CN103172664B - Preparation method of dialkylphosphinate with excellent flowing property - Google Patents
Preparation method of dialkylphosphinate with excellent flowing property Download PDFInfo
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- CN103172664B CN103172664B CN201310061973.1A CN201310061973A CN103172664B CN 103172664 B CN103172664 B CN 103172664B CN 201310061973 A CN201310061973 A CN 201310061973A CN 103172664 B CN103172664 B CN 103172664B
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- Prior art keywords
- dialkylphosphinic
- salt
- preparing
- mixture
- acid
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 47
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 35
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 34
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract 5
- 150000003839 salts Chemical class 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 36
- -1 phosphinic acid alkali metal salt Chemical class 0.000 claims description 36
- 238000002425 crystallisation Methods 0.000 claims description 35
- 230000008025 crystallization Effects 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 27
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 19
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 18
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 18
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 18
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical group [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229960002337 magnesium chloride Drugs 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009828 non-uniform distribution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 81
- LPFYDEANGXVAOA-UHFFFAOYSA-M sodium;diethylphosphinate Chemical compound [Na+].CCP([O-])(=O)CC LPFYDEANGXVAOA-UHFFFAOYSA-M 0.000 description 31
- 239000007787 solid Substances 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 27
- 229910021641 deionized water Inorganic materials 0.000 description 27
- 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 22
- 238000001816 cooling Methods 0.000 description 21
- 238000001035 drying Methods 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- 238000001914 filtration Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 16
- TZPNUVYGCPWJKV-UHFFFAOYSA-M sodium dipropylphosphinate Chemical compound C(CC)P([O-])(=O)CCC.[Na+] TZPNUVYGCPWJKV-UHFFFAOYSA-M 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 9
- GOJNABIZVJCYFL-UHFFFAOYSA-M dimethylphosphinate Chemical compound CP(C)([O-])=O GOJNABIZVJCYFL-UHFFFAOYSA-M 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- HHYXZVYUIJDJAH-UHFFFAOYSA-L magnesium;diethylphosphinate Chemical compound [Mg+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC HHYXZVYUIJDJAH-UHFFFAOYSA-L 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OTWVIISPZQRNGR-UHFFFAOYSA-M C[Al+]C.[O-][PH2]=O Chemical compound C[Al+]C.[O-][PH2]=O OTWVIISPZQRNGR-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IOGRQIWFIRKXQV-UHFFFAOYSA-K aluminum dipropylphosphinate Chemical compound C(CC)P([O-])(=O)CCC.[Al+3].C(CC)P([O-])(=O)CCC.C(CC)P([O-])(=O)CCC IOGRQIWFIRKXQV-UHFFFAOYSA-K 0.000 description 2
- DRYHXHUXMMIMPH-UHFFFAOYSA-L calcium;diethylphosphinate Chemical compound [Ca+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DRYHXHUXMMIMPH-UHFFFAOYSA-L 0.000 description 2
- DONULGYRZAGJQH-UHFFFAOYSA-L calcium;dimethylphosphinate Chemical compound [Ca+2].CP(C)([O-])=O.CP(C)([O-])=O DONULGYRZAGJQH-UHFFFAOYSA-L 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- WRMGSHJRBULEMY-UHFFFAOYSA-L diethylphosphinate iron(2+) Chemical compound C(C)P([O-])(=O)CC.[Fe+2].C(C)P([O-])(=O)CC WRMGSHJRBULEMY-UHFFFAOYSA-L 0.000 description 2
- MKNUZASDTKBRNE-UHFFFAOYSA-L magnesium;dimethylphosphinate Chemical compound [Mg+2].CP(C)([O-])=O.CP(C)([O-])=O MKNUZASDTKBRNE-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- MXMCTPBQIJWVBA-UHFFFAOYSA-L zinc;dimethylphosphinate Chemical compound [Zn+2].CP(C)([O-])=O.CP(C)([O-])=O MXMCTPBQIJWVBA-UHFFFAOYSA-L 0.000 description 2
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical group CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229960001040 ammonium chloride Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960002233 benzalkonium bromide Drugs 0.000 description 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of dialkylphosphinate with an excellent flowing property. The preparation method comprises the following steps of: (a) adding an auxiliary crystallizing agent into a dialkylphosphinate and/or dialkylphosphinate alkali metal water solution to obtain the dialkylphosphinate and/or dialkylphosphinate alkali metal water solution containing the auxiliary crystallizing agent; and (b) reacting a mixture of metal compounds and water with the obtained dialkylphosphinate and/or dialkylphosphinate alkali metal water solution containing the auxiliary crystallizing agent to generate dialkylphosphinate. The dialkylphosphinate prepared by adding the auxiliary crystallizing agent is good in flowing property, and a repose angle of dialkylphosphinate can reach 20-40 degrees, thus the problems of poor flowing property and nonuniform distribution of fire retardants in resin can be fundamentally solved. The method disclosed by the invention is simple in process and convenient to operate, the production cost is greatly reduced, the production equipment is simplified, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of flame retardant synthesis, and particularly relates to a preparation method of dialkyl phosphinate with good free-running property.
Background
High molecular materials (plastics, rubber, chemical fibers and the like) are widely applied to the fields of building industry, automobile industry, medical treatment and health and household appliances. However, the polymer materials are usually flammable or combustible, and the requirements for the flame retardant performance of the polymer materials are higher and higher in practical application. In order to ensure the safety of the synthetic materials and meet the requirement of environmental protection, the most effective method is to add halogen-free flame retardant into the synthetic materials.
The dialkylphosphinate has been proved to be a highly effective halogen-free flame retardant and widely used in synthetic materials, but the commonly used dialkylphosphinate flame retardant has poor free-running property, and when the solid which is not easy to run off is added into resin, the distribution of the flame retardant in the resin is affected, and the flame retardant performance of the material is reduced. In some industries, particularly in the micro-electronics industry, the flame retardant property of a product still can reach UL 94V-0 grade at 0.4mm, so that the used resin is required to have excellent fluidity, and the application of the resin added with the dialkyl phosphinate flame retardant with poor fluidity in the microelectronic industry is greatly limited.
US patent No. 0021676a1 discloses a method for improving the free-running properties of dialkylphosphinic salts by mixing dialkylphosphinic salts of Mg, Al, Ca, Ti, Zn or Na, metal soaps and metal compounds, which gives a higher free-running property than when one metal dialkylphosphinate is used alone.
U.S. Pat. No. 3, 0025643, 1 also reports that the combination of an aluminum dialkylphosphinate and a zinc dialkylphosphinate results in a higher free-flowing property than when aluminum dialkylphosphinate is used alone.
The above method has the following defects: only when the flame retardant is applied to resin, the fluidity of the flame retardant in the resin is improved by mutually matching various metal dialkylphosphinate salts, and the problems of poor fluidity and uneven distribution of the dialkyl phosphinate salts in the resin are not solved from the source; the mutual matching and use of various dialkyl phosphinic acid metal salts are complicated in operation and implementation, and the significance for improving the flowing property and distribution problem of the flame retardant in the resin is low.
Disclosure of Invention
In order to overcome the problem of poor free-running property of the existing dialkyl phosphinate, the invention aims to provide a preparation method of the dialkyl phosphinate with good free-running property.
Another subject of the invention is the use of the dialkylphosphinic salts prepared by the above-described process as flame retardants.
The invention is realized by the following technical scheme:
a method for preparing a dialkylphosphinic salt with good free-running properties, comprising the following steps:
a) adding a crystallization assistant into the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution to obtain the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution containing the crystallization assistant;
b) reacting a mixture of a metal compound and water with the obtained dialkyl phosphinic acid containing the crystallization assistant and/or the dialkyl phosphinic acid alkali metal salt aqueous solution to generate dialkyl phosphinate shown in the formula (I);
wherein the crystallization assistant is a cationic crystallization assistant, an anionic crystallization assistant, a nonionic crystallization assistant and/or a zwitterionic crystallization assistant;
wherein,
R1，R2identical or different, are linear or branched C1-C6 alkyl;
m is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn, preferably Ca, Al, Mg, Fe or Zn;
m is 2 to 4.
The cation crystallization assistant is ammonium chloride, benzalkonium bromide, cetylpyridinium chloride or cetylpyridinium bromide; the anion crystallization aid is sodium stearate, sodium polyacrylate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dodecyl benzene sulfonate or sodium dioctyl sulfosuccinate; the non-ionic crystallization assistant is a polysorbate compound, a polyoxyethylene fatty acid ester compound, a polyoxyethylene fatty alcohol ether or a polyoxyethylene-polyoxypropylene copolymer; the zwitterion crystallization assistant is lecithin, amino acid or betaine type compound.
The crystallization aid of the present invention is preferably sodium stearate, sodium polyacrylate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, and more preferably sodium polyacrylate or sodium dodecyl sulfate.
The dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt used in the process of preparing the dialkyl phosphinic acid metal salt by the method are synthesized according to Chinese patent CN 102050835A.
The mass fraction of the crystallization assistant is 0.1-50%, preferably 1-10% based on the mass of the dialkyl phosphinic acid or the dialkyl phosphinic acid alkali metal salt aqueous solution.
In the step a), the mass concentration of the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution is 10-90%, preferably 30-70%.
In the step b), the metal compound is selected from one or a mixture of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum oxide, aluminum hydroxide, ferric sulfate, ferric nitrate, ferric chloride, ferric acetate, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, calcium sulfate, calcium nitrate, calcium chloride and calcium acetate.
In the step b), the mass percent of the metal compound in the mixture of the metal compound and water is 10-100%, preferably 20-50%.
The molar ratio of the mixture of the metal compound and water to the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution is 10: 1-1: 10, preferably 1: 1-1: 8.
In step b), the reaction temperature of the mixture of the metal compound and water and the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution is 0-150 ℃, preferably 70-100 ℃.
In step b), the reaction time of the mixture of the metal compound and water and the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution is 0.1-10 h, preferably 0.1-1 h.
In step b), the mixture of the metal compound and the water is reacted with the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution containing the crystallization assistant, namely the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution containing the crystallization assistant is added into the mixture of the metal compound and the water for reaction, or the mixture of the metal compound and the water is added into the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution containing the crystallization assistant for reaction; preferably a mixture of a metal compound and water, is added to the dialkylphosphinic acid and/or the aqueous solution of the alkali metal salt of dialkylphosphinic acid containing the crystallization assistant to carry out the reaction.
In step b), the residual moisture content of the dialkylphosphinic salt is 0.01 to 10wt%, preferably 0.1 to 1 wt%.
In step b), the angle of repose of the dialkylphosphinic salt is 20°~40°Preferably 25°~35°。
In the step b), the particle size of the dialkyl phosphinate is 1-100 μm.
In the step b), the tap density of the dialkyl phosphinate is 500-800 g/L, preferably 600-800 g/L.
The dialkyl phosphinate prepared by the invention is used as a flame retardant and can be applied to PBT, PA, PET, PC, PS and the like to prepare high-performance flame-retardant polymer materials.
Compared with the prior art, the invention has the following beneficial effects:
the dialkyl phosphinate prepared by adding the crystallization assistant has good free-running property, and the angle of repose of the dialkyl phosphinate can reach 20°~40°The problems of poor flowability and uneven distribution of the flame retardant in the resin can be fundamentally solved.
The method has the advantages of simple process and convenient operation, greatly reduces the production cost, simplifies the production equipment and improves the production efficiency.
Detailed Description
The present invention is further illustrated by the following specific embodiments, which are not intended to limit the scope of the invention.
The dialkylphosphinic acids and/or alkali metal dialkylphosphinate salts used in the examples of the process according to the invention were synthesized according to the Chinese patent CN 102050835A.
The method for evaluating the fluidity of the dialkylphosphinic salt is a repose angle method, a scraping angle method, an outflow velocity method, a compression method and/or an aggregation method. Taking the angle of repose method as an example, the powder sample is poured into a funnel, and the sample is dropped onto a round flat plate with the radius r below the round flat plate through the funnel, and the powder is gradually stacked until the powder cannot be stacked continuously. Measuring the powder stacking height h, and calculating the repose angle alpha according to the formula (1)
tgα=h/r （1）
The smaller the α, the better the powder flowability. Generally, alpha is less than 30 degrees, and the powder can flow freely; alpha is between 30 and 40 degrees, and the powder can meet the processing requirement; however, alpha is more than 40 degrees, and the powder is difficult to meet the processing requirement.
The tap density test method of the metal dialkylphosphinate is determined by referring to a method GB5162 determination of tap density of metal powder.
The infrared absorption spectrum test method of the dialkyl phosphinate is determined by referring to the method of GB/T6040 general rule of Infrared Spectroscopy.
Example 1
480g (1.0 mol) of 30% sodium diethylphosphinate solution is heated to 90 ℃, 0.1% sodium polyacrylate solution by mass (based on the mass of the sodium diethylphosphinate solution) is added, 277.5g of a mixture of 40% aluminum sulfate (M = 666) and water is added dropwise within 45 minutes to generate a white solid, and the white solid is cooled, filtered, washed and precipitated by 3L of deionized water and dried at 200 ℃ for 10 hours to obtain 124.8g of aluminum diethylphosphinate, wherein the yield is 96.0% and the water content is 0.6%.
Tap density (g/L): 600, preparing a mixture; angle of repose: 38 degree
IR： 778cm-1, 1076 cm -1, 1151cm -1, 2881 cm -1, 2959 cm -1
Example 2
Preparation of aluminum diethylphosphinate as in example 1, 308.6g (1.5 mol) of 70% sodium diethylphosphinate solution was heated to 150 ℃, 0.5% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium polyacrylate solution was added, 832.5g of a mixture of 20% aluminum sulfate (M = 666) and water was added dropwise over 70 minutes to produce a white solid, which was cooled, filtered, washed with 3L of deionized water and precipitated, and dried at 200 ℃ for 10 hours to obtain 188.2g of aluminum diethylphosphinate, in a yield of 96.5% and a water content of 0.6%.
Tap density (g/L): 605; angle of repose: 35 degree
Example 3
Prepare aluminum diethylphosphinate as in example 1 by cooling 493.7g (1.2 mol) of 35% sodium diethylphosphinate solution to 0 ℃, adding 1% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium polyacrylate solution, adding 333g of a 40% aluminum sulfate (M = 666) and water mixture dropwise over 45 minutes to form a white solid, cooling, filtering, washing the precipitate with 3L of deionized water, and drying at 200 ℃ for 10 hours to obtain 150.1g of aluminum diethylphosphinate, wherein the yield is 96.2% and the water content is 0.6%.
Tap density (g/L): 615; angle of repose: at an angle of 32 °
Example 4
Aluminum diethylphosphinate was prepared as in example 1 by heating 360g (1.0 mol) of 40% sodium diethylphosphinate solution to 70 ℃, adding 5% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium polyacrylate solution, adding 555g of a mixture of 20% aluminum sulfate (M = 666) and water dropwise over 65 minutes to form a white solid, cooling, filtering, washing the precipitate with 3L of deionized water, and drying at 200 ℃ for 10 hours to obtain 126.8g of aluminum diethylphosphinate, with a yield of 97.5% and a water content of 0.4%.
Tap density (g/L): 670; angle of repose: 25 degree
Example 5
Prepare aluminum diethylphosphinate as in example 1 by heating 1152g (0.8 mol) of 10% sodium diethylphosphinate solution to 80 ℃, adding 10% sodium polyacrylate solution by mass (based on the mass of the sodium diethylphosphinate solution), adding 88.8g aluminum sulfate (M = 666) solid within 0.1 hour to produce a white solid, cooling, filtering, washing the precipitate with 2L deionized water, and drying at 200 ℃ for 10 hours to obtain 99.3g aluminum diethylphosphinate, with a yield of 95.5% and a water content of 0.9%.
Tap density (g/L): 630; angle of repose: 31 degree
Example 6
Aluminum diethylphosphinate was prepared as in example 1 by heating 384g (0.8 mol) of 30% sodium diethylphosphinate solution to 100 ℃ and adding 25% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium polyacrylate solution, dropping 177.6g of a 50% by mass mixture of aluminum sulfate (M = 666) and water over 30 minutes to form a white solid, cooling, filtering, washing the precipitate with 3L of deionized water, and drying at 200 ℃ for 10 hours to obtain 98.3g of aluminum diethylphosphinate, with an yield of 94.5% and a water content of 1.1%.
Tap density (g/L): 600, preparing a mixture; angle of repose: 37 degree
Example 7
The same procedure as in example 1 was followed to prepare aluminum diethylphosphinate by heating 320g (2.0 mol) of 90% sodium diethylphosphinate solution to 50 deg.C, adding 50% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium polyacrylate solution, dropwise adding 2220g of a 10% by mass mixture of aluminum sulfate (M = 666) and water over 10 hours to form a white solid, cooling, filtering, washing the precipitate with 4L of deionized water, and drying at 200 deg.C for 10 hours to obtain 243.4g of aluminum diethylphosphinate, with a yield of 93.6% and a water content of 1.3%.
Tap density (g/L): 590; angle of repose: 41 DEG degree
Example 8
The aluminum diethylphosphinate was prepared as in example 1, the crystallization promoter was sodium dodecylsulfate, 480g (1.0 mol) of 30% sodium diethylphosphinate solution was heated to 120 ℃, 5% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium dodecylsulfate solution was added, 370g of a mixture of 30% aluminum sulfate (M = 666) and water was added dropwise over 40 minutes to produce a white solid, which was cooled, filtered, washed with 3L of deionized water and precipitated, and dried at 200 ℃ for 10 hours to obtain 125.3g of aluminum diethylphosphinate, with a yield of 96.4% and a water content of 0.5%.
Tap density (g/L): 660; angle of repose: 27 degree
Example 9
Prepare aluminum diethylphosphinate as in example 1, with sodium stearate as the crystallization aid, heat 230.4g (0.8 mol) of 50% sodium diethylphosphinate solution to 90 ℃, add 5% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium stearate solution, drop-add 444g of a 20% aluminum sulfate (M = 666) and water mixture over 65 minutes to form a white solid, cool, filter, wash the precipitate with 2L of deionized water, dry at 200 ℃ for 10h to obtain 99.8g of aluminum diethylphosphinate, with a yield of 96.0% and a water content of 0.6%.
Tap density (g/L): 640; angle of repose: 30 degree
Example 10
Aluminum diethylphosphinate was prepared as in example 1, 480g (1.0 mol) of 30% sodium diethylphosphinate solution was heated to 60 ℃ with sodium dodecyl sulfate as a crystallization promoter, 5% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium dodecyl sulfate solution was added, 277.5g of a mixture of 40% aluminum sulfate (M = 666) and water was added dropwise over 30 minutes to produce a white solid, which was cooled, filtered, washed with 3L of deionized water and precipitated, and dried at 200 ℃ for 10 hours to produce 126.1g of aluminum diethylphosphinate, in 97.0% yield, with a water content of 0.5%.
Bulk density (g/L): 660; angle of repose: at 26 °
Example 11
Aluminum diethylphosphinate was prepared as in example 1, sodium dodecylbenzenesulfonate as crystallization aid, 493.7g (1.2 mol) of 35% sodium diethylphosphinate solution was heated to 100 ℃, 5% by mass (based on the mass of the sodium diethylphosphinate solution) of sodium dodecylbenzenesulfonate solution was added, 380.6g of a mixture of 35% aluminum sulfate (M = 666) and water was added dropwise over 50 minutes to produce a white solid, which was then cooled, filtered, washed with 3L of deionized water to precipitate, and dried at 200 ℃ for 10 hours to obtain 148.2g of aluminum diethylphosphinate, with a yield of 95.0% and a water content of 0.9%.
Tap density (g/L): 620; angle of repose: 31 degree
Example 12
Preparing zinc diethyl phosphinate, namely, adopting a zinc sulfate aqueous solution as a metal compound aqueous solution, heating 192g (0.4 mol) of 30% sodium diethyl phosphinate solution to 90 ℃, adding a sodium polyacrylate solution with the mass fraction of 5% (based on the mass of the sodium diethyl phosphinate solution), dropwise adding 191.7g of a mixture of 30% zinc sulfate (M = 287.54) and water within 30min to generate a white solid, cooling, filtering, washing and precipitating with 1L of deionized water, and drying at 200 ℃ for 10h to obtain 58.9g of zinc diethyl phosphinate, wherein the yield is 96.0% and the water content is 0.6%.
Tap density (g/L): 685 of raw materials; angle of repose: 27 degree
IR： 776cm-1, 1056 cm -1, 1133cm -1, 2882 cm -1, 2942 cm -1, 2972cm -1
Example 13
Preparing calcium diethylphosphinate, namely, adopting a calcium chloride aqueous solution as a metal compound aqueous solution, heating 493.7g (1.2 mol) of 35% sodium diethylphosphinate solution to 75 ℃, adding a 5% sodium stearate solution by mass (based on the mass of the sodium diethylphosphinate solution), dropwise adding a mixture of 190.3g of 35% calcium chloride (M = 111) by mass and water within 30min to generate a white solid, cooling, filtering, washing the precipitate with 2L of deionized water, and drying at 200 ℃ for 10h to obtain 153.1g of calcium diethylphosphinate, wherein the yield is 90.5% and the water content is 0.6%.
Tap density (g/L): 655; angle of repose: 30 degree
IR： 776cm-1, 1060 cm -1, 1108cm -1, 2880 cm -1, 2940cm -1, 2960cm -1
Example 14
Preparing iron diethylphosphinate, namely, adopting an aqueous solution of a metal compound, namely, an aqueous solution of iron chloride, heating 2160g (3 mol) of 20% sodium diethylphosphinate solution to 60 ℃, adding a sodium dodecyl sulfate solution with the mass fraction of 5% (based on the mass of the sodium diethylphosphinate solution), dropwise adding 270.8g of a mixture of 60% iron chloride (M = 162.5) and water within 45min to generate a white solid, cooling, filtering, washing and precipitating with 6L of deionized water, and drying at 200 ℃ for 10h to obtain 403.1g of iron diethylphosphinate, wherein the yield is 96.2% and the water content is 0.5%.
Tap density (g/L): 658; angle of repose: 31 degree
IR： 776cm-1, 1045 cm -1, 1108cm -1, 2880 cm -1, 2940 cm -1, 2960cm -1
Example 15
The preparation method comprises the steps of preparing magnesium diethylphosphinate, heating 493.7g (1.2 mol) of 35% sodium diethylphosphinate solution to 95 ℃ by using an aqueous magnesium sulfate solution as a metal compound solution, adding a 5% mass fraction (based on the mass of the sodium diethylphosphinate solution) sodium dodecyl benzene sulfonate solution, dropwise adding a mixture of 205.7g of 35% magnesium sulfate (M = 120) and water within 30min to generate a white solid, cooling, filtering, washing the precipitate with 3L of deionized water, and drying at 200 ℃ for 10h to obtain 155.5g of magnesium diethylphosphinate, wherein the yield is 97.4% and the water content is 0.3%.
Tap density (g/L): 676; angle of repose: 28 degree
IR： 776cm-1, 1088 cm -1, 1170cm -1, 2880 cm -1, 2940 cm -1, 2959 cm -1
Example 16
Preparing magnesium diethylphosphinate, namely heating 244g (1 mol) of 50% solution of the magnesium diethylphosphinate to 90 ℃, adding 5% by mass (based on the mass of the solution of the magnesium diethylphosphinate) solution of sodium polyacrylate, dropwise adding 300g of a mixture of 20% by mass of magnesium sulfate (M = 120) and water within 30min to generate a white solid, cooling, filtering, washing the precipitate with 3L of deionized water, and drying at 200 ℃ for 10h to obtain 129.0g of magnesium diethylphosphinate, wherein the yield is 97.0% and the water content is 0.4%.
Tap density (g/L): 668; angle of repose: 29 degree
Example 17
Preparing dimethyl aluminum phosphinate, heating 235g (1 mol) of 40% dimethyl phosphinic acid solution to 95 ℃, adding 5% sodium polyacrylate solution by mass (based on the mass of the dimethyl phosphinic acid solution), neutralizing with alkali, dropwise adding 370g of a mixture of 30% aluminum sulfate (M = 666) and water within 35min to generate a white solid, cooling, filtering, washing and precipitating with 2L of deionized water, and drying at 200 ℃ for 10h to obtain 99.1g of dimethyl aluminum phosphinate, wherein the yield is 97.2% and the water content is 0.4%.
Tap density (g/L): 667; angle of repose: 30 degree
IR： 776 cm -1, 1076cm -1, 1150 cm -1, 2879 cm -1, 2930 cm -1
Example 18
Preparing zinc dimethylphosphinate, heating 805.7g (3 mol) of 35% dimethylphosphinate solution to 90 ℃, adding 5% by mass (based on the mass of the dimethylphosphinate solution) of sodium polyacrylate solution, neutralizing with alkali, dropwise adding 1232.3g of a mixture of 35% by mass of zinc sulfate (M = 287.54) and water within 100min to generate a white solid, cooling, filtering, washing the precipitate with 6L of deionized water, and drying at 200 ℃ for 10h to obtain 362.9g of zinc dimethylphosphinate, wherein the yield is 96.4% and the water content is 0.5%.
Tap density (g/L): 680; angle of repose: 28 degree
IR： 776cm-1, 1081 cm -1, 1156cm -1, 2886cm -1, 2971cm -1
Example 19
Preparing calcium dimethylphosphinate, heating 313.3g (1 mol) of 30% dimethylphosphinate solution to 80 ℃, adding 5% by mass (based on the mass of the dimethylphosphinate solution) of sodium stearate solution, neutralizing with alkali, dropwise adding 185g of a mixture of 30% by mass of calcium chloride (M = 111) and water within 15min to generate a white solid, cooling, filtering, washing the precipitate with 2L of deionized water, and drying at 200 ℃ for 10h to obtain 100.5g of calcium dimethylphosphinate, wherein the yield is 88.9% and the water content is 0.6%.
Tap density (g/L): 650; angle of repose: 31 degree
IR： 777cm-1, 1076 cm -1, 1158cm -1, 2888 cm -1, 2960cm -1
Example 20
Preparing magnesium dimethylphosphinate, namely heating 2350g (5 mol) of 20% dimethyl phosphinic acid solution to 110 ℃ by adopting dimethyl phosphinic acid, adding a sodium dodecyl sulfate solution with the mass fraction of 5% (based on the mass of the dimethyl phosphinic acid solution), neutralizing with alkali, dropwise adding a mixture of 750g of magnesium sulfate (M = 120) with the mass percentage of 40% and water within 70min to generate a white solid, cooling, filtering, washing and precipitating with 10L of deionized water, and drying at 200 ℃ for 10h to obtain 510.8g of magnesium dimethylphosphinate, wherein the yield is 97.3%, and the water content is 0.3%.
Tap density (g/L): 653; angle of repose: 33 degree
IR： 776cm-1, 1072 cm -1, 1149cm -1, 2881 cm -1, 2952 cm -1
Example 21
Preparing iron dimethyl phosphinate, namely heating 537.1g (2 mol) of 35% solution of dimethyl phosphinate to 130 ℃, adding 5% by mass (based on the mass of the solution of dimethyl phosphinate) of sodium dodecyl benzene sulfonate solution, neutralizing with alkali, dropwise adding 309.5g of 35% mixture of iron chloride (M = 162.5) and water within 25min to generate white solid, cooling, filtering, washing and precipitating with 4L of deionized water, and drying at 200 ℃ for 10h to obtain 216.2g of iron dimethyl phosphinate, wherein the yield is 96.8% and the water content is 0.5%.
Tap density (g/L): 670; angle of repose: 30 degree
IR： 776cm-1, 1072 cm -1, 1145cm -1, 2878 cm -1, 2950 cm -1
Example 22
Preparing aluminum dipropylphosphinate, heating 1290g (1.5 mol) of 20% sodium dipropylphosphinate solution to 55 ℃, adding 5% sodium polyacrylate solution by mass (based on the mass of the sodium dipropylphosphinate solution), dropwise adding 555g of a mixture of 30% aluminum sulfate (M = 666) by mass and water within 50min to generate a white solid, cooling, filtering, washing the precipitate with 3L of deionized water, and drying at 200 ℃ for 10h to obtain 232.5g of aluminum dipropylphosphinate, wherein the yield is 98.1% and the water content is 0.2%.
Tap density (g/L): 675; angle of repose: 30 degree
IR： 775cm-1, 1070 cm -1, 1150cm -1, 2882 cm -1, 2989cm -1
Example 23
Preparing zinc dipropyl phosphinate, heating 1720g (5 mol) of 50% sodium dipropyl phosphinate solution to 85 ℃, adding 5% by mass of sodium polyacrylate solution (based on the mass of the sodium dipropyl phosphinate solution), dropwise adding 2396.2g of a mixture of 30% by mass of zinc sulfate (M = 287.54) and water within 150min to generate a white solid, cooling, filtering, washing the precipitate with 10L of deionized water, and drying at 200 ℃ for 10h to obtain 878.5g of zinc dipropyl phosphinate, wherein the yield is 96.8% and the water content is 0.4%.
Tap density (g/L): 690; angle of repose: 27 degree
IR： 778cm-1, 1069 cm -1, 1152cm -1, 2881 cm -1, 2960cm -1
Example 24
Preparing calcium dipropylphosphinate, heating 860g (1 mol) of 20% sodium dipropylphosphinate solution to 90 ℃, adding 5% of sodium stearate solution by mass (based on the mass of the sodium dipropylphosphinate solution), dropwise adding 185g of a mixture of 30% by mass of calcium chloride (M = 111) and water within 15min to generate a white solid, cooling, filtering, washing the precipitate with 2L of deionized water, and drying at 200 ℃ for 10h to obtain 152.9g of calcium dipropylphosphinate, wherein the yield is 90.5% and the water content is 0.4%.
Tap density (g/L): 667; angle of repose: 29 degree
IR： 776cm-1, 1059 cm -1, 1108cm -1, 2880 cm -1, 2940cm -1, 2960cm -1
Example 25
Preparing magnesium dipropylphosphinate, heating 1474.3g (3 mol) of 35% sodium dipropylphosphinate solution to 60 ℃ by adopting sodium dipropylphosphinate, adding a sodium dodecyl sulfate solution with the mass fraction of 5% (based on the mass of the sodium dipropylphosphinate solution), dropwise adding a mixture of 720g of magnesium sulfate (M = 120) with the mass percent of 25% and water within 70min to generate a white solid, cooling, filtering, washing the precipitate with 6L of deionized water, and drying at 200 ℃ for 10h to obtain 472.4g of magnesium dipropylphosphinate, wherein the yield is 97.8% and the water content is 0.3%.
Tap density (g/L): 665 (d); angle of repose: 30 degree
IR： 770cm-1, 1070cm -1, 1150cm -1, 2886 cm -1, 2978cm -1
Example 26
Preparing iron dipropyl phosphinate, heating 860g (2 mol) of 40% sodium dipropyl phosphinate solution to 40 ℃, adding 5% of sodium dodecyl benzene sulfonate solution by mass (based on the mass of the sodium dipropyl phosphinate solution), dropwise adding 541.7g of a mixture of 20% by mass of iron chloride (M = 162.5) and water within 50min to generate a white solid, cooling, filtering, washing the precipitate with 4L of deionized water, and drying at 180 ℃ for 20h to obtain 322.6g of iron dipropyl phosphinate, wherein the yield is 96.2% and the water content is 0.5%.
Tap density (g/L): 680; angle of repose: 28 degree
IR： 774cm-1, 1072 cm -1, 1151cm -1, 2881 cm -1, 2988cm -1
Comparative example 1
493.7g (1.2 mol) of 35% sodium diethylphosphinate solution is heated to 90 ℃, 380.6g of a mixture of 35% aluminum sulfate (M = 666) and water is added dropwise within 60min to generate a white solid, the white solid is cooled and filtered, 3L of deionized water is used for washing and precipitating, and drying is carried out for 10h at 200 ℃ to obtain 147.9g of aluminum diethylphosphinate, the yield is 94.8%, and the water content is 1%.
Tap density (g/L): 580; angle of repose: 42 DEG degree
Example 27
The dialkyl phosphinic acid metal salt obtained in examples 1 to 26 and comparative example 1 was mixed with PBT, glass fiber and an auxiliary agent at 230 to 260 ℃ in a weight ratio of 10:60:25:5, extruded from a twin-screw extruder, and subjected to sample preparation to test the combustion performance and mechanical properties, and the test results are shown in Table 1:
TABLE 1
The performance tests were carried out according to the following criteria:
tensile strength: GB1040-1992 test method for tensile properties of plastics;
bending strength: GB9341-2000 plastic bending property test method;
deflection: GB9341-2000 plastic bending property test method;
combustion performance: UL94 test for burning performance of plastics;
as can be seen from the above Table 1, the molding material prepared from the dialkylphosphinic salt prepared by the preparation method of the invention has excellent stretching, bending and flame retardant properties, and is suitable for preparing polymer molding materials.
Claims (25)
1. A method for preparing dialkyl phosphinate with good free-running property is characterized by comprising the following steps:
a) adding a crystallization assistant into the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution to obtain the dialkyl phosphinic acid and/or the dialkyl phosphinic acid alkali metal salt aqueous solution containing the crystallization assistant;
b) reacting a mixture of a metal compound and water with the obtained dialkyl phosphinic acid containing the crystallization promoter and/or the dialkyl phosphinic acid alkali metal salt aqueous solution to generate dialkyl phosphinate shown in the formula (I);
wherein the crystallization assistant agent is sodium stearate, sodium polyacrylate, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate; (ii) a
Wherein,
R1，R2identical or different, are linear or branched C1-C6 alkyl;
m is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn;
m is 2 to 4.
2. The method for preparing the dialkylphosphinic salt with good flowability of claim 1, wherein the crystallization promoter is sodium polyacrylate or sodium dodecyl sulfate.
3. The method for preparing the dialkylphosphinic salt with good flowability of the claim 1, wherein the mass fraction of the crystallization promoter is 0.1-50% based on the mass of the dialkylphosphinic acid and/or the aqueous solution of the alkali metal salt of dialkylphosphinic acid.
4. The method for preparing the dialkylphosphinic salt with good flowability of the claim 3, wherein the mass fraction of the crystallization assistant is 1-10% based on the mass of the dialkylphosphinic acid and/or the aqueous solution of the alkali metal salt of dialkylphosphinic acid.
5. The method for preparing the dialkylphosphinic salt with good flowability according to claim 1, wherein the mass concentration of the dialkylphosphinic acid and/or the aqueous solution of the alkali metal salt of dialkylphosphinic acid in step a) is 10-90%.
6. The method for preparing the dialkylphosphinic salt with good flowability of the claim 5, wherein the mass concentration of the dialkylphosphinic acid and/or the aqueous solution of the alkali metal salt of dialkylphosphinic acid in step a) is 30-70%.
7. The method for preparing dialkylphosphinic salts with good flowability according to claim 1, wherein the metal compound in step b) is selected from the group consisting of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum oxide, aluminum hydroxide, ferric sulfate, ferric nitrate, ferric chloride, ferric acetate, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, calcium sulfate, calcium nitrate, calcium chloride and calcium acetate.
8. The method for preparing the dialkylphosphinic salt with good dispersibility according to claim 1, wherein the mass percent of the metal compound in the mixture of the metal compound and water in the step b) is 10-100%.
9. The method for preparing the dialkylphosphinic salt with good dispersibility according to claim 8, wherein the mass percent of the metal compound in the mixture of the metal compound and water in the step b) is 20-50%.
10. The method for preparing the dialkylphosphinic salt with good flowability of the mixture of claim 1, wherein the molar ratio of the mixture of the metal compound and water to the aqueous solution of the dialkylphosphinic acid and/or the alkali metal salt of dialkylphosphinic acid in step b) is 10:1 to 1:10,
11. the method for preparing the dialkylphosphinic salt with good flowability of the mixture of claim 10, wherein the molar ratio of the mixture of the metal compound and water to the aqueous solution of dialkylphosphinic acid and/or the alkali metal salt of dialkylphosphinic acid in step b) is 1:1 to 1: 8.
12. The method for preparing a dialkylphosphinic salt with good flowability according to claim 1, wherein the reaction temperature of the mixture of the metal compound and water and the aqueous solution of dialkylphosphinic acid and/or the alkali metal salt of dialkylphosphinic acid in step b) is 0 to 150 ℃.
13. The method for preparing dialkylphosphinic salts with good dispersibility according to claim 12, wherein the reaction temperature of the mixture of the metal compound and water and the aqueous solution of dialkylphosphinic acid and/or the alkali metal salt of dialkylphosphinic acid in step b) is 70-100 ℃.
14. The method for preparing a dialkylphosphinic salt with good flowability according to claim 1, wherein the reaction time of the mixture of the metal compound and water with the aqueous solution of dialkylphosphinic acid and/or the alkali metal salt of dialkylphosphinic acid in step b) is 0.1 to 10 hours.
15. The method for preparing dialkylphosphinic salts with good dispersibility according to claim 14, wherein the reaction time of the mixture of the metal compound and water with the aqueous solution of dialkylphosphinic acid and/or the alkali metal salt of dialkylphosphinic acid in step b) is 0.1 to 1 hour.
16. The method for preparing a dialkylphosphinic salt with good flowability according to claim 1, wherein the step b) of reacting the mixture of metal compound and water with the aqueous solution of dialkylphosphinic acid and/or alkali metal salt containing a crystallization promoter means that the aqueous solution of dialkylphosphinic acid and/or alkali metal salt containing a crystallization promoter is added to the mixture of metal compound and water for reaction or the mixture of metal compound and water is added to the aqueous solution of dialkylphosphinic acid and/or alkali metal salt containing a crystallization promoter for reaction.
17. The method for preparing dialkylphosphinic salts with good flowability and dispersibility according to claim 16, wherein in step b), the mixture of metal compound and water is reacted with the crystallization assistant-containing dialkylphosphinic acid and/or the aqueous solution of alkali metal dialkylphosphinate, and the mixture of metal compound and water is added to the crystallization assistant-containing aqueous solution of alkali metal dialkylphosphinate and/or dialkylphosphinate for reaction.
18. The method for preparing a dialkylphosphinic salt with good flowability according to claim 1, wherein the residual moisture content of the dialkylphosphinic salt in step b) is 0.01 to 10 wt%.
19. The method for preparing a dialkylphosphinic salt with good flowability according to claim 18, wherein the residual moisture content of the dialkylphosphinic salt in step b) is 0.1 to 1 wt%.
20. The method for preparing a dialkylphosphinic salt with good flowability according to claim 1, wherein the angle of repose of the dialkylphosphinic salt in step b) is 20°~40°。
21. The method for preparing the dialkylphosphinic salt with good flowability of claim 20, wherein the angle of repose of the dialkylphosphinic salt in step b) is 25°~35°。
22. The method for preparing a dialkylphosphinic salt with good flowability according to claim 1, wherein the particle size of the dialkylphosphinic salt in step b) is 1 to 100 μm.
23. The method for preparing a dialkylphosphinic salt with good flowability according to claim 1, wherein the tap density of the dialkylphosphinic salt in step b) is 500-800 g/L.
24. The method for preparing the dialkylphosphinic salt with good flowability of the composition according to claim 23, wherein the tap density of the dialkylphosphinic salt in step b) is 600 to 800 g/L.
25. Use of a dialkylphosphinic salt prepared by the process according to any of claims 1 to 24 as a flame retardant.
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| CN201310061973.1A CN103172664B (en) | 2013-02-27 | 2013-02-27 | Preparation method of dialkylphosphinate with excellent flowing property |
| CN201410251925.3A CN104059101B (en) | 2013-02-27 | 2013-02-27 | A kind of dialkylphosphinic salts with good free-running property |
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| CN103951700B (en) * | 2014-05-15 | 2016-06-29 | 江苏利思德新材料有限公司 | Preparation method of a kind of dimethyl hypophosphites and products thereof and application |
| DE102016213280B4 (en) * | 2016-07-20 | 2024-03-07 | Clariant International Ltd | Diorganylphosphinic acid salts, a process for their preparation and their use |
| CN107828084A (en) | 2016-09-15 | 2018-03-23 | 科莱恩塑料和涂料有限公司 | Fire retardant combination of stabilizers for thermoplastic polymer |
| CN107828207B (en) | 2016-09-15 | 2020-12-25 | 科莱恩塑料和涂料有限公司 | Flame retardant-stabilizer combinations for thermoplastic polymers |
| CN106632464B (en) * | 2016-11-21 | 2019-07-02 | 浙江传化华洋化工有限公司 | A kind of preparation method and application of big partial size spherical shape dialkylphosphinic salts |
| CN107141511B (en) * | 2017-05-25 | 2019-07-12 | 广州铂钡信息科技有限公司 | A kind of additive and preparation method thereof for polymer |
| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
| CN109879909B (en) * | 2019-03-07 | 2021-10-01 | 清远市普塞呋磷化学有限公司 | Preparation method of dialkyl phosphinate with large particle size |
| CN111808133B (en) * | 2020-06-23 | 2023-05-02 | 浙江新化化工股份有限公司 | Diethyl phosphinate aluminum material and preparation method thereof |
| CN114478625B (en) * | 2022-03-10 | 2022-11-25 | 江苏利思德新材料股份有限公司 | Aluminum diethylphosphinate crystal with low fine powder content as well as preparation method and application thereof |
| CN114806249A (en) * | 2022-04-12 | 2022-07-29 | 广州龙文建材有限公司 | Building fireproof coating and preparation method thereof |
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| CN1280583A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acids |
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| US20070213563A1 (en) * | 2006-03-07 | 2007-09-13 | Clariant International Ltd | Mixtures composed of monocarboxy-functionalized dialkylphosphinic acid salts, their use und a process for their preparation |
| CN101356220A (en) * | 2005-12-01 | 2009-01-28 | 苏普雷斯塔有限责任公司 | Flame retardant compositions containing mixtures of disubstituted phosphinate salts and monosubstituted phosphinate salts |
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| CN1280583A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acids |
| CN1660857A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Salts of dialkylphosphinic acids |
| CN101356220A (en) * | 2005-12-01 | 2009-01-28 | 苏普雷斯塔有限责任公司 | Flame retardant compositions containing mixtures of disubstituted phosphinate salts and monosubstituted phosphinate salts |
| US20070213563A1 (en) * | 2006-03-07 | 2007-09-13 | Clariant International Ltd | Mixtures composed of monocarboxy-functionalized dialkylphosphinic acid salts, their use und a process for their preparation |
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| CN103172664A (en) | 2013-06-26 |
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