CN101985413A - Onium salt compound - Google Patents
Onium salt compound Download PDFInfo
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- CN101985413A CN101985413A CN2009101590128A CN200910159012A CN101985413A CN 101985413 A CN101985413 A CN 101985413A CN 2009101590128 A CN2009101590128 A CN 2009101590128A CN 200910159012 A CN200910159012 A CN 200910159012A CN 101985413 A CN101985413 A CN 101985413A
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- diethyl
- picoline
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Abstract
The invention relates to an onium salt compound, which comprises onium salt and organic base shown in formula (1), namely, the formula is shown as Q<+>.A<->, wherein Q<+> represents onium ions and A<-> represents PF6<-> in the formula.
Description
Technical field
The present invention relates to salt composition.
Background technology
Has phosphofluoric acid salt anionic (PF
6 -) salt, can be widely used in the electro chemical elements use ionogen, tensio-active agent, phase-transfer catalyst, antistatic agent, sterilant etc. of double layer capacitor etc.Yet, the easy moisture absorption of this salt, but also cause hydrolysis easily, so existence has toxicity and metal, resin is had corrosive hydrofluoric problem owing to the micro-moisture of unavoidably sneaking into causes hydrolysis, generation on preserving and on handling.
As storage stability good have a PF
6 -Salt, a kind of PF that has by specific solvent lining is disclosed in TOHKEMY 2001-48846 communique
6 -Salt, but should be by the PF that has of specific solvent lining
6 -Salt also can cause hydrolysis in time more than 60 ℃ because of the moisture of trace, stability can't be called fully.
Summary of the invention
The invention provides as inferior content:
＜1〉a kind of salt composition contains salt and the organic bases shown in the formula (1);
Q
+·A
- (1)
(in the formula, Q
+The expression ion, A
-Expression PF
6 -)
＜2〉according to＜1〉described salt composition, also contain solvent;
＜3〉according to＜1〉or＜2〉described salt composition, wherein, ion is a quaternary ammonium cation Huo quaternary phosphine positively charged ion;
＜4〉according to＜1 〉～＜3 in each described salt composition, wherein, organic bases is tertiary amine or tertiary phosphine;
＜5〉according to＜4〉described salt composition, wherein, tertiary amine is to be selected from least a in aliphatic tertiary amine, aromatic nitrile base, pyridines and the imidazoles;
＜6〉according to＜1 〉～＜5 in each described salt composition, wherein, the content of organic bases is 10～5000ppm with respect to the salt shown in the formula (1);
＜7〉a kind of stabilization method of salt is characterized in that, salt shown in the formula (1) and organic bases are mixed;
＜8〉a kind of store method of salt is characterized in that, the salt shown in the formula (1) is preserved in the presence of organic bases.
Embodiment
In the formula of the salt shown in the formula (1) (following brief note is salt (1)), as Q
+The expression ion can be enumerated quaternary ammonium cation, quaternary phosphine positively charged ion etc.
As quaternary ammonium cation, can enumerate tetraalkylammonium cation, tetramethyleneimine positively charged ion, morpholine positively charged ion, glyoxaline cation, tetrahydropyrimidine positively charged ion, piperazine positively charged ion, piperidines positively charged ion, pyridylium etc.As the quaternary phosphine positively charged ion, can enumerate Si Wan Ji phosphonium cation.
As tetraalkylammonium cation, can enumerate tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, the TBuA positively charged ion, the four pentyl ammonium cation, the tetrahexyl ammonium positively charged ion, four heptyl ammonium cations, four octyl group ammonium cations, four nonyl ammonium cations, four decyl ammonium cations, four (dodecyl) ammonium cation, the ethyl-trimethyl ammonium cation, the diethyl-dimethyl ammonium cation, triethyl ammonium methyl positively charged ion, tetraethylammonium cation, trimethylammonium propyl ammonium positively charged ion, the trimethyl isopropyl ammonium cation, ethyl dimethyl propyl ammonium cation, ethyl dimethyl sec.-propyl ammonium cation, diethylmethyl propyl ammonium positively charged ion, diethylmethyl sec.-propyl ammonium cation, dimethyl dipropylammonium positively charged ion, dimethyl propyl sec.-propyl ammonium cation, dimethyl di-isopropyl ammonium cation, triethyl propyl ammonium positively charged ion, butyl trimethyl ammonium positively charged ion, isobutyl-trimethyl ammonium positively charged ion, tertiary butyl trimethyl ammonium positively charged ion, triethyl sec.-propyl ammonium cation, ethyl-methyl dipropylammonium positively charged ion, ethyl-methyl di-isopropyl ammonium cation, butyl ethyl Dimethyl Ammonium positively charged ion, isobutyl-ethyl Dimethyl Ammonium positively charged ion, tertiary butyl ethyl Dimethyl Ammonium positively charged ion, diethyl dipropylammonium positively charged ion, diethyl propyl group di-isopropyl ammonium cation, diethyl dipropylammonium positively charged ion, methyl tripropyl ammonium cation, methyl dipropyl sec.-propyl ammonium cation, methyl-propyl di-isopropyl ammonium cation, butyl triethyl ammonium positively charged ion, isobutyl-triethyl ammonium positively charged ion, tertiary butyl triethyl ammonium positively charged ion, dibutyl Dimethyl Ammonium positively charged ion, diisobutyl Dimethyl Ammonium positively charged ion, di-t-butyl Dimethyl Ammonium positively charged ion, butyl isobutyl-Dimethyl Ammonium positively charged ion, butyl tertiary butyl Dimethyl Ammonium positively charged ion, isobutyl-tertiary butyl Dimethyl Ammonium positively charged ion, tricaprylmethylammonium positively charged ion etc.
As the tetramethyleneimine positively charged ion, can enumerate following 1 of the alkyl that on the carbon atom of pyrrolidine ring, has, 1-dialkyl group tetramethyleneimine positively charged ion: 1,1-dimethyl pyrrolidine positively charged ion, 1-ethyl-1-crassitude positively charged ion, 1,1-diethyl tetramethyleneimine positively charged ion, 1,1,2-trimethylammonium tetramethyleneimine positively charged ion, 1,1,3-trimethylammonium tetramethyleneimine positively charged ion, 1-ethyl-1,2-dimethyl pyrrolidine positively charged ion, 1-ethyl-1,3-dimethyl pyrrolidine positively charged ion, 2-ethyl-1,1-dimethyl pyrrolidine positively charged ion, 3-ethyl-1,1-dimethyl pyrrolidine positively charged ion, 1,1-diethyl-2-crassitude positively charged ion, 1,1-diethyl-3-crassitude positively charged ion, 1,2-diethyl-1-crassitude positively charged ion, 1,3-diethyl-1-crassitude positively charged ion, 1,1,2-triethyl tetramethyleneimine positively charged ion, 1,1,3-triethyl tetramethyleneimine positively charged ion, 1,1,2,2-tetramethylpyrrolidi-e positively charged ion, 1,1,2,3-tetramethylpyrrolidi-e positively charged ion, 1,1,2,4-tetramethylpyrrolidi-e positively charged ion, 1,1,2,5-tetramethylpyrrolidi-e positively charged ion, 1,1,3,4-tetramethylpyrrolidi-e positively charged ion, 1,1,3,3-tetramethylpyrrolidi-e positively charged ion, 1,1-dimethyl pyrrolidine positively charged ion, 1-ethyl-1-crassitude positively charged ion, 1,1-diethyl tetramethyleneimine positively charged ion, 1,1,2-trimethylammonium tetramethyleneimine positively charged ion, 1,1,3-trimethylammonium tetramethyleneimine positively charged ion, 1-ethyl-1,2-dimethyl pyrrolidine positively charged ion, 1-ethyl-1,3-dimethyl pyrrolidine positively charged ion, 2-ethyl-1,1-dimethyl pyrrolidine positively charged ion, 3-ethyl-1,1-dimethyl pyrrolidine positively charged ion, 1,1-diethyl-2-crassitude positively charged ion, 1,1-diethyl-3-crassitude positively charged ion, 1,2-diethyl-1-crassitude positively charged ion, 1,3-diethyl-1-crassitude positively charged ion, 1,1,2-triethyl tetramethyleneimine positively charged ion, 1,1,3-triethyl tetramethyleneimine positively charged ion, 1,1,2,2-tetramethylpyrrolidi-e positively charged ion, 1,1,2,3-tetramethylpyrrolidi-e positively charged ion, 1,1,2,4-tetramethylpyrrolidi-e positively charged ion, 1,1,2,5-tetramethylpyrrolidi-e positively charged ion, 1,1,3,4-tetramethylpyrrolidi-e positively charged ion, 1,1,3,3-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,2-trimethylammonium tetramethyleneimine positively charged ion, 2-ethyl-1,1,3-trimethylammonium tetramethyleneimine positively charged ion, 3-ethyl-1,1,2-trimethylammonium tetramethyleneimine positively charged ion, 3-ethyl-1,1,3-trimethylammonium tetramethyleneimine positively charged ion, 2-ethyl-1,1,4-trimethylammonium tetramethyleneimine positively charged ion, 4-ethyl-1,1,2-trimethylammonium tetramethyleneimine positively charged ion, 2-ethyl-1,1,5-trimethylammonium tetramethyleneimine positively charged ion, 5-ethyl-1,1,2-trimethylammonium tetramethyleneimine positively charged ion, 3-ethyl-1,1,4-trimethylammonium tetramethyleneimine positively charged ion, 4-ethyl-1,1,3-trimethylammonium tetramethyleneimine positively charged ion, 1-ethyl-1,2,2-trimethylammonium tetramethyleneimine positively charged ion, 1-ethyl-1,2,3-trimethylammonium tetramethyleneimine positively charged ion, 1-ethyl-1,3,3-trimethylammonium tetramethyleneimine positively charged ion, 1-ethyl-1,2,4-trimethylammonium tetramethyleneimine positively charged ion, 1-ethyl-1,2,5-trimethylammonium tetramethyleneimine positively charged ion, 1-ethyl-1,3,4-trimethylammonium tetramethyleneimine positively charged ion, 2,2-diethyl-1,1-dimethyl pyrrolidine positively charged ion, 2,3-diethyl-1,1-dimethyl pyrrolidine positively charged ion, 3,3-diethyl-1,1-dimethyl pyrrolidine positively charged ion, 2,4-diethyl-1,1-dimethyl pyrrolidine positively charged ion, 2,5-diethyl-1,1-dimethyl pyrrolidine positively charged ion, 3,4-diethyl-1,1-dimethyl pyrrolidine positively charged ion, 1,2-diethyl-1,2-dimethyl pyrrolidine positively charged ion, 1,2-diethyl-1,3-dimethyl pyrrolidine positively charged ion, 1,3-diethyl-1,2-dimethyl pyrrolidine positively charged ion, 1,3-diethyl-1,3-dimethyl pyrrolidine positively charged ion, 1,2-diethyl-1,4-dimethyl pyrrolidine positively charged ion, 1,4-diethyl-1,2-dimethyl pyrrolidine positively charged ion, 1,2-diethyl-1,5-dimethyl pyrrolidine positively charged ion, 1,5-diethyl-1,2-dimethyl pyrrolidine positively charged ion, 1,3-diethyl-1,4-dimethyl pyrrolidine positively charged ion, 1,1,2,2,3-pentamethyl-tetramethyleneimine positively charged ion, 1,1,2,2,4-pentamethyl-tetramethyleneimine positively charged ion, 1,1,2,2,5-pentamethyl-tetramethyleneimine positively charged ion, 1,1,2,3,4-pentamethyl-tetramethyleneimine positively charged ion, 1,1,2,3,5-pentamethyl-tetramethyleneimine positively charged ion, 1,1,3,3,4-pentamethyl-tetramethyleneimine positively charged ion, 1,1,3,3,5-pentamethyl-tetramethyleneimine positively charged ion, 1-ethyl-1,2,2,3-tetramethylpyrrolidi-e positively charged ion, 1-ethyl-1,2,2,4-tetramethylpyrrolidi-e positively charged ion, 1-ethyl-1,2,2,5-tetramethylpyrrolidi-e positively charged ion, 1-ethyl-1,2,3,4-tetramethylpyrrolidi-e positively charged ion, 1-ethyl-1,2,3,5-tetramethylpyrrolidi-e positively charged ion, 1-ethyl-1,2,4,5-tetramethylpyrrolidi-e positively charged ion, 1-ethyl-1,3,3,4-tetramethylpyrrolidi-e positively charged ion, 1-ethyl-1,3,3,5-tetramethylpyrrolidi-e positively charged ion, 1-ethyl-1,3,4,5-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,2,3-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,2,4-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,2,5-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,3,3-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,3,4-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,3,5-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,4,4-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,4,5-tetramethylpyrrolidi-e positively charged ion, 2-ethyl-1,1,5,5-tetramethylpyrrolidi-e positively charged ion, 3-ethyl-1,1,2,2-tetramethylpyrrolidi-e positively charged ion, 3-ethyl-1,1,2,3-tetramethylpyrrolidi-e positively charged ion, 3-ethyl-1,1,2,4-tetramethylpyrrolidi-e positively charged ion, 3-ethyl-1,1,2,5-tetramethylpyrrolidi-e positively charged ion, 3-ethyl-1,1,3,4-tetramethylpyrrolidi-e positively charged ion, 3-ethyl-1,1,4,4-tetramethylpyrrolidi-e positively charged ion, 3-ethyl-1,1,4,5-tetramethylpyrrolidi-e positively charged ion, 1,1,2,2,3,3-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,2,3,4-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,2,3,5-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,2,4,4-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,2,4,5-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,2,5,5-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,3,3,4-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,3,3,5-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,3,4,4-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,3,5,5-hexamethyl tetramethyleneimine positively charged ion, 1,1,2,3,4,5-hexamethyl tetramethyleneimine positively charged ion etc.
As the morpholine positively charged ion, can enumerate the following 4-alkyl morpholine positively charged ion that on the carbon atom of morpholine ring, has alkyl: 4,4-thebaine positively charged ion, 4-ethyl-4-methylmorpholine positively charged ion, 4,4-diethyl morpholine positively charged ion, 3,4,4-trimethylammonium morpholine positively charged ion, 2,4,4-trimethylammonium morpholine positively charged ion, 3-ethyl-4,4-thebaine positively charged ion, 3,4-dimethyl-4-ethyl morpholine positively charged ion, 2,4-dimethyl-4-ethyl morpholine positively charged ion, 3-methyl-4,4-diethyl morpholine positively charged ion, 2,4-dimethyl-4-ethyl morpholine positively charged ion, 2-methyl-4,4-diethyl morpholine positively charged ion, 3,4-diethyl-4-methylmorpholine positively charged ion, 2,4-diethyl-4-methylmorpholine positively charged ion, 3,4,4-triethyl morpholine positively charged ion, 2,4,4-triethyl morpholine positively charged ion, 3,3,4,4-tetramethyl-morpholine positively charged ion, 2,3,4,4-tetramethyl-morpholine positively charged ion, 2,4,4,5-tetramethyl-morpholine positively charged ion, 3,4,4,5-tetramethyl-morpholine positively charged ion, 2,2,4,4-tetramethyl-morpholine positively charged ion, 2,4,4,6-tetramethyl-morpholine positively charged ion, 2,4,4-trimethylammonium-3-ethyl morpholine positively charged ion, 2-ethyl-3,4,4-trimethylammonium morpholine positively charged ion, 2,4,4-trimethylammonium-5-ethyl morpholine positively charged ion, 2-ethyl-4,4,5-trimethylammonium morpholine positively charged ion, 3-ethyl-4,4,6-trimethylammonium morpholine positively charged ion, 2-ethyl-4,4,5-trimethylammonium morpholine positively charged ion, 2-ethyl-4,4,6-trimethylammonium morpholine positively charged ion, 2,3-dimethyl-4,4-diethyl morpholine positively charged ion, 2,5-dimethyl-4,4-diethyl morpholine positively charged ion, 3,5-dimethyl-4,4-diethyl morpholine positively charged ion, 2,6-dimethyl-4,4-diethyl morpholine positively charged ion, 2,4-dimethyl-3,4-diethyl morpholine positively charged ion, 2,4-diethyl-3,4-thebaine positively charged ion, 2,4-dimethyl-4,5-diethyl morpholine positively charged ion, 2,4-diethyl-4,5-thebaine positively charged ion, 3,4-diethyl-4,5-thebaine positively charged ion, 2,4-diethyl-4,6-thebaine positively charged ion, 2,3-diethyl-4,4-thebaine positively charged ion, 2,5-diethyl-4,4-thebaine positively charged ion, 3,5-diethyl-4,4-thebaine positively charged ion, 2,6-diethyl-4,4-thebaine positively charged ion, 2,3,4,4,6-pentamethyl-morpholine positively charged ion, 2,3,4,4,5-pentamethyl-morpholine positively charged ion, 2,6,4,4-tetramethyl--3-ethyl morpholine positively charged ion, 2,4,4,5-tetramethyl--3-ethyl morpholine positively charged ion, 2-ethyl-3,4,4,6-tetramethyl-morpholine positively charged ion, 2-ethyl-3,4,4,5-tetramethyl-morpholine positively charged ion, 2,3,4,4,5,6-hexamethyl morpholine positively charged ion etc.
As glyoxaline cation, can enumerate following 1 of the alkyl that on the carbon atom of imidazole ring, has, 3-dialkylimidazolium positively charged ion: 1,3-methylimidazole positively charged ion, 1-ethyl-3-Methylimidazole positively charged ion, 1,3-diethyl glyoxaline cation, 1,2,3-tri-methylimidazolium positively charged ion, 1,3,4-tri-methylimidazolium positively charged ion, 1-ethyl-2,3-methylimidazole positively charged ion, 1-ethyl-3,4-methylimidazole positively charged ion, 1-ethyl-3,5-methylimidazole positively charged ion, 2-ethyl-1,3-methylimidazole positively charged ion, 4-ethyl-1,3-methylimidazole positively charged ion, 1,2-diethyl-3-Methylimidazole positively charged ion, 1,4-diethyl-3-Methylimidazole positively charged ion, 1,5-diethyl-3-Methylimidazole positively charged ion, 1,3-diethyl-glyoxal ethyline positively charged ion, 1,3-diethyl-4-methylimidazole positively charged ion, 1,2,3-triethyl glyoxaline cation, 1,3,4-triethyl glyoxaline cation, 1,2,3,4-tetramethyl-glyoxaline cation, 1-ethyl-2,3,4-tri-methylimidazolium positively charged ion, 1-ethyl-2,3,5-tri-methylimidazolium positively charged ion, 1-ethyl-3,4,5-tri-methylimidazolium positively charged ion, 2-ethyl-1,3,4-tri-methylimidazolium positively charged ion, 4-ethyl-1,2,3-tri-methylimidazolium positively charged ion, 1,2-diethyl-3,4-methylimidazole positively charged ion, 1,3-diethyl-2,4-methylimidazole positively charged ion, 1,4-diethyl-2,3-methylimidazole positively charged ion, 2,4-diethyl-1,3-methylimidazole positively charged ion, 4,5-diethyl-1,3-methylimidazole positively charged ion, 1,2,3-triethyl-4-methylimidazole positively charged ion, 1,2,4-triethyl-3-Methylimidazole positively charged ion, 1,2,5-triethyl-3-Methylimidazole positively charged ion, 1,3,4-triethyl-glyoxal ethyline positively charged ion, 1,3,4-triethyl-5-Methylimidazole positively charged ion, 1,4,5-triethyl-3-Methylimidazole positively charged ion, 1,2,3,4,5-pentamethyl-glyoxaline cation, 1-methyl-3-propyl imidazole positively charged ion etc.
As the tetrahydropyrimidine positively charged ion, can enumerate following 1 of the alkyl that on the carbon atom of tetrahydropyrimidine ring, has, 3-dialkyl group tetrahydropyrimidine positively charged ion: 1,3-dimethyl tetrahydro pyrimidine positively charged ion, 1-ethyl-3-methyl tetrahydropyrimidine positively charged ion, 1,3-diethyl tetrahydropyrimidine positively charged ion, 1,2,3-trimethylammonium tetrahydropyrimidine positively charged ion, 1,3,4-trimethylammonium tetrahydropyrimidine positively charged ion, 1,3,5-trimethylammonium tetrahydropyrimidine positively charged ion, 1-ethyl-2,3-dimethyl tetrahydro pyrimidine positively charged ion, 1-ethyl-3,4-dimethyl tetrahydro pyrimidine positively charged ion, 1-ethyl-3,5-dimethyl tetrahydro pyrimidine positively charged ion, 1-ethyl-3,6-dimethyl tetrahydro pyrimidine positively charged ion, 2-ethyl-1,3-dimethyl tetrahydro pyrimidine positively charged ion, 4-ethyl-1,3-dimethyl tetrahydro pyrimidine positively charged ion, 5-ethyl-1,3-dimethyl tetrahydro pyrimidine positively charged ion, 1,2,3,4-tetramethyl-tetrahydropyrimidine positively charged ion, 1,2,3,5-tetramethyl-tetrahydropyrimidine positively charged ion, 1-ethyl-2,3,4-trimethylammonium tetrahydropyrimidine positively charged ion, 1-ethyl-2,3,5-trimethylammonium tetrahydropyrimidine positively charged ion, 1-ethyl-2,3,6-trimethylammonium tetrahydropyrimidine positively charged ion, 2-ethyl-1,3,4-trimethylammonium tetrahydropyrimidine positively charged ion, 2-ethyl-1,3,5-trimethylammonium tetrahydropyrimidine positively charged ion, 4-ethyl-1,2,3-trimethylammonium tetrahydropyrimidine positively charged ion, 4-ethyl-1,3,5-trimethylammonium tetrahydropyrimidine positively charged ion, 4-ethyl-1,3,6-trimethylammonium tetrahydropyrimidine positively charged ion, 5-ethyl-1,2,3-trimethylammonium tetrahydropyrimidine positively charged ion, 5-ethyl-1,3,4-trimethylammonium tetrahydropyrimidine positively charged ion, 1,2-diethyl-3,4-dimethyl tetrahydro pyrimidine positively charged ion, 1,2-diethyl-3,5-dimethyl tetrahydro pyrimidine positively charged ion, 1,2-diethyl-3,6-dimethyl tetrahydro pyrimidine positively charged ion, 1,3-diethyl-2,4-dimethyl tetrahydro pyrimidine positively charged ion, 1,3-diethyl-2,5-dimethyl tetrahydro pyrimidine positively charged ion, 1,4-diethyl-2,3-dimethyl tetrahydro pyrimidine positively charged ion, 1,4-diethyl-3,5-dimethyl tetrahydro pyrimidine positively charged ion, 1,4-diethyl-3,6-dimethyl tetrahydro pyrimidine positively charged ion, 1,5-diethyl-2,3-dimethyl tetrahydro pyrimidine positively charged ion, 1,5-diethyl-3,4-dimethyl tetrahydro pyrimidine positively charged ion, 1,5-diethyl-3,6-dimethyl tetrahydro pyrimidine positively charged ion, 2,4-diethyl-1,3-dimethyl tetrahydro pyrimidine positively charged ion, 2,5-diethyl-1,3-dimethyl tetrahydro pyrimidine positively charged ion, 4,5-diethyl-1,3-dimethyl tetrahydro pyrimidine positively charged ion, 4,6-diethyl-1,3-dimethyl tetrahydro pyrimidine positively charged ion, 1,2,3,4,5-pentamethyl-tetrahydropyrimidine positively charged ion, 1,2,3,4,6-pentamethyl-tetrahydropyrimidine positively charged ion, 1,2,3,4,5,6-hexamethyl tetrahydropyrimidine positively charged ion etc.
As the piperazine positively charged ion, can enumerate following 1,1 of the alkyl that on the carbon atom of piperazine ring, has, 4,4-tetraalkyl piperazine positively charged ion: 1,1,4,4-tetramethyl-piperazine positively charged ion, 1-ethyl-1,4,4-tri methyl piperazine positively charged ion, 1,1-diethyl-4,4-lupetazin positively charged ion, 1,1,4-triethyl-4-methylpiperazine positively charged ion, 1,1,4,4-tetraethyl-piperazine positively charged ion, 1,1,2,4,4-pentamethyl-piperazine positively charged ion, 1,1,3,4,4-pentamethyl-piperazine positively charged ion, 1,1,2,3,4,4-hexamethyl piperazine positively charged ion, 1,1,2,4,4,5-hexamethyl piperazine positively charged ion, 1,1,2,4,4,6-hexamethyl piperazine positively charged ion, 1,1,3,4,4,5-hexamethyl piperazine positively charged ion, 1-ethyl-1,2,4,4-tetramethyl-piperazine positively charged ion, 1-ethyl-1,3,4,4-tetramethyl-piperazine positively charged ion, 2-ethyl-1,1,4,4-tetramethyl-piperazine positively charged ion, 1-ethyl-1,2,4,4-tetramethyl-piperazine positively charged ion, 1-ethyl-1,3,4,4-tetramethyl-piperazine positively charged ion, 1,1-diethyl-2,4,4-tri methyl piperazine positively charged ion, 1,4-diethyl-1,2,4-tri methyl piperazine positively charged ion, 1,2-diethyl-1,4,4-tri methyl piperazine positively charged ion, 1,3-diethyl-1,4,4-tri methyl piperazine positively charged ion etc.
As the piperidines positively charged ion, can enumerate following 1 of the alkyl that on the carbon atom of piperidine ring, has, 1-dialkyl piperidine positively charged ion: 1,1-lupetidine positively charged ion, 1-ethyl-1-methyl piperidine positively charged ion, 1,1-diethyl piperidines positively charged ion, 1,1,2-trimethyl-piperidine positively charged ion, 1,1,3-trimethyl-piperidine positively charged ion, 1,1,4-trimethyl-piperidine positively charged ion, 1,1,2,2-tetramethyl piperidine positively charged ion, 1,1,2,3-tetramethyl piperidine positively charged ion, 1,1,2,4-tetramethyl piperidine positively charged ion, 1,1,2,5-tetramethyl piperidine positively charged ion, 1,1,2,6-tetramethyl piperidine positively charged ion, 1,1,3,3-tetramethyl piperidine positively charged ion, 1,1,3,4-tetramethyl piperidine positively charged ion, 1,1,3,5-tetramethyl piperidine positively charged ion, 1-ethyl-1,2-lupetidine positively charged ion, 1-ethyl-1,3-lupetidine positively charged ion, 1-ethyl-1,4-lupetidine positively charged ion, 1-ethyl-1,2,3-trimethyl-piperidine positively charged ion, 1-ethyl-1,2,4-trimethyl-piperidine positively charged ion, 1-ethyl-1,2,5-trimethyl-piperidine positively charged ion, 1-ethyl-1,2,6-trimethyl-piperidine positively charged ion, 1-ethyl-1,3,4-trimethyl-piperidine positively charged ion, 1-ethyl-1,3,5-trimethyl-piperidine positively charged ion, 1,1-diethyl-pipecoline positively charged ion, 1,1-diethyl-3-methyl piperidine positively charged ion, 1,1-diethyl-4-methyl piperidine positively charged ion, 1,1-diethyl-2,3-lupetidine positively charged ion, 1,1-diethyl-2,4-lupetidine positively charged ion, 1,1-diethyl-2,5-lupetidine positively charged ion, 1,1-diethyl-2,6-lupetidine positively charged ion, 1,1-diethyl-3,4-lupetidine positively charged ion, 1,1-diethyl-3,5-lupetidine positively charged ion, 2-ethyl-1,1,3-trimethyl-piperidine positively charged ion, 2-ethyl-1,1,4-trimethyl-piperidine positively charged ion, 2-ethyl-1,1,5-trimethyl-piperidine positively charged ion, 2-ethyl-1,1,6-trimethyl-piperidine positively charged ion, 3-ethyl-1,1,2-trimethyl-piperidine positively charged ion, 3-ethyl-1,1,4-trimethyl-piperidine positively charged ion, 3-ethyl-1,1,5-trimethyl-piperidine positively charged ion, 3-ethyl-1,1,6-trimethyl-piperidine positively charged ion, 4-ethyl-1,1,2-trimethyl-piperidine positively charged ion, 4-ethyl-1,1,3-trimethyl-piperidine positively charged ion, 1,2-diethyl-1,3-lupetidine positively charged ion, 1-ethyl-1,2,4-trimethyl-piperidine positively charged ion, 1,2-diethyl-1,5-lupetidine positively charged ion, 1,2-diethyl-1,6-lupetidine positively charged ion, 1,3-diethyl-1,5-lupetidine positively charged ion, 1,3-diethyl-1,4-lupetidine positively charged ion, 1,3-diethyl-1,5-lupetidine positively charged ion, 1,3-diethyl-1,6-lupetidine positively charged ion, 1,4-diethyl-1,2-lupetidine positively charged ion, 1,4-diethyl-1,3-lupetidine positively charged ion, 1,1,2-triethyl-3-methyl piperidine positively charged ion, 1,1,2-triethyl-4-methyl piperidine positively charged ion, 1,1,2-triethyl-5-methyl piperidine positively charged ion, 1,1,2-triethyl-6-methyl piperidine positively charged ion, 1,1,3-triethyl-pipecoline positively charged ion, 1,1,3-triethyl-4-methyl piperidine positively charged ion, 1,1,3-triethyl-5-methyl piperidine positively charged ion, 1,1,3-triethyl-6-methyl piperidine positively charged ion, 1,1,4-triethyl-pipecoline positively charged ion, 1,1,4-triethyl-3-methyl piperidine positively charged ion, 2-ethyl-1,1-lupetidine positively charged ion, 3-ethyl-1,1-lupetidine positively charged ion, 4-ethyl-1,1-lupetidine positively charged ion, 2,3-diethyl-1,1-lupetidine positively charged ion, 2,4-diethyl-1,1-lupetidine positively charged ion, 2,5-diethyl-1,1-lupetidine positively charged ion, 2,6-diethyl-1,1-lupetidine positively charged ion, 3,4-diethyl-1,1-lupetidine positively charged ion, 3,5-diethyl-1,1-lupetidine positively charged ion, 1,2-diethyl-1-methyl piperidine positively charged ion, 1,3-diethyl-1-methyl piperidine positively charged ion, 1,4-diethyl-1-methyl piperidine positively charged ion, 1,2,3-triethyl-1-methyl piperidine positively charged ion, 1,2,4-triethyl-1-methyl piperidine positively charged ion, 1,2,5-triethyl-1-methyl piperidine positively charged ion, 1,2,6-triethyl-1-methyl piperidine positively charged ion, 1,3,4-triethyl-1-methyl piperidine positively charged ion, 1,3,5-triethyl-1-methyl piperidine positively charged ion, 1,1,2-triethyl piperidines positively charged ion, 1,1,2-triethyl piperidines positively charged ion, 1,1,4-triethyl piperidines positively charged ion, 1,1,2,3-tetraethyl-piperidines positively charged ion, 1,1,2,4-tetraethyl-piperidines positively charged ion, 1,1,2,5-tetraethyl-piperidines positively charged ion, 1,1,2,6-tetraethyl-piperidines positively charged ion, 1,1,3,4-tetraethyl-piperidines positively charged ion, 1,1,3,5-tetraethyl-piperidines positively charged ion etc.
As pyridylium, can enumerate the following 1-alkyl pyridine positively charged ion that on the carbon atom of pyridine ring, has alkyl: 1-picoline positively charged ion, 1-ethylpyridine positively charged ion, 1-propyl group pyridylium, 1-butyl-pyridinium positively charged ion, 1-pentyl pyridine positively charged ion, 1-hexyl pyridylium, 1-heptyl pyridylium, 1-octyl group pyridylium, 1-nonyl pyridylium, 1-decyl pyridylium, 1,2-lutidine positively charged ion, 1,3-lutidine positively charged ion, 1,4-lutidine positively charged ion, 1-ethyl-2-picoline positively charged ion, 2-ethyl-1-picoline positively charged ion, 1-ethyl-3-picoline positively charged ion, 3-ethyl-1-picoline positively charged ion, 1-ethyl-4-picoline positively charged ion, 4-ethyl-1-picoline positively charged ion, 1,2-parvoline positively charged ion, 1,3-parvoline positively charged ion, 1,4-parvoline positively charged ion, 1,2,3-trimethylpyridine positively charged ion, 1,2,4-trimethylpyridine positively charged ion, 1,3,4-trimethylpyridine positively charged ion, 1,3,5-trimethylpyridine positively charged ion, 1,2,5-trimethylpyridine positively charged ion, 1,2,6-trimethylpyridine positively charged ion, 1-ethyl-2,3-lutidine positively charged ion, 1-ethyl-2,4-lutidine positively charged ion, 1-ethyl-2,5-lutidine positively charged ion, 1-ethyl-2,6-lutidine positively charged ion, 1-ethyl-3,4-lutidine positively charged ion, 1-ethyl-3,5-lutidine positively charged ion, 2-ethyl-1,3-lutidine positively charged ion, 2-ethyl-1,4-lutidine positively charged ion, 2-ethyl-1,5-lutidine positively charged ion, 2-ethyl-1,6-lutidine positively charged ion, 3-ethyl-1,2-lutidine positively charged ion, 3-ethyl-1,4-lutidine positively charged ion, 3-ethyl-1,5-lutidine positively charged ion, 3-ethyl-1,6-lutidine positively charged ion, 4-ethyl-1,2-lutidine positively charged ion, 4-ethyl-1,3-lutidine positively charged ion, 1,2-diethyl-3-picoline positively charged ion, 1,2-diethyl-4-picoline positively charged ion, 1,2-diethyl-5-picoline positively charged ion, 1,2-diethyl-6-picoline positively charged ion, 1,3-diethyl-2-picoline positively charged ion, 1,3-diethyl-4-picoline positively charged ion, 1,3-diethyl-5-picoline positively charged ion, 1,3-diethyl-6-picoline positively charged ion, 1,4-diethyl-2-picoline positively charged ion, 1,4-diethyl-3-picoline positively charged ion, 2,3-diethyl-1-picoline positively charged ion, 2,4-diethyl-1-picoline positively charged ion, 2,5-diethyl-1-picoline positively charged ion, 2,6-diethyl-1-picoline positively charged ion, 3,4-diethyl-1-picoline positively charged ion, 3,5-diethyl-1-picoline positively charged ion, 1,2,3,4,5-pentamethyl-pyridylium, 1,2,3,4,6-pentamethyl-pyridylium, 1,2,3,5,6-pentamethyl-pyridylium, 1,2,3,4,5,6-hexamethyl pyridylium, 1-methyl-4-picoline positively charged ion, 1-ethyl-4-picoline positively charged ion, 1-propyl group-4-picoline positively charged ion, 1-butyl-4-picoline positively charged ion, 1-amyl group-4-picoline positively charged ion, 1-hexyl-4-picoline positively charged ion, 1-heptyl-4-picoline positively charged ion, 1-octyl group-4-picoline positively charged ion, 1-nonyl-4-picoline positively charged ion, 1-decyl-4-picoline positively charged ion etc.
As Si Wan Ji phosphonium cation, can enumerate the tetramethyl phosphonium positively charged ion, Si Yi Ji phosphonium cation, Si Bing Ji phosphonium cation, the 4-butyl-phosphonium positively charged ion, Si Wu Ji phosphonium cation, Si Ji Ji phosphonium cation, Si Geng Ji phosphonium cation, Si Xin Ji phosphonium cation, four Ren Ji phosphonium cations, Si Gui Ji phosphonium cation, the tetraphenylphosphoniphenolate positively charged ion, 1,1,1-tributyl-1-Xin Ji phosphonium cation, 1,1,1-tributyl-1-Ren Ji phosphonium cation, 1,1,1-tributyl-1-Gui Ji phosphonium cation, 1,1,1-tributyl-1-Shi Yi Wan Ji phosphonium cation, 1,1,1-tributyl-1-Shi Er Wan Ji phosphonium cation, 1,1,1-tributyl-1-Shi San Wan Ji phosphonium cation, 1,1,1-tributyl-1-Shi Si Wan Ji phosphonium cation, 1,1,1-tributyl-1-Shi five Wan Ji phosphonium cations, 1,1,1-tributyl-1-Shi Liu Wan Ji phosphonium cation, 1,1,1-tributyl-1-17 Wan Ji phosphonium cations, 1,1,1-tributyl-1-Shi Ba Wan Ji phosphonium cation, 1,1,1-tributyl-1-nonadecane Ji phosphonium cation, 1,1,1-tributyl-1-two Shi Wan Ji phosphonium cations, 1,1,1-three amyl groups-1-octyl group Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-nonyl Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-decyl Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-Shi Yi Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-Shi Er Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-Shi San Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-Shi Si Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-Shi five Wan Ji phosphonium cations, 1,1,1-three amyl groups-1-Shi Liu Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-17 Wan Ji phosphonium cations, 1,1,1-three amyl groups-1-Shi Ba Wan Ji phosphonium cation, 1,1,1-three amyl groups-1-nonadecane Ji phosphonium cation, 1,1,1-three amyl groups-1-two Shi Wan Ji phosphonium cations, 1,1,1-three hexyls-1-Xin Ji phosphonium cation, 1,1,1-three hexyls-1-Ren Ji phosphonium cation, 1,1,1-three hexyls-1-Gui Ji phosphonium cation, 1,1,1-three hexyls-1-Shi Yi Wan Ji phosphonium cation, 1,1,1-three hexyls-1-Shi Er Wan Ji phosphonium cation, 1,1,1-three hexyls-1-Shi San Wan Ji phosphonium cation, 1,1,1-three hexyls-1-Shi five Wan Ji phosphonium cations, 1,1,1-three hexyls-1-Shi Liu Wan Ji phosphonium cation, 1,1,1-three hexyls-1-17 Wan Ji phosphonium cations, 1,1,1-three hexyls-1-Shi Ba Wan Ji phosphonium cation, 1,1,1-three hexyls-1-nonadecane Ji phosphonium cation, 1,1,1-three hexyls-1-two Shi Wan Ji phosphonium cations, 1,1,1-three heptyl-1-Xin Ji phosphonium cation, 1,1,1-three heptyl-1-Ren Ji phosphonium cation, 1,1,1-three heptyl-1-Gui Ji phosphonium cation, 1,1,1-three heptyl-1-Shi Yi Wan Ji phosphonium cation, 1,1,1-three heptyl-1-Shi Er Wan Ji phosphonium cation, 1,1,1-three heptyl-1-Shi San Wan Ji phosphonium cation, 1,1,1-three heptyl-1-Shi Si Wan Ji phosphonium cation, 1,1,1-three heptyl-1-Shi five Wan Ji phosphonium cations, 1,1,1-three heptyl-1-Shi Liu Wan Ji phosphonium cation, 1,1,1-three heptyl-1-17 Wan Ji phosphonium cations, 1,1,1-three heptyl-1-Shi Ba Wan Ji phosphonium cation, 1,1,1-three heptyl-1-nonadecane Ji phosphonium cation, 1,1,1-three heptyl-1-two Shi Wan Ji phosphonium cations, 1,1,1,1-Si Xin Ji phosphonium cation, 1,1,1-trioctylphosphine-1-Ren Ji phosphonium cation, 1,1,1-trioctylphosphine-1-Gui Ji phosphonium cation, 1,1,1-trioctylphosphine-1-Shi Yi Wan Ji phosphonium cation, 1,1,1-trioctylphosphine-1-Shi Er Wan Ji phosphonium cation, 1,1,1-trioctylphosphine-1-Shi San Wan Ji phosphonium cation, 1,1,1-trioctylphosphine-1-Shi Si Wan Ji phosphonium cation, 1,1,1-trioctylphosphine-1-Shi five Wan Ji phosphonium cations, 1,1,1-trioctylphosphine-1-Shi Liu Wan Ji phosphonium cation, 1,1,1-trioctylphosphine-1-17 Wan Ji phosphonium cations, 1,1,1-trioctylphosphine-1-Shi Ba Wan Ji phosphonium cation, 1,1,1-trioctylphosphine-1-nonadecane Ji phosphonium cation, 1,1,1-trioctylphosphine-1-two Shi Wan Ji phosphonium cations etc.
In these ions, preferred tricaprylmethylammonium positively charged ion, 1-methyl-3-propyl imidazole positively charged ion, 1-hexyl-4-picoline positively charged ion, 1-octyl group-4-picoline positively charged ion and 1-octyl group pyridylium.
A
-The negatively charged ion of expression is phosphofluoric acid salt anionic (PF
6 -), as salt (1), preferred tricaprylmethylammonium=hexafluorophosphate, 1-methyl-3-propyl imidazole=hexafluorophosphate, 1-hexyl-4-picoline=hexafluorophosphate, 1-octyl group-4-picoline=hexafluorophosphate and 1-octyl group pyridine=hexafluorophosphate.
Salt (1) shown in for example can through type (2)=ion exchange reaction of the acid shown in halogenide and the formula (3) or its an alkali metal salt and making.This ion exchange reaction can be carried out according to known method.
Q
+·X
- (2)
(in the formula, Q
+Represent the meaning same as described above, X
-Expression halogen ion.)
M
+·A
- (3)
(in the formula, M
+Expression hydrogen ion or alkalimetal ion, A
-Represent the meaning same as described above.)
As organic bases, can enumerate organo phosphorous compoundss such as organic nitrogen compounds such as primary amine, secondary amine, tertiary amine, tertiary phosphine etc.Wherein, preferred tertiary amine and tertiary phosphine.As tertiary amine, can enumerate aliphatic tertiary amines such as Trimethylamine, triethylamine, tripropylamine, tributylamine, three amylamines, three hexyl amines, three heptyl amine, trioctylphosphine amine, three nonyl amine, three decyl amine; N, accelerine, N, aromatic nitrile bases such as N-Diethyl Aniline, N-benzyl-N-ethylaniline; Pyridine, 2-picoline, 3-picoline, 4-picoline, 2,6-lutidine, 3,5-lutidine, 2,3,5-trimethylpyridine, 3,5-parvoline, 2,2 '-dipyridyl, 2,4 '-dipyridyl, 4, pyridines such as 4 '-dipyridyl; The imidazoles of 1-Methylimidazole etc. etc.As tertiary phosphine, can enumerate tri octyl phosphine, triphenylphosphine etc.Wherein, preferred tributylamine, trioctylphosphine amine, N-benzyl-N-ethylaniline, pyridine, 2-picoline, 3-picoline, 4-picoline, 3,5-parvoline, 2,2 '-dipyridyl, 1-Methylimidazole, tri octyl phosphine and triphenylphosphine.
Salt composition of the present invention contains salt (1) and organic bases.The content of organic bases is generally more than the 1ppm with respect to salt (1), is preferably 10～5000ppm, more preferably 10～1000ppm.
Salt composition of the present invention for example can be by adding organic bases and carrying out the blended method and wait and make in salt (1).Temperature when adding organic bases, so long as can be equably that both blended temperature are just unrestricted, but normally more than 10 ℃, preferred 15 ℃～100 ℃, preferred especially 20 ℃～50 ℃.
Salt composition can also contain solvent.As solvent, so long as be that the inert solvent is just unrestricted to salt (1) and organic bases.Particularly, can enumerate aliphatic solventss such as pentane, hexane, heptane, octane, decane; Alcoholic solvents such as methyl alcohol, ethanol, butanols, amylalcohol, hexanol; Ester solvent such as methyl acetate, ethyl acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Aromatic hydrocarbon solvents such as benzene,toluene,xylene etc., preferred ester solvent, more preferably ethyl acetate.These solvents can use separately, also can mix two or more uses.When salt composition of the present invention contained solvent, the content of this solvent was generally 1～100 weight % with respect to salt (1), preferred 1～50 weight %.
Embodiment
Below, according to embodiment the present invention is carried out specific description more, but the invention is not restricted to these embodiment.In addition, among the following embodiment, moisture uses capital of a country Electronics Industry Company system karl Fischer moisture determination device (MKA-520) to measure fluorion (F
-) use DIONEX corporate system ion chromatograph (DX-100) to measure that (detection is limited to 10ppm.)。
Production Example 1
Tricaprylmethylammonium=muriate 39.6g, water 51.3g, potassium=hexafluorophosphate 18.0g and methyl ethyl ketone 51.3g are mixed.The mixture that obtains was stirred 1 hour at 25 ℃, make its reaction.After reaction finishes, utilize the separatory operation that organic layer is separated from the reaction mixture of gained.The organic layer water 32.2g that obtains is washed 2 times.The organic layer of gained is concentrated.With the concentrated residue drying under reduced pressure of gained, obtain tricaprylmethylammonium=hexafluorophosphate (following brief note is TOMA-PF6) 49.3g.(yield 98%, moisture 400ppm).
Production Example 2
Except in Production Example 1, use 1-methyl-3-propyl imidazole=bromide replacement tricaprylmethylammonium=muriate and use methylene dichloride to replace beyond the methyl ethyl ketone, all the other and Production Example 1 are similarly implemented, obtain 1-methyl-3-propyl imidazole=hexafluorophosphate (following brief note is MPIM-PF6) 24.2g (yield 91%, moisture 900ppm).
Production Example 3
Except in Production Example 2, use 1-hexyl-4-picoline=bromide to replace beyond 1-methyl-3-propyl imidazole=bromide, all the other and Production Example 2 are similarly implemented, obtain 1-hexyl-4-picoline=hexafluorophosphate (following brief note is HMPy-PF6) 30.6g (yield 96%, moisture 600ppm).
Production Example 4
Except in Production Example 2, use 1-octyl group-4-picoline-bromide to replace beyond 1-methyl-3-propyl imidazole=bromide, all the other and Production Example 2 are similarly implemented, obtain 1-octyl group-4-picoline=hexafluorophosphate (following brief note is OMPy-PF6) 33.5g (yield 97%, moisture 600ppm).
Production Example 5
Except in Production Example 2, use 1-octyl group pyridine=bromide to replace beyond 1-methyl-3-propyl imidazole=bromide, all the other and Production Example 2 are similarly implemented, and obtain 1-octyl group pyridine=hexafluorophosphate (following brief note is OPy-PF6) 32.1g (yield 97%, moisture 200ppm).
Embodiment 1
In Glass Containers, measure 100g TOMA-PF6 and 0.05g trioctylphosphine amine after, airtight in atmosphere, utilize the rotary rotor stirrer at room temperature to mix 1 hour, preparation contains the salt composition of TOMA-PF6 and trioctylphosphine amine.The Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the fluorion (F in the sample
-) concentration.Show the result in table 1.
Embodiment 2
Except use 4-picoline replacement trioctylphosphine amine in embodiment 1, all the other are implemented similarly to Example 1, and preparation contains the salt composition of TOMA-PF6 and 4-picoline.Similarly to Example 1, the Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 1.
Embodiment 3
Except using MPIM-PF6 to replace TOMA-PF6 in embodiment 1 and using the 1-Methylimidazole to replace the trioctylphosphine amine, all the other are implemented similarly to Example 1, and preparation contains the salt composition of MPIM-PF6 and 1-Methylimidazole.Similarly to Example 1, the Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 1.
Embodiment 4
Except use 4-picoline replacement 1-Methylimidazole in embodiment 3, all the other are implemented similarly to Example 3, and preparation contains the salt composition of MPIM-PF6 and 4-picoline.Similarly to Example 3, the Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 1.
Embodiment 5
Except use HMPy-PF6 replacement MPIM-PF6 in embodiment 4, all the other are implemented similarly to Example 4, and preparation contains the salt composition of HMPy-PF6 and 4-picoline.Similarly to Example 4, the Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 1.
Embodiment 6
Except use OMPy-PF6 replacement MPIM-PF6 in embodiment 4, all the other are implemented similarly to Example 4, and preparation contains the salt composition of OMPy-PF6 and 4-picoline.Similarly to Example 4, the Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 1.
Embodiment 7
Except using OPy-PF6 to replace TOMA-PF6 in embodiment 1 and using 3, the 5-parvoline replaces beyond the trioctylphosphine amine, and all the other are implemented similarly to Example 1, and preparation contains OPy-PF6 and 3, the salt composition of 5-parvoline.Similarly to Example 1, the Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 1.In addition, in table 1, " F
-Detecting fate " expression detects the above F of 1000ppm
-The preservation fate of sample, " F
-Concentration " expression F at this moment
-The concentration determination value.
[table 1]
| Salt (1) (amount of moisture) | Organic bases | F -Detect fate (F -Concentration) | |
| Embodiment 1 | TOMA-PF6 (400ppm) | Trioctylphosphine amine | After 30 days still is below the detectability |
| Embodiment 2 | TOMA-PF6 (400ppm) | The 4-picoline | After 30 days still is below the detectability |
| Embodiment 3 | MPIM-PF6 (900ppm) | The 1-Methylimidazole | After 30 days still is below the detectability |
| Embodiment 4 | MPIM-PF6 (900ppm) | The 4-picoline | After 30 days still is below the detectability |
| Embodiment 5 | HMPy-PF6 (600ppm) | The 4-picoline | After 30 days still is below the detectability |
| Embodiment 6 | OMPy-PF6 (600ppm) | The 4-picoline | After 30 days still is below the detectability |
| Embodiment 7 | OPy-PF6 (200ppm) | 3, the 5-parvoline | After 30 days still is below the detectability |
As shown in Table 1, salt composition of the present invention even there is the moisture of trace, was still stablized 30 days at 80 ℃.
Comparative example 1
Except do not use trioctylphosphine amine in embodiment 1, all the other are implemented similarly to Example 1.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 2.In addition, in table 2, " F
-Detecting fate " expression detects the above F of 1000ppm
-The preservation fate of concentrations samples, " (F
-Concentration) " expression F at this moment
-The concentration determination value.
Comparative example 2
Except do not use the 1-Methylimidazole in embodiment 3, all the other are implemented similarly to Example 3.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 2.
Comparative example 3
Except do not use the 4-picoline in embodiment 5, all the other are implemented similarly to Example 5.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 2.
Comparative example 4
Except do not use the 4-picoline in embodiment 6, all the other are implemented similarly to Example 6.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 2.
Comparative example 5
Except do not use 3 in embodiment 7, beyond the 5-parvoline, all the other are implemented similarly to Example 7.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 2.
Table 2
| Salt (1) (amount of moisture) | Organic bases | F -Detect fate (F -Concentration) | |
| Comparative example 1 | TOMA-PF6 (400ppm) | Do not have | 4 days (2500ppm) |
| Comparative example 2 | MPIM-PF6 (900ppm) | Do not have | 1 day (1800ppm) |
| Comparative example 3 | HMPy-PF6 (600ppm) | Do not have | 1 day (1600ppm) |
| Comparative example 4 | OMPy-PF6 (600ppm) | Do not have | 1 day (1300ppm) |
| Comparative example 5 | OPy-PF6 (200ppm) | Do not have | 1 day (1100ppm) |
Embodiment 8～18
Except the organic bases that uses record in the table 3 in embodiment 5 replaced the 4-picoline, all the other were implemented similarly to Example 5, the preparation salt composition.The Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Consequently, even through F after 30 days
-Concentration still is below the detectability.By this result as can be known, salt composition of the present invention even there is the moisture of trace, was still being stablized 30 days at 80 ℃.
Table 3
| Organic bases | |
| Embodiment 8 | Tributylamine |
| Embodiment 9 | Trioctylphosphine amine |
| Embodiment 10 | N-benzyl-N-ethylaniline |
| Embodiment 11 | Pyridine |
| Embodiment 12 | The 2-picoline |
| Embodiment 13 | The 3-picoline |
| Embodiment 14 | The 1-Methylimidazole |
| Embodiment 15 | 3, the 5-parvoline |
| Embodiment 16 | Tri octyl phosphine |
| Embodiment 17 | Triphenylphosphine |
| Embodiment 18 | 2,2 '-dipyridyl |
Comparative example 6～12
Except the compound that uses record in the table 4 in embodiment 5 replaced the 4-picoline, all the other were implemented similarly to Example 5, and salt composition is relatively used in preparation.To contain relatively in 80 ℃ thermostatic bath, preserving of gained with the Glass Containers of salt composition.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.It the results are shown in table 4.In addition, in table 4, " F
-Detecting fate " expression detects the above F of 1000ppm
-The preservation fate of concentrations samples, " (F
-Concentration) " expression F at this moment
-The concentration determination value.
Table 4
| Compound | F -Detect fate (F -Concentration) | |
| Comparative example 6 | Sodium hydroxide | 1 day (1800ppm) |
| Comparative example 7 | Sodium-chlor | 1 day (2000ppm) |
| Comparative example 8 | Potassium hydroxide | 1 day (1900ppm) |
| Comparative example 9 | Repone K | 1 day (1800ppm) |
| Comparative example 10 | Yellow soda ash | 1 day (1800ppm) |
| Comparative example 11 | Salt of wormwood | 1 day (1800ppm) |
| Comparative example 12 | Acetate | 1 day (3900ppm) |
Embodiment 19
After in Glass Containers, measuring the ethyl acetate of the 4-picoline of HMPy-PF6,0.05g of 100g and 50g, airtight in atmosphere, utilize the rotary rotor stirrer at room temperature to mix 1 hour, preparation contains the salt composition of HMPy-PF6 and 4-picoline.The Glass Containers that will contain the salt composition of gained is preserved in 60 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the fluorion (F in the sample
-) concentration.Show the result in table 5.In addition, in table 5, " F
-Detecting fate " expression detects the above F of 1000ppm
-The preservation fate of concentrations samples, " (F
-Concentration) " expression F at this moment
-The concentration determination value.
Embodiment 20
Except the usage quantity of 4-picoline being made as 0.01g in embodiment 19, all the other are implemented similarly to Example 19.The results are shown in table 5.
Comparative example 13
Except do not use the 4-picoline in embodiment 19, all the other are implemented similarly to Example 19.The results are shown in table 5.
Comparative example 14
Except not using the 4-picoline and the usage quantity of ethyl acetate is made as the 25g in embodiment 19, all the other are implemented similarly to Example 19.The results are shown in table 5.
Comparative example 15
Except use Virahol replacement ethyl acetate in comparative example 14, all the other and comparative example 14 are similarly implemented.The results are shown in table 5.
Table 5
| Organic bases (content) | Solvent (content) | F -Detect fate (F -Concentration) | |
| Embodiment 19 | 4-picoline (500ppm) | Ethyl acetate (50 weight %) | After 30 days still is below the detectability |
| Embodiment 20 | 4-picoline (100ppm) | Ethyl acetate (50 weight %) | 20 days (3100ppm) |
| Comparative example 13 | Do not have | Ethyl acetate (50 weight %) | 2 days (1900ppm) |
| Comparative example 14 | Do not have | Ethyl acetate (25 weight %) | 1 day (1800ppm) |
| Comparative example 15 | Do not have | Virahol (25 weight %) | 1 day (1800ppm) |
Embodiment 21～24
Except in embodiment 5 usage quantity of 4-picoline being replaced with the amount shown in the table 6, all the other are implemented similarly to Example 5, and preparation contains the salt composition of HMPy-PF6 and 4-picoline.Similarly to Example 5, the Glass Containers that will contain the salt composition of gained is preserved in 80 ℃ thermostatic bath.Gather the sample of specified amount every day, measure the F in the sample
-Concentration.Show the result in table 6.In addition, in table 6, " F
-Detecting fate " expression detects the above F of 1000ppm
-The preservation fate of concentrations samples, " (F
-Concentration) " expression F at this moment
-The concentration determination value.
Table 6
| Organic bases (content) | F -Detect fate (F -Concentration) | |
| Embodiment 21 | 4-picoline (100ppm) | After 30 days still is below the detectability |
| Embodiment 22 | 4-picoline (50ppm) | After 30 days still is below the detectability |
| Embodiment 23 | 4-picoline (25ppm) | After 30 days still is below the detectability |
| Embodiment 24 | 4-picoline (10ppm) | After 30 days still is below the detectability |
Salt composition of the present invention owing to be difficult to cause hydrolysis because of micro-moisture and thermal conductance, therefore from handling and the angle of prolonged preservation, can be kept stability.In addition, the method according to this invention contains organic bases by making it, can suppress salt (1) because of the hydrolysis that micro-moisture and thermal conductance cause, and can stably preserve salt (1).
Claims (8)
1. a salt composition is characterized in that, contains salt and the organic bases shown in the formula (1),
Q
+·A
- (1)
In the formula, Q
+The expression ion, A
-Expression PF
6 -
2. salt composition according to claim 1 wherein, also contains solvent.
3. salt composition according to claim 1 and 2, wherein, ion is a quaternary ammonium cation Huo quaternary phosphine positively charged ion.
4. according to each described salt composition in the claim 1～3, wherein, organic bases is tertiary amine or tertiary phosphine.
5. salt composition according to claim 4, wherein, tertiary amine is to be selected from least a in aliphatic tertiary amine, aromatic nitrile base, pyridines and the imidazoles.
6. according to each described salt composition in the claim 1～5, wherein, the content of organic bases is 10～5000ppm with respect to the salt shown in the formula (1).
7. the stabilization method of a salt is characterized in that, salt shown in the formula (1) and organic bases are mixed.
8. the store method of a salt is characterized in that, the salt shown in the formula (1) is preserved in the presence of organic bases.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001048846A (en) * | 1999-08-03 | 2001-02-20 | Mitsubishi Chemicals Corp | Quaternary ammonium salt and its production |
| WO2009077452A1 (en) * | 2007-12-14 | 2009-06-25 | Basf Se | Method for improving the hydrolysis stability of ionic liquids |
-
2009
- 2009-07-29 CN CN2009101590128A patent/CN101985413A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001048846A (en) * | 1999-08-03 | 2001-02-20 | Mitsubishi Chemicals Corp | Quaternary ammonium salt and its production |
| WO2009077452A1 (en) * | 2007-12-14 | 2009-06-25 | Basf Se | Method for improving the hydrolysis stability of ionic liquids |
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Application publication date: 20110316 |