Method for preparing quaternary phosphonium salts

Patent metadata

Field	Value
Publication number	US-9365596-B2
Application number	US-201414565250-A
Country	US
Kind code	B2
Filing date	Dec 9, 2014
Priority date	Dec 13, 2013
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

A two-step pathway for preparing high pure quaternary phosphonium salts is disclosed. In the first step, hydrogen phosphide (PH 3 ) or a higher phosphine reacts with a protonic compound to produce a phosphonium salt, which then reacts with a carbonic acid diester to produce a quaternary phosphonium salt in the second step. On one hand, hydrogen phosphide (PH 3 ) and higher phosphines, including primary phosphines, secondary phosphines, and tertiary phosphines, after neutralization with protonic compound, become sufficiently reactive and can be alkylated by carbonic acid diester to form quaternary phosphonium cations. On the other hand, as an anion-exchange procedure is completely avoided, the process not only gives quaternary phosphonium salts of high purity, but also gives people freedom to design the cation and the anion of a quaternary phosphonium salt synchronously by choosing a preferred phosphine and a protonic compound that can supply a desired anion.

First claim

The invention claimed is:

1. A process for preparing a quaternary phosphonium salt comprising:
(a) a first step of reacting hydrogen phosphide or a higher phosphine with a protonic compound to produce a phosphonium salt, and
(b) a second step of reacting the phosphonium salt obtained from the first step with a carbonic acid diester to produce a quaternary phosphonium salt.

2. The process as claimed in claim 1 , wherein the phosphine is selected from the group consisting of primary phosphines, secondary phosphines, and tertiary phosphines.

3. The process as claimed in claim 2 , wherein the phosphine is selected from the group consisting of methyl phosphine, ethyl phospine, n-propyl phosphine, cyclohexyl phosphine, phenyl phosphine, dimethyl phosphine, diethyl phosphine, di-i-propyl phosphine, diphenyl phosphine, di-i-butyl phosphine, dicyclohexyl phosphine, diphenyl phosphine, ethyl methyl phosphine, trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tri-i-butyl phosphine, tri-n-butyl phosphine, tri-n-pentyl phosphine, tricyclohexyl phosphine, tri-n-hexyl phosphine, tri-n-octyl phosphine, triphenyl phosphine, dimethyl phenyl phosphine, diethyl phenyl phosphine, butyl diphenyl phosphine, tribenzyl phosphine, tris(hydroxymethyl) phosphine, diethyl 2-chloroethyl phosphine, tris(pentafluoroethyl) phosphine, 1-ethyl phosphoran, 1-phenyl phosphoran, 1-phenyl phosphane, and 1-phenyl phosphepane.

4. The process as claimed in claim 1 , wherein the protonic compound is selected from a group of inorganic acids.

5. The process as claimed in claim 4 , wherein the protonic compound is selected from a group consisting of HAlO 2 , HAl(OH) 4 , H 3 AsO 4 , HAsO 2 , H 3 AsO 3 , H 4 As 2 O 7 , H 3 BO 3 , (HBO 2 ) n , H 2 B 4 O 7 , HBO 3 , H 5 BW 12 O 40 , HBrO 3 , HBrO 2 , HBrO, HBrO 4 , H 4 CO 4 , H 2 C 2 O 6 , H 2 CO 4 (or H 2 CO 3 .H 2 O 2 ), HClO 3 , HClO 4 , HClO 2 , HClO, HONC, HOCN, HNCO, HIO 3 , HIO (or IOH, HIO 4 ), H 5 IO 6 , H 4 I 2 O 9 , HNO 3 , HNO 2 , H 3 PO 4 , H 5 PO 5 , (HPO 3 )n, H 3 PO 3 , H 4 P 2 O 5 , HPO 2 , H 3 PO 2 , H 4 P 2 O 6 , H 4 P 2 O 7 , H 2 SO 4 , H 2 SO 3 , H 2 S 2 O 3 , H 2 S 2 O 7 , H 2 SO 2 , H 2 S x O 6 (x=2˜6), H 6 SO 6 , H 2 S 2 O 4 , H 2 SO 5 , H 2 S 2 O 8 , HSO 3 Cl, HSO 3 F, H 2 SiO 3 (or SiO 2 .H 2 O), H 4 SiO 4 , H 2 Si 2 O 5 (or SiO 2 .H 2 O), H 4 Si 3 O 8 , H 6 Si 2 O 7 (or 2SiO 2 .3H 2 O), H[CHB 11 Cl 11 ], H 2 S, H 2 CS 4 , H 2 CS 3 , HCN, HSeCN, HSCN, HBF 4 , H 2 SiF 6 , HPF 6 , HF, HCl, HBr, and HI.

6. The process as claimed in claim 1 , wherein the protonic compound is selected from a group of organic acids.

7. The process as claimed in claim 6 , wherein the protonic compound is selected from a group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanic acid, lauric acid, tridecanic acid, myristic acid, pentacanic acid, palmitic acid, heptadecanic acid, stearic acid, nonadecanic acid, arachidic acid, isobutyric acid, isovaleric acid, isocaproi acid, ethyl butyric acid, methyl valeric acid, isocaprylic acid, propyl valeric acid, ethyl caproic acid, isocapric acid, tuberculostearic acid, pivalic acid, 2,2-dimethylbutani acid, 2,2-dimethylpentanic acid, 2,2-dimethylhexanic acid, 2,2-dimethylheptanic acid, 2,2-dimethyloctanic acid, 2-methyl-2-ethylbutanic acid, 2-methyl-2-ethylpentanic acid, 2-methyl-2-ethylhexanic acid, 2-methyl-2-ethyl-jeptanic acid, 2-methyl-2-propylpentanic acid, 2-methyl-2-propylhexanic acid, 2-methyl-2-propylheptanic acid, acrylic acid, crotonic acid, isocrotonic acid, 3-butenic acid, pentenic acid, hexenic acid, heptenic acid, octenic acid, nonenic acid, decenic acid, undecenic acid, dodecinic acid, tuzuic acid, physteric acid, goshuyuic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, methacrylic acid, 3-methylcrotonic acid, tiglic acid, methyl pentenic acid, cyclopentacarboxylic acid, cyclohexanecarboxylic acid, trifluoroacetic acid, phenylacetic acid, chloroacetic acid, glycoric acid, lactic acid, citric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane diacid, dodecane diacid, tridecane diacid, tetradecane diacid, pentadecane diacid, hexadecane diacid, heptadecane diacid, octadecane diacid, noncadecane diacid, eicosane diacid, methyl malonic acid, ethyl malonic acid, propyl malonic acid, butyl malonic acid, hexyl malonic acid, dimethyl malonic acid, methyl ethyl malonic acid, diethylmalonic acid, methyl propyl malonic acid, methyl butyl malonic acid, ethyl propyl malonic acid, dipropyl malonic acid, ethyl butyl malonic acid, propyl butyl malonic acid, dibutylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2-methyl-glutaric acid, maleic acid, citraconic acid, itaconic acid, methyleneglutaric acid, monomethyl maleate, 1,5-octanedicarboxylic acid, 5,6-decanedicarboxylic acid, 1,7-decanedicarboxylic acid, 4,6-dimethyl-4-nonene-1,2-dicarboxylic acid, 4,6-dimethyl-1,2-nonanedicarboxylic acid, 1,7-dodecanedicarboxylic acid, 5-ethyl-1,10-decanedicarboxylic acid, 6-methyl-6-dodecene-1,12-dicatboxylic acid, 6-methyl-1,12-dodecanedicarboxylic acid, 6-ethylene-1,12-dodecanedicarboxylic acid, 7-methyl-7-tetradecene-1,14-dicarboxylic acid, 7-methyl-1,14-tetradecanedicarboxylic acid, 3-hexyl-4-decene-1,2-dicarboxylic acid, 3-hexyl-1,12-decanedicarboxylic acid, 6-ethylene-9-hexadecene-1,16-dicarboxylic acid, 6-ethyl-1,16-hexadecanedicarboxylic acid, 6-phenyl-1,12-dodecanedicarboxylic acid, 7,12-dimethyl-7,11-octadecanediene-1,18-dicarboxylic acid, 7,12-dimethyl-1,18-octadecanedicarboxylic acid, 6,8-diphenyl-1,14-tetradecanedicarboxylic acid, 1,1-cyclopen-tanedicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 5-nobor-nene-2,3-dicarboxylic acid, malic acid, glutamic acid, tartaric acid, citric acid, benzoic acid, toluic acid, ethylbenzoic acid, propylbenzoic acid, isopropylbenzoic acid, butylbenzoic acid, sec-butylbenzoic acid, tert-butylbenzoic acid, hydroxybenzoic acid, anisic acid, ethoxybenzoic acid, propoxybenzoic acid, isopropoxybenzoic acid, butoxybenzoic acid, isobutoxybenzoic acid, sec-butoxybenzoic acid, tert-butoxybenzoic acid, aminobenzoic acid, N-methylaminobenzoic acid, N-ethylaminobenzoic acid, N-propylaminobenzoic acid, N-isopropylaminobenzoic acid, N-butylaminobenzoic acid, N-isobutylaminobenzoic acid, N-sec-butylaminobenzoic acid, N-tert-butylaminobenzoic acid, N,N-dimethylaminobenzoic acid, N,N-diezoic acid, resorcinic acid, nitrophthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, and pyromellitic acid.

8. The process as claimed in claim 1 , wherein the protonic compound is selected from a group of non-acid protonic compounds having at least one proton activated by the neighboring groups that are electron-withdrawing.

9. The process as claimed in claim 8 , wherein the protonic compound is selected from a group of phenol, p-fluorophenol, β-naphthol, o-nitrophenol, p-nitrophenol, p-aminophenol, catechol, 2,4-dichlorophenol, and 4,4′-dihydroxydiphenyl-2,2-propane.

10. The process as claimed in claim 8 , wherein the protonic compound is selected from a group of HN(C m F 2m+1 SO 2 )(C n F 2n+1 SO 2 ), HN(C n F 2n+1 SO 2 ) 2 , and HNC m F 2m SO 2 , wherein m, n are integral numbers of from 1 to 10.

11. The process as claimed in claim 10 , wherein the protonic compound is selected from a group of

12.

Assignees

• Microvast Power Systems Co Ltd
• Microvast Power Systems Co Ltd

Inventors

• Zheng Zhuoqun
• Shen Dawei
• Nie Yunhua
• Qiu Jian
• Zhang Yumei

Classifications

• C07F9/5442

  Aromatic phosphonium compounds (P-C aromatic linkage) · CPC title

• H01M10/0566

  Liquid materials · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• Y02E60/122

  Cross-Sectional Technologies · mapped topic

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title