CN105731412A - Preparation method of difluorophosphate - Google Patents
Preparation method of difluorophosphate Download PDFInfo
- Publication number
- CN105731412A CN105731412A CN201511017628.3A CN201511017628A CN105731412A CN 105731412 A CN105731412 A CN 105731412A CN 201511017628 A CN201511017628 A CN 201511017628A CN 105731412 A CN105731412 A CN 105731412A
- Authority
- CN
- China
- Prior art keywords
- preparation
- alkyl
- formulas
- fluoride
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention provides a preparation method of difluorophosphate. The preparation method comprises the following steps: (A) mixing a non-aqueous solvent, fluoride salts, and compounds having a structure represented by the formula (I), and stirring to obtain suspension liquid; (B) introducing PF5 gas into the suspension liquid, heating the suspension liquid to carry out reactions, and performing recrystallization to obtain difluorophosphate. In the formula (I), R1 to R6 individually represent H, a C1-C50 hydrocarbyl group, a C1-C50 substituted hydrocarbyl group, or a group having a structure represented by the formula (II); or two or more of R1 to R6 are combined with each other to form a ring structure, in the formula (II), R7 to R9 individually represent H, a C1-C50 hydrocarbyl group, or a C1-C50 substituted hydrocarbyl group, or one or more of R7 to R9 is further substituted by a group having a structure represented by the formula (II).
Description
Technical field
The invention belongs to difluorophosphoric acid salt technical field, the preparation method being specifically related to a kind of difluorophosphoric acid salt.
Background technology
Difluorophosphoric acid salt is industrially of many uses, such as can as the stabilizer (No. 2846412 description of U.S. Patent No.) of vinyl chloride-base polymer, the catalyst (Japanese Unexamined Patent Publication 5-255133 publication) of reaction lubricating oil, the antibacterial (Japanese Kohyo 10-503196 publication) of toothbrush, and the preservative agent of timber (Japanese Unexamined Patent Publication 2002-501034 publication), and lithium secondary battery additive (Japanese Unexamined Patent Publication 08-078053 publication, Japanese Unexamined Patent Publication 11-185804 publication, publication number is the Chinese patent of CN102134065B, publication number is the Chinese patent of CN102064345B, publication number is the Chinese patent of CN101507041B) use.
Preparation method as difluorophosphoric acid salt, it is possible to the reaction represented according to following reaction equation (i), (ii) carry out (JournalofFluorineChemistry (1988), 38 (3), 297.；InorganicChemistry (1967), 6 (10), 1915.).Wherein, in following reaction equation (i)～(v), M represents metallic atom, and L represents dentate.
P2O3F4+ML→MPO2F2+LPOF2(i)
P2O3F4+MO→2MPO2F2(ii)
It addition, it is known that the reaction (InorganicNuclearChemistryLetters (1969), 5 (7), 581.) that following reaction equation (iii) represents.
HPO2F2+MOH→MPO2F2+H2O(iii)
It is also known that the reaction that following reaction equation (iv) represents (JournalofFluorineChemistry (1988), 38 (3), 297.；BerichtederDeutschenChemischenGesellschaftzuBerlin (1929), 62,786.；BulletiondelaSocieteChimiquedeFrance (1968), 1675.).
P2O5+NH4F→NH4PO2F2+(NH4)2POF3(iv)
It is also known that the reaction that following reaction equation (v) represents (ZhurnalNeorganicheskoiKhimii (1966), 11 (12), 2694.).
MPF6+MPO3→MPO2F2(v)
In recent years, Mitsubishi chemical Co., Ltd's research is found that the new method (CN102134065B) preparing difluorophosphoric acid salt, reaction equation (vi) is one of them embodiment, this reaction is by solwution method, the solvent selected is a class chain type carbonic ester, and multiplex in embodiment is dimethyl carbonate.
LiPF6+(CH3)3Si-O-Si(CH3)3→LiPO2F2+(CH3)3SiF(vi)
In addition, the research worker of Belgian SOLVAYSA group has also used another method preparing difluorophosphoric acid salt (US20130129595), reaction equation (vii) and (viii) are the reaction mechanisms provided in this patent, this reaction is gas-particle two-phase reaction, has LiF and LiPF after reaction6Two kinds of by-products.
PF5+Li3PO4→2LiPO2F2+LiF(vii)
2PF5+Li3PO4→2LiPO2F2+LiPF6(viii)
Additionally, SOLVAYSA group has also used another solid state reaction to prepare the method (US20130108933) of difluorophosphoric acid salt, this reaction requires that reaction temperature cannot be below 250 DEG C, and the product purity being obtained by reacting is not high yet.Reaction equation (ix) is expressed as follows:
P4O10+6LiF→3LiPO2F2+Li3PO4(ix)
As it has been described above, difluorophosphoric acid salt is available in various uses, it is highly useful.Although it addition, as it has been described above, its preparation method is known several, but these preparation methoies have problem below.
The preparation method adopting the reaction that above-mentioned reaction equation (i), (ii) represent, it is necessary to use unstable and strong toxicity, the industrial gas being difficult to obtain (such as P2O3F4) etc. be raw material.
The preparation method adopting the reaction that above-mentioned reaction equation (iii) represents, it is difficult to obtain highly purified raw material.Further, since generation water byproduct, the difluorophosphoric acid salt of generation has the probability of hydrolysis.
The preparation method adopting the reaction that above-mentioned reaction equation (iv) represents, is only capable of the compound preparing specific one kind (such as NH4PO2F2(NH4)2POF3)。
Adopt above-mentioned reaction equation (v) and the preparation method of reaction that (ix) represents, react owing to make solid melt, it is therefore desirable to high temperature, in order to obtain high purity product, it is necessary to special equipment and technology.
It addition, when generating by-product in the above-mentioned methods, remove this by-product and be also required to cost.In addition, it is difficult to completely remove these by-products, it is necessary to numerous and diverse purification procedures.
The preparation method adopting the reaction that above-mentioned reaction equation (vi) represents, compared to other method above-mentioned, this method simple and effective ground and the material that is readily available can prepare highly purified difluorophosphoric acid salt.But required raw material is lithium hexafluoro phosphate, lithium hexafluoro phosphate is an intermediate, cheap raw material that neither be the most initial.
And the preparation method adopting reaction that above-mentioned reaction equation (vii) and (viii) represent, owing to make gas-particle two-phase react, productivity is low, and crude product purity is low.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is in that to provide a kind of difluorophosphoric acid salt and preparation method thereof, and preparation method provided by the invention is simple, and cheaper starting materials is easy to get, and the difluorophosphoric acid salt productivity prepared is high, and product purity is high.
The preparation method that the invention provides a kind of difluorophosphoric acid salt, comprises the following steps:
A) by nonaqueous solvent, fluoride salt and the compound mix and blend with Formulas I structure, suspension is obtained；
B) in described suspension, PF is passed into5After gas heating reaction, recrystallization, obtain difluorophosphoric acid salt；
Formulas I；
In Formulas I, R1～R6Separately selected from the alkyl of H, C1～C50, the substituted hydrocarbon radical of C1～C50 or have the group of Formula II structure；Or, R1～R6In any two or two or more group be combined with each other and form circulus；
Formula II；
In Formula II, R7～R9Separately selected from the substituted hydrocarbon radical of the alkyl of H, C1～C50, C1～C50, or R7～R9In any one or more groups replaced by the group with Formula II structure further.
Preferably, there is the compound of Formulas I structure selected from the compound with formula III, Formulas I V or Formula V structure described in；
Formula III；
Formulas I V；
Formula V；
Wherein, R '1～R '14Separately selected from the substituted hydrocarbon radical of the alkyl of H, C1～C50, C1～C50；m≥0；n≥3；Q >=1, p >=2, and p+q=4.
Preferably, described R '1～R '14Separately selected from replacement alkyl, the alkylene of C1～C25, the substituted olefine base of C1～C25, the alkynes base of C1～C25, the replacement alkynes base of C1～C25, phenyl, the substituted-phenyl of the alkyl of H, C1～C25, C1～C25；M is the integer of 0～5；N is the integer of 3～10；Q >=1, p >=2, and p+q=4.
Preferably, there is the compound of Formulas I structure selected from hexamethyl disiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane, hexamethyl cyclotrisiloxane, octaphenylcyclotetrasiloxane or trifluoro propyl methyl cyclotrisiloxane described in.
Preferably, there is described in the mol ratio > 2 of-Si-O-Si-in the compound of Formulas I structure and described fluoride salt.
Preferably, described fluoride salt is selected from salt and the season of the metal in periodic chart in I main group, ii main group and V main groupOne or more in salt.
Preferably, described fluoride salt is selected from lithium fluoride, sodium fluoride, potassium fluoride, ammonium fluoride or calcium fluoride.
Preferably, step A) particularly as follows:
Fluoride salt is dissolved in nonaqueous solvent, obtains mixed solution；
By mixed solution and siloxane compound mix and blend, obtain suspension；
Volume ratio >=2mol the L of the amount of substance of described fluoride salt and described nonaqueous solvent-1。
Preferably, described nonaqueous solvent is selected from one or more in acetone, glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME and Propylene Glycol Dimethyl Ether.
Preferably, the temperature of described temperature reaction is 40～80 DEG C, and the time of described temperature reaction is 6～15h.
Compared with prior art, the preparation method that the invention provides a kind of difluorophosphoric acid salt, comprise the following steps: A) by nonaqueous solvent, fluoride salt and the compound mix and blend with Formulas I structure, obtain suspension；B) in described suspension, PF is passed into5After gas heating reaction, recrystallization, obtain difluorophosphoric acid salt；Formulas I；In Formulas I, R1～R6Separately selected from the alkyl of H, C1～C50, the substituted hydrocarbon radical of C1～C50 or have the group of Formula II structure；Or, R1～R6In any two or two or more group be combined with each other and form circulus；Formula II；In Formula II, R7～R9Separately selected from the substituted hydrocarbon radical of the alkyl of H, C1～C50, C1～C50, or R7～R9In any one or more groups replaced by the group with Formula II structure further.Method provided by the invention can be prepared difluorophosphoric acid salt by material that is cheap and that be readily available in simple and effective ground, and can reduce the cost of difluorophosphoric acid salt further.The difluorophosphoric acid salt productivity that the present invention prepares is high, and product purity is high.
It is shown that the productivity of difluorophosphoric acid salt that preparation method provided by the invention prepares is more than 85%, purity is more than 98%.
Detailed description of the invention
The preparation method of a kind of difluorophosphoric acid salt, it is characterised in that comprise the following steps:
A) by nonaqueous solvent, fluoride salt and the compound mix and blend with Formulas I structure, suspension is obtained；
B) in described suspension, PF is passed into5After gas heating reaction, recrystallization, obtain difluorophosphoric acid salt；
Formulas I；
In Formulas I, R1～R6Separately selected from the alkyl of H, C1～C50, the substituted hydrocarbon radical of C1～C50 or have the group of Formula II structure；Or, R1～R6In any two or two or more group be combined with each other and form circulus；
Formula II；
In Formula II, R7～R9Separately selected from the substituted hydrocarbon radical of the alkyl of H, C1～C50, C1～C50, or R7～R9In any one or more groups replaced by the group with Formula II structure further.
In the present invention, first by nonaqueous solvent, fluoride salt and the compound mix and blend with Formulas I structure, suspension is obtained.Wherein, described fluoride salt can be dissolved in nonaqueous solvent, obtains mixed solution, then again with the compound mix and blend with Formulas I structure, obtain suspension.
The salt of described fluoride salt metal in I main group, ii main group and V main group in periodic chart and seasonOne or more in salt.It is preferably lithium fluoride, sodium fluoride, potassium fluoride, ammonium fluoride or calcium fluoride.
Described nonaqueous solvent is selected from the nonaqueous solvent that can be dissolved by fluoride salt, it is preferred to one or more in acetone, glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME and Propylene Glycol Dimethyl Ether.
In the present invention, the compound described in Formulas I structure is:
Formulas I；
In Formulas I, R1～R6Separately selected from the alkyl of H, C1～C50, the substituted hydrocarbon radical of C1～C50 or have the group of Formula II structure.
The described compound with Formulas I structure is when carrying out the preparation of difluorophosphoric acid salt, it is possible to be used alone one, it is also possible to use two or more with ratio combine in any combination.
Wherein, described alkyl is aliphatic alkyl or aromatic hydrocarbyl, and described aliphatic alkyl is preferably the aliphatic group of C1～C50, and described aromatic radical is preferably phenyl.Described substituted hydrocarbon radical is for replacing aliphatic alkyl or substituted aromatic alkyl, and the substituent group in described substituted hydrocarbon radical is preferably one or more in halogen, hydroxyl, amino, nitro, cyano group, carboxyl, alkoxyl and aldehyde radical, more preferably halogen, it is most preferred that for fluorine.
In the present invention, the group described in Formula II structure is:
Formula II；
In Formula II, R7～R9Separately selected from the substituted hydrocarbon radical of the alkyl of H, C1～C50, C1～C50, or R7～R9In any one or more groups replaced by the group with Formula II structure further and become the group that is connected to multiple groups with Formula II structure.In the present invention, when the compound with Formulas I structure is connected to the group of multiple same-sign, described group can be the same or different, and described same-sign represents R7～R9The group represented respectively.
In the present invention, the compound described in Formulas I structure can also be by the R of Formulas I structure1～R6In any two or two or more group be combined with each other and form circulus.
It is furthermore preferred that described in there is the compound of Formulas I structure selected from the compound with formula III, Formulas I V or Formula V structure；
Formula III；
Formulas I V；
Formula V；
Wherein, R '1～R '14Separately selected from the substituted hydrocarbon radical of the alkyl of H, C1～C50, C1～C50；m≥0；n≥3；Q >=1, p >=2, and p+q=4.Preferably, described R '1～R '14Separately selected from replacement alkyl, the alkylene of C1～C25, the substituted olefine base of C1～C25, the alkynes base of C1～C25, the replacement alkynes base of C1～C25, phenyl, the substituted-phenyl of the alkyl of H, C1～C25, C1～C25；M is the integer of 0～5；N is the integer of 3～10；Q >=1, p >=2, and p+q=4.In the present invention, when the compound with formula III, Formulas I V or Formula V structure is connected to the group of multiple same-sign, described group can be the same or different, and described same-sign represents R '1～R '14The group represented respectively.
Preferably, in the compound of described formula III structure, R '1～R '8Any two or the plural substituent group of middle expression can mutually be closed and form circulus；
The compound of described Formulas I V structure is that n the group with Formula IV structure is connected with each other the cyclic compound formed,
Formula IV；
In the compound of same Formulas I V structure, different R '9And R '10Can be identical can also be difference.
Preferably, in the compound of described Formulas I V structure, R '9～R '10Any two or the plural substituent group of middle expression are mutually closed and are formed circulus；
In the compound of described Formula V structure, R '11～R '14Any two or the plural substituent group of middle expression are mutually closed and are formed circulus.
Work as R '1～R '14During for the substituted hydrocarbon radical of the alkyl of C1～C50 or C1～C50, the kind of alkyl in described alkyl or described substituted hydrocarbon radical is not had particular restriction by the present invention, can also be able to be aromatic hydrocarbyl for aliphatic group, it is also possible to be aliphatic group and the alkyl of aryl radical combination formation.When described alkyl is aliphatic group, described aliphatic alkyl is alkyl, alkylene or alkynes base, it is preferred to alkyl；Described aliphatic group can also be able to be cyclic hydrocarbon group for chain alkyl, it is also possible to is connected, with cyclic hydrocarbon group combination, the aliphatic group formed for chain alkyl.Described chain alkyl can also be able to be branched hydrocarbyl for straight-chain alkyl.
Work as R '1～R '14Independent when substituted hydrocarbon radical, described alkyl can be replaced by more than one substituent group.Described substituent group is preferably one or more in halogen, hydroxyl, amino, nitro, cyano group, carboxyl, alkoxyl and aldehyde radical, more preferably halogen, it is most preferred that for fluorine.When the number of described substituent group is more than two, said two or plural substituent group can be the same or different.
Work as R '1～R '14Independent when alkyl, the number of described carbon atom is preferably 1～50, more preferably 1～25；The kind of alkyl is not limited by the present invention, it is preferred to chain-like alkyl, cyclic alkyl or have the alkyl of cage structure.Described chain-like alkyl can be straight-chain can also be branched.At described cyclic alkyl or have the alkyl of cage structure, the present invention is to not restrictions such as member's numbers of the number of ring and each ring.When described cyclic alkyl or the ring in having the alkyl of cage structure are multiple, described ring can also condensation.Further, it is also possible to chain-like alkyl, cyclic alkyl and the two or more structures be combineding with each other during there is the alkyl of cage structure.
nullWhen described alkyl is chain-like alkyl，It is preferably methyl、Ethyl、N-pro-pyl、1-Methylethyl、Normal-butyl、1-methyl-propyl、2-methyl-propyl、1，1-dimethyl ethyl、N-pentyl、1-methyl butyl、1-ethyl propyl、2-methyl butyl、3-methyl butyl、2，2-dimethyl propyl、1，1-dimethyl propyl、1，2-dimethyl propyl、N-hexyl、1-methyl amyl、1-ethyl-butyl、2-methyl amyl、3-methyl amyl、4-methyl amyl、2-ethyl-butyl、2，2-dimethylbutyl、2，3-dimethylbutyl、3，3-dimethylbutyl、1，1-dimethylbutyl、1，2-dimethylbutyl、1，1，2-thmethylpropyl、1，2，2-thmethylpropyl、1-Ethyl-2-Methyl propyl group、1-ethyl-1-methyl-propyl、N-octyl or positive decyl.
nullWhen described alkyl is cyclic alkyl，It is preferably cyclopenta、2-methylcyclopentyl、3-methylcyclopentyl、2，2-dimethylcyclopentyl、2，3-dimethylcyclopentyl、2，4-dimethylcyclopentyl、2，5-dimethylcyclopentyl、3，3-dimethylcyclopentyl、3，4-dimethylcyclopentyl、2-ethylcyclopentyl、3-ethylcyclopentyl、Cyclohexyl、2-methylcyclohexyl、3-methylcyclohexyl、4-methylcyclohexyl、2，2-Dimethylcyclohexyl、2，3-Dimethylcyclohexyl、2，4-Dimethylcyclohexyl、2，5-Dimethylcyclohexyl、2，6-Dimethylcyclohexyl、3，4-Dimethylcyclohexyl、3，5-Dimethylcyclohexyl、2-ethylcyclohexyl、3-ethylcyclohexyl、4-ethylcyclohexyl、Dicyclo [3，2，1] pungent-1-base or dicyclo [3，2，1] pungent-2-base.
When described alkyl is the alkyl with cage structure, it is preferably 2-phenylcyclopentyl, 3-phenylcyclopentyl, 2, 3-diphenyl cyclopenta, 2, 4-diphenyl cyclopenta, 2, 5-diphenyl cyclopenta, 3, 4-diphenyl cyclopenta, 2-phenylcyclohexyl, 3-phenylcyclohexyl, 4-phenylcyclohexyl, 2, 3-diphenylcyclo base, 2, 4-diphenylcyclo base, 2, 5-diphenylcyclo base, 2, 6-diphenylcyclo base, 3, 4-diphenylcyclo base, 3, 5-diphenylcyclo base, 2-(2-fluorophenyl) cyclohexyl, 2-(3-fluorophenyl) cyclohexyl, 2-(4-fluorophenyl) cyclohexyl, 3-(2-fluorophenyl) cyclohexyl, 4-(2-fluorophenyl) cyclohexyl or 2, double, two (2-fluorophenyl) cyclohexyl of 3-.
When alkyl is aromatic radical, the kind of described aromatic radical is not had particular restriction by the present invention, it is possible to be monocycle can also be multi-ring.Further, the present invention to the quantity of described aromatic rings and member's number of aromatic rings medium ring also without restriction.When aromatic rings has multiple ring, can also condensation between each ring.In the present invention, the carbon number of described aromatic radical is preferably 6～30, more preferably 6～12.When the carbon number of aromatic radical is too much, with the reactive reduction of fluoride salt.When aromatic radical has alkyl or aryl alternatively base, the total carbon atom number of the substituted aryl comprising these substituent groups is preferably 6～30, more preferably 6～12.
When the aromatic radical of alkyl alternatively base is preferably: phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2, 3-3,5-dimethylphenyl, 2, 4-3,5-dimethylphenyl, 2, 5-3,5-dimethylphenyl, 2, 6-3,5-dimethylphenyl, 2, 3, 4-trimethylphenyl, 2, 3, 5-trimethylphenyl, 2, 3, 6-trimethylphenyl, 2, 4, 5-trimethylphenyl, 2, 3, 6-trimethylphenyl, 2, 5, 6-trimethylphenyl, 3, 4, 5-trimethylphenyl, 2, 3, 4, 5-tetramethylphenyl, 2, 3, 4, 6-tetramethylphenyl, 2, 4, 5, 6-tetramethylphenyl, pentamethyl phenyl, 1-naphthyl, 2-naphthyl.
The aromatic radical of described aromatic radical alternatively base is preferably: 2-phenyl, 3-phenyl or 4-phenyl.
Work as R '1～R '14Independent when the alkyl that aliphatic group and aryl radical combination are formed, described alkyl is preferably: phenyl methyl, diphenyl methyl, trityl group, 1-phenylethyl, 2-phenylethyl, (1-fluorophenyl) methyl, (2-fluorophenyl) methyl, (3-fluorophenyl) methyl, (1,2-difluorophenyl) methyl etc..
Work as R '1～R '14Independent in time replacing alkyl, described alkyl can be replaced by more than one substituent group.Described substituent group is preferably one or more in halogen, hydroxyl, amino, nitro, cyano group, carboxyl, alkoxyl and aldehyde radical, more preferably halogen, it is most preferred that for fluorine.When the number of described substituent group is more than two, said two or plural substituent group can be the same or different.
Work as R '1～R '14Independent when the alkyl of the chain structure replaced by halogen atom, described replacement alkyl be preferably: methyl fluoride, difluoromethyl, trifluoromethyl, trifluoro propyl, 1-fluoro ethyl, 2-fluoro ethyl, 1,1-bis-fluoro ethyl, 1,2-bis-fluoro ethyl, 2,2-bis-fluoro ethyl, 1,1,2-trifluoroethyl, chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 1,1-Dichloroethyl, 1,2-Dichloroethyl, 2,2-Dichloroethyl or 1,1,2-trichloroethyl.
Work as R '1～R '14nullIndependent when the cyclic alkyl replaced by halogen atom，Described replacement alkyl is preferably: 2-fluorine cyclopenta、3-fluorine cyclopenta、2，3-Difluorocyclopentyl、2，4-Difluorocyclopentyl、2，5-Difluorocyclopentyl、3，4-Difluorocyclopentyl、2-fluorine cyclohexyl、3-fluorine cyclohexyl、4-fluorine cyclohexyl、2，3-difiuorocyclohexyl、2，4-difiuorocyclohexyl、2，5-difiuorocyclohexyl、2，6-difiuorocyclohexyl、3，4-difiuorocyclohexyl、3，5-difiuorocyclohexyl、2，3，4-trifluoro cyclohexyl、2，3，5-trifluoro cyclohexyl、2，3，6-trifluoro cyclohexyl、2，4，5-trifluoro cyclohexyl、2，4，6-trifluoro cyclohexyl、2，5，6-trifluoro cyclohexyl、3，4，5-trifluoro cyclohexyl、2，3，4，5-ptfe ring hexyl、2，3，4，6-ptfe ring hexyl、2，3，5，6-ptfe ring hexyl or five fluorine cyclohexyl.
Work as R '1～R '14Independent when the aromatic radical replaced by halogen atom, described substituted aromatic base is preferably: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyls, 2,4-difluorophenyl, 2,5-difluorophenyls, 2,6-difluorophenyls, 2,3,4-trifluorophenyls, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyls, 2,4,5-trifluorophenyls, 2,4,6-trifluorophenyl, 2,5,6-trifluorophenyls, 3,4,5-trifluorophenyls, 2,3,4,5-tetrafluoro phenyl, 2,3,4,6-tetrafluoro phenyl, 2,4,5,6-tetrafluoro phenyl or pentafluorophenyl groups.
It is furthermore preferred that from the viewpoint of reactive and being readily available property, described R '1～R '14Independent any one in methyl, ethyl, n-pro-pyl, n-hexyl, n-octyl, positive decyl, vinyl and phenyl, it is preferred to methyl, ethyl, n-pro-pyl or vinyl, more preferably methyl, ethyl or n-pro-pyl.
In the present invention, have described in that the compound of Formulas I structure is preferably in the compound of following structure one or more:
Object lesson as the compound with Formulas I structure of the present invention, it is preferable that the compound of the structure being set forth below.It addition, when the compound of the structure being exemplified below has asymmetric center, this compound can be any optical isomer.
It addition, the weight average molecular weight of the described compound with Formulas I structure is not particularly limited by the present invention, as long as the effect significantly not damaging the present invention is exactly arbitrary, it is preferred to 150～100, more preferably 160～500.
Most preferred, described in there is the compound of Formulas I structure selected from hexamethyl disiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane, hexamethyl cyclotrisiloxane, octaphenylcyclotetrasiloxane or trifluoro propyl methyl cyclotrisiloxane.
The source of the described compound with Formulas I structure is not had particular restriction by the present invention, it is possible to for generally commercially available, it is also possible to prepare voluntarily.Described preparation method is not had particular restriction by the present invention, the preparation method that well known to a person skilled in the art the compound with Formulas I structure.
In the present invention, there is the mol ratio > 2 of-Si-O-Si-in the compound of Formulas I structure and described fluoride salt, it is preferred to 2～5 described in.
Volume ratio >=2mol the L of the amount of substance of described fluoride salt and described nonaqueous solvent-1, it is preferred to 2～4.5mol L-1, more preferably 3～4mol L-1, it is most preferred that for 4mol L-1。
After obtaining suspension, in described suspension, pass into PF5After gas heating reaction, recrystallization, obtain difluorophosphoric acid salt.
In the present invention, described in suspension, PF is passed into5The temperature of gas is 0～25 DEG C, it is preferred to 10 DEG C.Pass into PF5After gas terminates, carrying out temperature reaction, wherein, the temperature that described temperature reaction carries out is 40～80 DEG C, it is preferred to 60 DEG C, and the time of described temperature reaction is 6～15h, it is preferred to 12h.
Described product is lowered the temperature after terminating by reaction, filters, by filtrate rotary evaporation, obtains the crude product of difluorophosphoric acid salt, the crude product of described difluorophosphoric acid salt is carried out recrystallization and obtains difluorophosphoric acid salt.The method of described recrystallization is not had particular restriction by the present invention, the method that well known to a person skilled in the art recrystallization.
Method provided by the invention can be prepared difluorophosphoric acid salt by material that is cheap and that be readily available in simple and effective ground, and can reduce the cost of difluorophosphoric acid salt further.The difluorophosphoric acid salt productivity that the present invention prepares is high, and product purity is high.
It is shown that the productivity of difluorophosphoric acid salt that preparation method provided by the invention prepares is more than 85%, purity is more than 98%.
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preparation method of difluorophosphoric acid salt provided by the invention being illustrated, protection scope of the present invention is not limited by the following examples.
Embodiment 1～22
Embodiment 1-22 is specifically described; its specific experiment operating procedure is: fluoride salt, the compound with Formulas I structure and nonaqueous solvent are joined in the closing container of dry inert gas shielding; and it is mixed into suspension; it is cooled to low temperature (10 DEG C) again, and passes into a certain amount of PF at this temperature5Gas, then heat to 60 DEG C of reaction 12h, reaction is cooled to room temperature after terminating, and is filtered to remove the complete fluoride salt of unreacted and other insoluble impurities, and then rotary evaporation removes solvent, highly purified difluorophosphoric acid salt is prepared again through recrystallization, it is filtered to remove recrystallization solvent (acetone: absolute ether=1:4, v/v), by the crystal that obtains 80 DEG C of drying under reduced pressure 6 hours, weigh the white powder obtained, calculate productivity.Result is in reaction condition and result that Table 1 is embodiment 1～22.
As embodiment 1～22, the combination of the experiment condition that each embodiment is all recorded according to table 1 below reacts, and carries out the preparation of difluorophosphoric acid salt.Additionally, carry out the evaluation about each embodiment, its result is also shown in Table 1 in the lump.
Solid drying under reduced pressure obtained by the chromatography of ions is analyzed, it is thus identified that mainly generating thing is difluorophosphoric acid salt, and obtains its purity, and result is in Table 1.
Being dissolved in deionized water by difluorophosphoric acid salt, concentration is 1mmol/L, then carries out chromatography of ions detection according to the examination criteria of EPA300.1 and analyzes.In the chromatography of ions, as chromatographic column, use the ICS-3000 of DIONEX company.
Gas chromatography is adopted to be monitored judging reaction end to the concentration in the compound in reaction system with Formulas I structure.In gas chromatography, as chromatographic column, use the TC-1 (internal diameter 0.32mm × 30m × thickness 0.25 μm) of GLScience company, start to warm up from 40 DEG C with the programming rates of 5 DEG C per minute, be measured.
The concentration of Bronsted acid in reaction system (lithium hexafluoro phosphate) is obtained, it is assumed that this Bronsted acid is entirely HF by acid-base titrations, will by above-mentioned F-Anion concentration deducts the concentration of above-mentioned Bronsted acid and the residual concentration that obtains is as F-Anion concentration.Utilize the chromatography of ions, acid-base titrations that reactant liquor is analyzed, carry out F-The analysis of anion concentration.The lower limit of the quantitative values that can trust is 1.0 × 10-2mol·kg-1。
Utilize31P-NMR and19The difluorophosphoric acid salt that embodiment 8 is prepared by F-NMR is analyzed, and NMR is with deuterated acetone for solvent, carries out with TMS for benchmark.Result is as follows:
19F-NMR(400MHz；Deuterated acetone solution):
-84.54ppm (bimodal, respectively-83.33ppm and-85.75ppm, coupling constant is 968Hz)；
31P-NMR(202.61MHz；Deuterated acetone solution):
-18.00ppm (three peaks, respectively-12.30ppm ,-18.00ppm and-23.71ppm；Coupling constant is 1155Hz).
Additionally, confirm following result by above-mentioned NMR and above-mentioned gas chromatography: owing to being absent from being declared the peak of the product beyond the by-product coming from theoretical generation and these by-products, therefore do not detect impurity.
The reaction condition of table 1 embodiment 1～22 and result
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention; can also making some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of a difluorophosphoric acid salt, it is characterised in that comprise the following steps:
A) by nonaqueous solvent, fluoride salt and the compound mix and blend with Formulas I structure, suspension is obtained；
B) in described suspension, PF is passed into5After gas heating reaction, recrystallization, obtain difluorophosphoric acid salt；
In Formulas I, R1～R6Separately selected from the alkyl of H, C1～C50, the substituted hydrocarbon radical of C1～C50 or have the group of Formula II structure；Or, R1～R6In any two or two or more group be combined with each other and form circulus；
In Formula II, R7～R9Separately selected from the substituted hydrocarbon radical of the alkyl of H, C1～C50, C1～C50, or R7～R9In any one or more groups replaced by the group with Formula II structure further.
2. preparation method according to claim 1, it is characterised in that described in there is the compound of Formulas I structure selected from the compound with formula III, Formulas I V or Formula V structure；
Wherein, R '1～R '14Separately selected from the substituted hydrocarbon radical of the alkyl of H, C1～C50, C1～C50；m≥0；n≥3；Q >=1, p >=2, and p+q=4.
3. preparation method according to claim 2, it is characterised in that described R '1～R '14Separately selected from replacement alkyl, the alkylene of C1～C25, the substituted olefine base of C1～C25, the alkynes base of C1～C25, the replacement alkynes base of C1～C25, phenyl, the substituted-phenyl of the alkyl of H, C1～C25, C1～C25；M is the integer of 0～5；N is the integer of 3～10；Q >=1, p >=2, and p+q=4.
4. preparation method according to claim 3, it is characterized in that, described in there is the compound of Formulas I structure selected from hexamethyl disiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane, hexamethyl cyclotrisiloxane, octaphenylcyclotetrasiloxane or trifluoro propyl methyl cyclotrisiloxane.
5. preparation method according to claim 1, it is characterised in that described in there is the mol ratio > 2 of-Si-O-Si-in the compound of Formulas I structure and described fluoride salt.
6. preparation method according to claim 1, it is characterised in that the salt of described fluoride salt metal in I main group, ii main group and V main group in periodic chart and seasonOne or more in salt.
7. preparation method according to claim 6, it is characterised in that described fluoride salt is selected from lithium fluoride, sodium fluoride, potassium fluoride, ammonium fluoride or calcium fluoride.
8. preparation method according to claim 1, it is characterised in that step A) particularly as follows:
Fluoride salt is dissolved in nonaqueous solvent, obtains mixed solution；
By mixed solution and siloxane compound mix and blend, obtain suspension；
Volume ratio >=2mol the L of the amount of substance of described fluoride salt and described nonaqueous solvent-1。
9. preparation method according to claim 1, it is characterised in that described nonaqueous solvent is selected from one or more in acetone, glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME and Propylene Glycol Dimethyl Ether.
10. preparation method according to claim 1, it is characterised in that the temperature of described temperature reaction is 40～80 DEG C, the time of described temperature reaction is 6～15h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511017628.3A CN105731412B (en) | 2015-12-29 | 2015-12-29 | A kind of preparation method of difluorophosphoric acid salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511017628.3A CN105731412B (en) | 2015-12-29 | 2015-12-29 | A kind of preparation method of difluorophosphoric acid salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105731412A true CN105731412A (en) | 2016-07-06 |
| CN105731412B CN105731412B (en) | 2018-02-23 |
Family
ID=56296373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511017628.3A Active CN105731412B (en) | 2015-12-29 | 2015-12-29 | A kind of preparation method of difluorophosphoric acid salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105731412B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106976853A (en) * | 2017-04-18 | 2017-07-25 | 江苏国泰超威新材料有限公司 | A kind of preparation method of difluorophosphate |
| WO2019018999A1 (en) * | 2017-07-25 | 2019-01-31 | 江苏长园华盛新能源材料有限公司 | Method for preparing lithium difluorophosphate |
| CN109455688A (en) * | 2017-09-06 | 2019-03-12 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphoric acid salt |
| CN111224164A (en) * | 2019-12-13 | 2020-06-02 | 九江天赐高新材料有限公司 | Preparation method of lithium difluorophosphate |
| EP3617140A4 (en) * | 2018-06-22 | 2020-10-21 | Chun Bo. Ltd. | Method for preparing lithium difluorophosphate crystal with high purity, and non-aqueous electrolyte solution for secondary battery using same |
| CN112537763A (en) * | 2020-12-23 | 2021-03-23 | 九江天赐高新材料有限公司 | Method for synthesizing lithium difluorophosphate by gas-solid-liquid three-phase method |
| CN113148970A (en) * | 2021-03-12 | 2021-07-23 | 九江天赐高新材料有限公司 | Preparation method of high-purity lithium difluorophosphate |
| US11148949B2 (en) | 2018-06-21 | 2021-10-19 | Chun Bo., Ltd | Method of preparing high-purity lithium difluorophosphate crystal and non-aqueous electrolyte solution for secondary battery including the crystal |
| CN115321510A (en) * | 2022-08-30 | 2022-11-11 | 珠海正杏新材料科技有限公司 | Preparation method of lithium difluorophosphate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005219994A (en) * | 2004-02-09 | 2005-08-18 | Mitsubishi Chemicals Corp | Method for producing lithium difluorophosphate and non-aqueous electrolyte solution and non-aqueous electrolyte secondary battery using the solution |
| CN102134065A (en) * | 2006-08-22 | 2011-07-27 | 三菱化学株式会社 | Lithium difluorophosphate,electrolytic solution preparation and difluorophosphate nonaqueous-electrolytic-solution secondary cell employing the same |
| CN102985361A (en) * | 2010-07-08 | 2013-03-20 | 索尔维公司 | Manufacture of LiPO2F2 and crystalline LiPO2F2 |
| CN104114487A (en) * | 2012-03-14 | 2014-10-22 | 斯特拉化工公司 | Method for producing difluorophosphate |
-
2015
- 2015-12-29 CN CN201511017628.3A patent/CN105731412B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005219994A (en) * | 2004-02-09 | 2005-08-18 | Mitsubishi Chemicals Corp | Method for producing lithium difluorophosphate and non-aqueous electrolyte solution and non-aqueous electrolyte secondary battery using the solution |
| CN102134065A (en) * | 2006-08-22 | 2011-07-27 | 三菱化学株式会社 | Lithium difluorophosphate,electrolytic solution preparation and difluorophosphate nonaqueous-electrolytic-solution secondary cell employing the same |
| CN102985361A (en) * | 2010-07-08 | 2013-03-20 | 索尔维公司 | Manufacture of LiPO2F2 and crystalline LiPO2F2 |
| CN104114487A (en) * | 2012-03-14 | 2014-10-22 | 斯特拉化工公司 | Method for producing difluorophosphate |
Non-Patent Citations (1)
| Title |
|---|
| 李景虹: "《先进电池材料》", 30 June 2004 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106976853A (en) * | 2017-04-18 | 2017-07-25 | 江苏国泰超威新材料有限公司 | A kind of preparation method of difluorophosphate |
| WO2019018999A1 (en) * | 2017-07-25 | 2019-01-31 | 江苏长园华盛新能源材料有限公司 | Method for preparing lithium difluorophosphate |
| CN109455688A (en) * | 2017-09-06 | 2019-03-12 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphoric acid salt |
| CN109455688B (en) * | 2017-09-06 | 2022-04-29 | 东莞东阳光科研发有限公司 | Preparation method of difluorophosphate |
| US11148949B2 (en) | 2018-06-21 | 2021-10-19 | Chun Bo., Ltd | Method of preparing high-purity lithium difluorophosphate crystal and non-aqueous electrolyte solution for secondary battery including the crystal |
| EP3617140A4 (en) * | 2018-06-22 | 2020-10-21 | Chun Bo. Ltd. | Method for preparing lithium difluorophosphate crystal with high purity, and non-aqueous electrolyte solution for secondary battery using same |
| US11225417B2 (en) | 2018-06-22 | 2022-01-18 | Chun Bo., Ltd | Method of preparing high-purity lithium difluorophosphate crystal and non-aqueous electrolyte solution for secondary battery including the crystal |
| CN111224164A (en) * | 2019-12-13 | 2020-06-02 | 九江天赐高新材料有限公司 | Preparation method of lithium difluorophosphate |
| CN111224164B (en) * | 2019-12-13 | 2022-07-15 | 九江天赐高新材料有限公司 | Preparation method of lithium difluorophosphate |
| CN112537763A (en) * | 2020-12-23 | 2021-03-23 | 九江天赐高新材料有限公司 | Method for synthesizing lithium difluorophosphate by gas-solid-liquid three-phase method |
| CN112537763B (en) * | 2020-12-23 | 2023-08-22 | 九江天赐高新材料有限公司 | Method for synthesizing lithium difluorophosphate by gas-solid-liquid three-phase |
| CN113148970A (en) * | 2021-03-12 | 2021-07-23 | 九江天赐高新材料有限公司 | Preparation method of high-purity lithium difluorophosphate |
| CN115321510A (en) * | 2022-08-30 | 2022-11-11 | 珠海正杏新材料科技有限公司 | Preparation method of lithium difluorophosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105731412B (en) | 2018-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105731412A (en) | Preparation method of difluorophosphate | |
| KR101287705B1 (en) | Low-viscosity ionic liquids | |
| CN104755418B (en) | It is used to prepare the method for the imide salts containing fluorosulfonyl group | |
| KR101395663B1 (en) | Process for preparing lithium difluorobis(oxalato)phosphate, lithium tetrafluoro(oxalato)phosphate, or their mixture | |
| CN106543473B (en) | Biradical molecule fire retardant of a kind of phosphonitrile/triazine based on dopen Nano level metallic compound in situ and preparation method thereof | |
| KR20190003710A (en) | Method for producing bis (fluorosulfonyl) imide alkali metal salt and method for producing non-aqueous liquid electrolyte | |
| JP2008222592A (en) | New phosphonium salt ionic liquid and reaction solvent using the same | |
| JP2014015343A (en) | Method for producing lithium dihalogenophosphate | |
| JP6336969B2 (en) | Bicyclic aromatic anion salts for LI ion batteries | |
| KR101937318B1 (en) | Imidic acid compound having divalent anion, and manufacturing method therefor | |
| WO2010086131A1 (en) | Novel tricyanoborates | |
| CN107244663B (en) | A kind of preparation method of difluorophosphate | |
| CN109678694A (en) | A kind of preparation method of tetrafluoro oxalic acid lithium phosphate | |
| KR102570659B1 (en) | Manufacturing method for high-purity crystallization of lithium difluorophosphate with excellet solubility and Non-aqueous electrolyte for secondary battery | |
| KR20100092938A (en) | Gelling agent containing fluoroalkyl derivative | |
| JP2018177670A (en) | Method for producing asymmetric imide tertiary ammonium salt | |
| JP2002138095A (en) | Fluoroalkyl phosphate used in electrochemical cell | |
| JP5484915B2 (en) | Compounds containing organofluorochlorophosphate anions | |
| CN106976853A (en) | A kind of preparation method of difluorophosphate | |
| KR101062097B1 (en) | Lithium salt and its manufacturing method | |
| JP2013508340A (en) | Lithium salt containing pentafluorophenylamide anion, its preparation and use thereof | |
| TW527740B (en) | Fluoroalkylphosphate salts, and process for the preparation of these substances | |
| EP2279192B1 (en) | Ionic liquids | |
| CN112189278A (en) | Preparation method of flame-retardant lithium ion battery electrolyte easy to dissolve in organic solvent | |
| US20130023661A1 (en) | Fluorinating reagents with (perfluoralkyl) fluorophosphate anion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |