preparation method of dialkyl phosphinate |
CN202110008008.2 | 2021-01-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022147941A1 true WO2022147941A1 (en) | 2022-07-14 |
Family
ID=75412959
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2021/094487 WO2022147941A1 (en) | 2021-01-05 | 2021-05-19 | Dialkyl phosphinate preparation method |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN112661790B (en) |
WO (1) | WO2022147941A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112778368B (en) * | 2021-01-05 | 2022-08-23 | 江苏利思德新材料有限公司 | Dialkyl phosphinate containing active epoxy group and preparation and application thereof |
CN112661790B (en) * | 2021-01-05 | 2022-07-01 | 江苏利思德新材料有限公司 | Preparation method of dialkyl phosphinate |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103951700A (en) * | 2014-05-15 | 2014-07-30 | 江苏利思德新材料有限公司 | Preparation method as well as product and application of dimethyl hypophosphite |
CN103980306A (en) * | 2014-04-28 | 2014-08-13 | 湖南大学 | Preparation method for hypophosphorous acid / phosphorous acid/ phosphate compounds by adopting P(O)-OH-contained compounds |
CN112661790A (en) * | 2021-01-05 | 2021-04-16 | 江苏利思德新材料有限公司 | Preparation method of dialkyl phosphinate |
CN112778368A (en) * | 2021-01-05 | 2021-05-11 | 江苏利思德新材料有限公司 | Dialkyl phosphinate containing active epoxy group and preparation and application thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106117394B (en) * | 2016-04-22 | 2018-06-01 | 中山大学 | A kind of phosphonic acid ester photoinitiator containing fluorocarbon chain and preparation method thereof |
-
2021
- 2021-01-05 CN CN202110008008.2A patent/CN112661790B/en active Active
- 2021-05-19 WO PCT/CN2021/094487 patent/WO2022147941A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103980306A (en) * | 2014-04-28 | 2014-08-13 | 湖南大学 | Preparation method for hypophosphorous acid / phosphorous acid/ phosphate compounds by adopting P(O)-OH-contained compounds |
CN103951700A (en) * | 2014-05-15 | 2014-07-30 | 江苏利思德新材料有限公司 | Preparation method as well as product and application of dimethyl hypophosphite |
CN112661790A (en) * | 2021-01-05 | 2021-04-16 | 江苏利思德新材料有限公司 | Preparation method of dialkyl phosphinate |
CN112778368A (en) * | 2021-01-05 | 2021-05-11 | 江苏利思德新材料有限公司 | Dialkyl phosphinate containing active epoxy group and preparation and application thereof |
Non-Patent Citations (2)
Title |
---|
GOLUBSKI ZBIGNIEW E.: "Alkylation of Phosphinic Acid salts in the presence of Crown Ethers", SYNTHESIS, vol. 8, 31 August 1980 (1980-08-31), pages 632 - 634, XP055949836, DOI: 10.1055/s-1980-29147 * |
XIONG BIQUAN; YE QIANQIAN; FENG XIAOFENG; ZHU LONGZHI; CHEN TIEQIAO; ZHOU YONGBO; AU CHAK-TONG; YIN SHUANG-FENG: "Base-promotedO-deprotonation/alkylation reaction of P(O)–OH compounds with alkyl hal", TETRAHEDRON, ELSEVIER SIENCE PUBLISHERS, AMSTERDAM, NL, vol. 70, no. 47, 13 October 2014 (2014-10-13), AMSTERDAM, NL , pages 9057 - 9063, XP029088647, ISSN: 0040-4020, DOI: 10.1016/j.tet.2014.10.013 * |
Also Published As
Publication number | Publication date |
---|---|
CN112661790B (en) | 2022-07-01 |
CN112661790A (en) | 2021-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022147941A1 (en) | Dialkyl phosphinate preparation method | |
JP4865701B2 (en) | Method for alkylating phosphorus-containing compounds | |
WO2022147942A1 (en) | Dialkyl phosphonate compound containing active epoxy group, preparation and application thereof | |
US3493639A (en) | Process for producing pentavalent phosphorus derivatives | |
TWI721011B (en) | Manufacturing method of alkenyl phosphorus compound | |
JP5666535B2 (en) | Diarylalkylphosphonates and methods for their preparation | |
BR112014027792B1 (en) | ETHYLENE TETRAMERIZATION | |
US20100120930A1 (en) | Use of low triphenylphosphate, high phosphorous content isopropyl phenyl phosphates as flame retardants in polyurethane or polyisocyanurate foams | |
US3751460A (en) | Process for preparing isomeric cyclic 5-membered unsaturated phosphine dihalides | |
JP4245050B2 (en) | Novel fluorine-containing polyether phosphonate compound and process for producing the same | |
JPH068311B2 (en) | Method for producing phosphazene esters | |
US20120108849A1 (en) | Polyfluoroalkylphosphonic acid ester and process for producing the same | |
CN109400643A (en) | Methylethyl phosphinicacid ethyl ester and Methylethyl phosphinic acids aluminium salt preparation process | |
JP2000038399A (en) | Production of phosphonous ester | |
JP2012525438A5 (en) | ||
CN104447859A (en) | Synthesis process of phosphinate containing alkylaryl | |
KR101864260B1 (en) | Phosphoric acid ester production method | |
CN101981042B (en) | Slurry process for phosphoromonochloridite synthesis | |
CN100999450A (en) | Preparation technology of polyhalogenated aryl allyl ether compound | |
US2117283A (en) | Organic phosphates | |
JP4128279B2 (en) | An improved method for the preparation of phosphites. | |
CN102448971A (en) | Method for the manufacture of dialkylphosphites | |
KR950001703B1 (en) | Method of preparing trialkylphosphate | |
WO2023054663A1 (en) | Method for producing vinylphosphonic acid monoester | |
US3737487A (en) | Process for preparing aryl alkyl phosphates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21916656 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21916656 Country of ref document: EP Kind code of ref document: A1 |