JP6210065B2 - Method for producing cyclic carbonate - Google Patents

Description

  The present invention relates to a method for producing a cyclic carbonate that is widely used in various applications such as an electrolytic solution of a lithium ion secondary battery and a plastic raw material. More specifically, the present invention relates to a method for producing a cyclic carbonate using carbon dioxide.

  In recent years, carbon dioxide in the atmosphere has been steadily increasing and is regarded as a problem as a cause of global warming. On the other hand, if carbon dioxide can be effectively utilized and converted into a functional material or the like, carbon dioxide can be regarded as one of resources that can be obtained inexhaustibly.

  Since cyclic carbonates that can be synthesized from carbon dioxide are widely used in various applications such as electrolytes for lithium ion secondary batteries, plastic raw materials, and the like, various synthesis methods have been studied. However, most of the synthesis methods require either high temperature (100 to 150 ° C.), high pressure (several tens of atmospheres) or both of them, and have not yet been put into practical use in consideration of reduction of environmental load. It is the actual situation. Specifically, for example, a method using lithium bromide which is a metal salt (for example, Non-Patent Document 1) is a method which requires high temperature conditions under normal pressure conditions, and a method using quaternary ammonium salts, for example. (For example, Non-Patent Document 2) is a method that requires high-pressure conditions in addition to high-temperature conditions while being metal-free (metal-free). In addition to these methods, various methods for synthesizing cyclic carbonates are known (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Non-Patent Document 3, Non-Patent Document 4, Non-Patent Document 5, Non-Patent Document 6, etc.) and any of the synthesis methods are methods that require either high temperature, high pressure, or both conditions.

  Recently, a composite catalyst having both characteristics of a metal and a quaternary ammonium salt has been developed and used for a carbonate reaction under normal temperature and normal pressure conditions (for example, Non-Patent Document 7). However, since this composite catalyst is an expensive metal coordination catalyst that requires multiple steps for its synthesis, there is a difficulty in practicality.

JP 47-31981 JP-A 62-45584 JP-A-5-202022 International Publication No. WO2005 / 084841

J. Org. Chem., 1993, 58, 6198-6202. J. Mol. Catal. A: Chem., 2006, 249, 143-148. Adv. Synth. Catal., 2010, 352, 2233-2240. Green Chem., 2012, 14, 209-216. J. Org. Chem., 2003, 68, 6705-6709. Eur. J. Org. Chem., 2004, 3080-3089. Dalton Trans., 2011, 40, 3885-3902.

  As described above, various methods for synthesizing cyclic carbonates using carbon dioxide have been known for a long time, but these methods require the use of metals such as alkali metals that require high temperature and high pressure conditions. There is still a problem in terms of environmental load, such as the need for a removal step because of the use of the catalyst, and the high cost of the catalyst. For this reason, even today, there is a demand for establishment of a method for synthesizing a cyclic carbonate in consideration of reducing the environmental burden.

  In view of the situation described above, the object of the present invention is not only to produce a wide variety of cyclic carbonates in high yields, but also to reduce environmental impact, even if the reaction is conducted under mild conditions such as normal temperature and normal pressure. Is to provide a practical method for producing a cyclic carbonate in consideration of the above. As a result of intensive research on such a production method, the present inventors have made a hydrogen bond with a phosphonium salt having an iodine anion as a counter anion and an oxygen atom of the epoxide in the reaction of epoxide (oxirane) with carbon dioxide. It has been found that the object described above can be achieved by using a compound having a hydrogen atom to be obtained, and the present invention has been completed.

  The present invention relates to a method for producing a cyclic carbonate, characterized by reacting an epoxide and carbon dioxide in the presence of a phosphonium salt having an iodine anion and a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide. It is an invention.

  In producing cyclic carbonate by reaction of epoxide (oxirane) and carbon dioxide, by using a phosphonium salt having iodine anion as a counter anion and a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide, Even under mild conditions such as normal pressure, the cyclic carbonate can be produced with good yield.

  In the production method of the present invention, when a phosphonium salt having an iodine anion as a counter anion and a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide are used, the reason why the above-described effect can be obtained is as follows. Conceivable. That is, a hydrogen atom in a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide is coordinated to an oxygen atom of epoxide (oxirane), and iodine anion is applied to epoxide (oxirane) coordinated with hydrogen atom. The cyclic phosphonium salt (hereinafter sometimes abbreviated as the phosphonium salt according to the present invention) acts effectively as a catalyst to produce a cyclic carbonate in a high yield even under mild conditions such as normal temperature and normal pressure. It is considered possible.

  Further, when such a phosphonium salt according to the present invention is a polymer as described later, it can be easily separated from a cyclic carbonate as a product as compared with a monomer and recovered. The production method of the present invention using the polymer is useful from the viewpoint of green chemistry because it can be reused, and is a practical production method that takes environmental load reduction into consideration.

  In the method for producing a cyclic carbonate of the present invention, the reaction of epoxide (oxirane) and carbon dioxide is carried out in the presence of a phosphonium salt having iodine anion and a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide. It is characterized by.

  In the production method of the present invention, epoxide (oxirane) is used as a raw material for producing cyclic carbonate. The epoxide (oxirane) is not particularly limited as long as it is usually used in this field, and may have at least one oxirane ring, and may have two or more oxirane rings. You may have other functional groups, such as an ether group and an acyl group. Specific examples of the epoxide (oxirane) include those selected from epoxides (oxiranes) represented by the following general formula [I] and epoxides (oxiranes) represented by the following general formula [II].

（式中、Ａ_１、Ａ_２、Ａ_３及びＡ_４はそれぞれ独立して、水素原子又はヘテロ原子を有していてもよい炭素数１〜２０の１価の炭化水素基を表す。なお、Ａ_１とＡ_２、Ａ_１とＡ_４又はＡ_３とＡ_４とで環状構造を形成していてもよい。）

(In the formula, A ₁ , A ₂ , A ₃ and A ₄ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom. A ₁ and A ₂ , A ₁ and A ₄ or A ₃ and A ₄ may form a cyclic structure.)

（式中、Ａ_５、Ａ_６、Ａ_７、Ａ_８、Ａ_９及びＡ_１０はそれぞれ独立して、水素原子又はヘテロ原子を有していてもよい炭素数１〜２０の１価の炭化水素基を表し、Ｔは、ヘテロ原子を有していてもよい炭素数１〜２０の２価の炭化水素基を表す。なお、Ａ_５とＡ_６、Ａ_５とＡ_７、Ａ_８とＡ_１０又はＡ_９とＡ_１０とで環状構造を形成していてもよい。）

(In the formula, A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ are each independently a monovalent hydrocarbon having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom. T represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hetero atom, A ₅ and A ₆ , A ₅ and A ₇ , A ₈ and A ₁₀ Alternatively, A ₉ and A ₁₀ may form a cyclic structure.)

As the monovalent hydrocarbon group represented by A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II], Specific examples include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group.

It has a hetero atom represented by A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II]. Specific examples of the hetero atom in the monovalent hydrocarbon group having 1 to 20 carbon atoms may include an oxygen atom, a sulfur atom, for example, a halogen atom such as a fluorine atom and a chlorine atom.

In the general formulas [I] and [II], the monovalent hydrocarbon groups represented by A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ are alkyl. Specific examples in the case of a group, that is, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II] The alkyl group which may have a heteroatom shown may be linear, branched or cyclic. Specific examples of the case where the alkyl group has no hetero atom include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, Cyclobutyl group, n-pentyl group, isopentyl group, s-pentyl group, t-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group , Isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, n-heptyl Group, isoheptyl group, s-heptyl group, t-heptyl group, neoheptyl group, cycloheptyl group, n-octyl group, isooctyl group, s-octyl group, t -Octyl, neooctyl, 2-ethylhexyl, cyclooctyl, n-nonyl, isononyl, s-nonyl, t-nonyl, neononyl, cyclononyl, n-decyl, isodecyl, s- Decyl, t-decyl, neodecyl, cyclodecyl, n-undecyl, cycloundecyl, n-dodecyl, cyclododecyl, n-tridecyl, cyclotridecyl, n-tetradecyl, cyclotetra Decyl group, n-pentadecyl group, cyclopentadecyl group, n-hexadecyl group, cyclohexadecyl group, n-heptadecyl group, cycloheptadecyl group, n-octadecyl group, cyclooctadecyl group, n-nonadecyl group, cyclononadecyl group, n-icosyl group, cycloicosyl group, norbornyl group, bornyl group, menthyl group, adamantyl group, Examples thereof include alkyl groups having 1 to 20 carbon atoms such as tiladamantyl group and decahydronaphthyl group. Among them, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s- Butyl, t-butyl, cyclobutyl, n-pentyl, isopentyl, s-pentyl, t-pentyl, neopentyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl , Cyclopentyl group, n-hexyl group, isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl Group, cyclohexyl group, n-heptyl group, isoheptyl group, s-heptyl group, t-heptyl group, neoheptyl group, cycloheptyl group, n-octyl , Isooctyl group, s-octyl group, t-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, s-nonyl group, t-nonyl group, neononyl group, cyclononyl group, Straight chain having 1 to 10 carbon atoms such as n-decyl group, isodecyl group, s-decyl group, t-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group, menthyl group, adamantyl group, decahydronaphthyl group, etc. , Branched or cyclic alkyl groups are preferred. In the specific examples described above, n- represents a normal isomer, s- represents a sec isomer, and t- represents a tert isomer.

In addition, the alkyl group which may have a hetero atom represented by A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ has a hetero atom. Specific examples of the case include, for example, methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, methoxyhexyl group, methoxyheptyl group, methoxyoctyl group, methoxynonyl group, methoxydecyl group, methoxyunyl group. Decyl group, methoxydodecyl group, methoxytridecyl group, methoxytetradecyl group, methoxypentadecyl group, methoxyhexadecyl group, methoxyheptadecyl group, methoxyoctadecyl group, methoxynonadecyl group, ethoxymethyl group, ethoxyethyl group, ethoxy Propyl group, ethoxybutyl group, ethoxypentyl group, Toxihexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, ethoxyundecyl, ethoxydodecyl, ethoxytridecyl, ethoxytetradecyl, ethoxypentadecyl, ethoxyhexadecyl, ethoxyhepta Decyl group, ethoxyoctadecyl group, propoxymethyl group, propoxyethyl group, propoxybutyl group, propoxypentyl group, propoxyhexyl group, propoxyheptyl group, propoxyoctyl group, propoxynonyl group, propoxydecyl group, propoxyundecyl group, propoxide dodecyl Group, propoxytridecyl group, propoxytetradecyl group, propoxypentadecyl group, propoxyhexadecyl group, propoxyheptadecyl group, butoxymethyl group, butoxy Ethyl group, butoxypropyl group, butoxybutyl group, butoxypentyl group, butoxyhexyl group, butoxyheptyl group, butoxyoctyl group, butoxynonyl group, butoxydecyl group, butoxyundecyl group, butoxydodecyl group, butoxytridecyl group, butoxy Tetradecyl group, butoxypentadecyl group, butoxyhexadecyl group, pentyloxymethyl group, pentyloxyethyl group, pentyloxypropyl group, pentyloxybutyl group, pentyloxypentyl group, pentyloxyhexyl group, pentyloxyheptyl group, pentyl Oxyoctyl group, pentyloxynonyl group, pentyloxydecyl group, pentyloxyundecyl group, pentyloxide decyl group, pentyloxytridecyl group, pentyloxytetradecyl group, pen Tyloxypentadecyl group, hexyloxymethyl group, hexyloxyethyl group, hexyloxypropyl group, hexyloxybutyl group, hexyloxypentyl group, hexyloxyhexyl group, hexyloxyheptyl group, hexyloxyoctyl group, hexyloxynonyl group Hexyloxydecyl group, hexyloxyundecyl group, hexyloxide decyl group, hexyloxytridecyl group, hexyloxytetradecyl group, heptyloxymethyl group, heptyloxyethyl group, heptyloxypropyl group, heptyloxybutyl group, heptyl Oxypentyl group, heptyloxyhexyl group, heptyloxyheptyl group, heptyloxyoctyl group, heptyloxynonyl group, heptyloxydecyl group, heptyloxyundecyl group, Ptyl oxide decyl group, heptyloxy tridecyl group, octyloxymethyl group, octyloxyethyl group, octyloxypropyl group, octyloxybutyl group, octyloxypentyl group, octyloxyhexyl group, octyloxyheptyl group, octyloxyoctyl group Octyloxynonyl group, octyloxydecyl group, octyloxyundecyl group, octyloxydecyl group, nonyloxymethyl group, nonyloxyethyl group, nonyloxypropyl group, nonyloxybutyl group, nonyloxypentyl group, nonyloxypentyl group Group, nonyloxyheptyl group, nonyloxyoctyl group, nonyloxynonyl group, nonyloxydecyl group, nonyloxyundecyl group, decyloxymethyl group, decyloxyethyl group, decyloxy group Cypropyl group, Decyloxybutyl group, Decyloxypentyl group, Decyloxyhexyl group, Decyloxyheptyl group, Decyloxyoctyl group, Decyloxynonyl group, Decyloxydecyl group, Undecyloxymethyl group, Undecyloxyethyl group, Undecyloxypropyl, undecyloxybutyl, undecyloxypentyl, undecyloxyhexyl, undecyloxyheptyl, undecyloxyoctyl, undecyloxynonyl, dodecyloxymethyl, dodecyloxyethyl Group, dodecyloxypropyl group, dodecyloxybutyl group, dodecyloxypentyl group, dodecyloxyhexyl group, dodecyloxyheptyl group, dodecyloxyoctyl group, tridecyloxymethyl group, tridecyloxyethyl group Tyl group, tridecyloxypropyl group, tridecyloxybutyl group, tridecyloxypentyl group, tridecyloxyhexyl group, tridecyloxyheptyl group, tetradecyloxymethyl group, tetradecyloxyethyl group, tetradecyloxypropyl group , Tetradecyloxybutyl group, tetradecyloxypentyl group, tetradecyloxyhexyl group, pentadecyloxymethyl group, pentadecyloxyethyl group, pentadecyloxypropyl group, pentadecyloxybutyl group, pentadecyloxypentyl group, hexa Decyloxymethyl, hexadecyloxyethyl, hexadecyloxypropyl, hexadecyloxybutyl, heptadecyloxymethyl, heptadecyloxyethyl, heptadecyloxypropyl, Alkyl groups having 2 to 20 carbon atoms having an ether group (oxygen atom) such as a tadecyloxymethyl group, octadecyloxyethyl group, nonadecyloxymethyl group, such as formyloxymethyl group, formyloxyethyl group, formyloxypropyl group , Acetoxymethyl group (acetyloxymethyl group), acetoxyethyl group (acetyloxyethyl group), acetoxypropyl group (acetyloxypropyl group), propionyloxymethyl group, propionyloxyethyl group, propionyloxypropyl group, butyryloxymethyl group Group, butyryloxyethyl group, butyryloxypropyl group, valeryloxymethyl group (pentanoyloxymethyl group), valeryloxyethyl group (pentanoyloxyethyl group), valeryloxypropyl group (pentanoyl) Oxypropyl group), caproyloxymethyl group (hexanoyloxymethyl group), caproyloxyethyl group (hexanoyloxyethyl group), caproyloxypropyl group (hexanoyloxypropyl group), enanthoyloxymethyl group ( C2-C20 alkyl having a carbonyloxy group (oxygen atom) such as heptanoyloxymethyl group), enanthoyloxyethyl group (heptanoyloxyethyl group), enanthoyloxypropyl group (heptanoyloxypropyl group), etc. Groups such as perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorode Sil group, perfluoroundecyl group, perfluorododecyl group, perfluorotridecyl group, perfluorotetradecyl group, perfluoropentadecyl group, perfluorohexadecyl group, perfluoroheptadecyl group, perfluorooctadecyl group, perfluoro Examples thereof include C1-C20 alkyl groups having a fluoro group (fluorine atom) such as fluorononadecyl group and perfluoroicosyl group. Among them, for example, methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxy Butyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, ethoxyheptyl , Ethoxyoctyl group, propoxymethyl group, propoxyethyl group, propoxybutyl group, propoxypentyl group, propoxyhexyl group, propoxyheptyl group, butoxymethyl group, butoxyethyl group, butoxypropyl group, butoxybutyl group, butoxypentyl group, butoxy Hexyl, pentyloxymethyl, pentyloxyethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, heptyloxy Carbon having ether group (oxygen atom) such as methyl group, heptyloxyethyl group, heptyloxypropyl group, octyloxymethyl group, octyloxyethyl group, nonyloxymethyl group 1-10 linear, branched or cyclic alkyl groups such as formyloxymethyl, formyloxyethyl, formyloxypropyl, acetoxymethyl (acetyloxymethyl), acetoxyethyl (acetyloxyethyl) Group), acetoxypropyl group (acetyloxypropyl group), propionyloxymethyl group, propionyloxyethyl group, propionyloxypropyl group, butyryloxymethyl group, butyryloxyethyl group, butyryloxypropyl group, valeryloxymethyl group Group (pentanoyloxymethyl group), valeryloxyethyl group (pentanoyloxyethyl group), valeryloxypropyl group (pentanoyloxypropyl group), caproyloxymethyl group (hexanoyloxymethyl group), caproylio Xylethyl group (hexanoyloxyethyl group), caproyloxypropyl group (hexanoyloxypropyl group), enanthyloxymethyl group (heptanoyloxymethyl group), enanthyloxyethyl group (heptanoyloxyethyl group), enanthate A linear, branched or cyclic alkyl group having 2 to 10 carbon atoms having a carbonyloxy group (oxygen atom) such as an yloxypropyl group (heptanoyloxypropyl group), such as a perfluoromethyl group or a perfluoroethyl group Group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, etc. Directly having 1 to 10 carbon atoms Jo, alkyl group branched or cyclic are preferred. In the specific examples described above, the alkyl group is not limited to the normal-form, but may be a branched or cyclo-form alkyl group such as a sec-form, tert-form, iso-form, or neo-form. May be.

The monovalent hydrocarbon group represented by A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II] is alkenyl. Specific examples in the case of a group, that is, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II] The alkenyl group which may have a heteroatom shown may be linear, branched or cyclic. Specific examples of the case where the alkenyl group does not have a hetero atom include, for example, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group. , Tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, etc. A linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms such as pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group and the like is preferable. Specific examples of the alkenyl group having a hetero atom include, for example, vinyloxymethyl group, vinyloxyethyl group, vinyloxypropyl group, propenyloxymethyl group, propenyloxyethyl group, propenyloxypropyl group, butenyl Ether groups such as oxymethyl group, butenyloxyethyl group, butenyloxypropyl group, pentenyloxymethyl group, pentenyloxyethyl group, pentenyloxypropyl group, hexenyloxymethyl group, hexenyloxyethyl group, hexenyloxypropyl group ( An oxygen atom) having 3 to 20 carbon atoms, such as acryloyloxymethyl group, acryloyloxyethyl group, acryloyloxypropyl group, methacryloyloxymethyl group, methacryloyloxyethyl group, Tacryloyloxypropyl group, Crotonoyloxymethyl group, Crotonoyloxyethyl group, Crotonoyloxypropyl group, Tigroyloxymethyl group, Tigroyloxyethyl group, Tigroyloxypropyl group, Angeloyloxymethyl group, Angeloyl Carbonyloxy groups such as oxyethyl group, angeloyloxypropyl group, senecioyloxymethyl group, senecioyloxyethyl group, senecioyloxypropyl group, solvoyloxymethyl group, solvoyloxyethyl group, sorboyloxypropyl group (Oxygen atom) having 4 to 20 carbon atoms such as perfluorovinyl group, perfluoropropenyl group, perfluorobutenyl group, perfluoropentenyl group, perfluorohexenyl group, perfluorohept group Nyl group, perfluorooctenyl group, perfluorononenyl group, perfluorodecenyl group, perfluoroundecenyl group, perfluorododecenyl group, perfluorotridecenyl group, perfluorotetradecenyl Group, perfluoropentadecenyl group, perfluorohexadecenyl group, perfluoroheptadecenyl group, perfluorooctadecenyl group, perfluorononadecenyl group, perfluoroicosenyl group, etc. Examples thereof include C2-C20 alkenyl groups having a fluoro group (fluorine atom). Among them, for example, vinyloxymethyl group, vinyloxyethyl group, vinyloxypropyl group, propenyloxymethyl group, propenyloxyethyl group, Propenyloxypropyl group, butenyloxymethyl group, butenyloxyethyl group, butenyloxy C3-C10 straight chain having an ether group (oxygen atom) such as a xylpropyl group, pentenyloxymethyl group, pentenyloxyethyl group, pentenyloxypropyl group, hexenyloxymethyl group, hexenyloxyethyl group, hexenyloxypropyl group , Branched or cyclic alkenyl groups such as acryloyloxymethyl group, acryloyloxyethyl group, acryloyloxypropyl group, methacryloyloxymethyl group, methacryloyloxyethyl group, methacryloyloxypropyl group, crotonoyloxymethyl group, crotonoyl Oxyethyl group, Crotonoyloxypropyl group, Tigroyloxymethyl group, Tigroyloxyethyl group, Tigroyloxypropyl group, Angeloyloxymethyl group, Angeloyloxyethyl Groups, angeloyloxypropyl groups, senecioyloxymethyl groups, senecioyloxyethyl groups, senecioyloxypropyl groups, solvoyloxymethyl groups, solvoyloxyethyl groups, solvoyloxypropyl groups, and other carbonyloxy groups (oxygen A linear, branched or cyclic alkenyl group having 4 to 10 carbon atoms, such as a perfluorovinyl group, a perfluoropropenyl group, a perfluorobutenyl group, a perfluoropentenyl group, a perfluorohexenyl group, C2-C10 linear, branched or cyclic having a fluoro group (fluorine atom) such as perfluoroheptenyl group, perfluorooctenyl group, perfluorononenyl group and perfluorodecenyl group Alkenyl groups are preferred. In the above specific examples, the alkenyl group is not limited to the normal-form, but is a branched alkenyl group such as a sec-form, tert-form, iso-form, or neo-form, or a cyclo-form. May be. Further, the position of the double bond in the alkenyl group is not limited to the 1st position, and may be an alkenyl group having a double bond at a position different from the 1st position such as the 2nd position, the 3rd position, and the ω position.

The monovalent hydrocarbon groups represented by A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II] are aryl. Specific examples in the case of a group, that is, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II] The aryl group which may have a hetero atom shown may be either monocyclic or condensed polycyclic. Specific examples of the aryl group having no hetero atom include, for example, a phenyl group, a naphthyl group, an azulenyl group, a biphenylyl group, an indacenyl group, an acenaphthylenyl group, a phenanthryl group, an anthryl group (anthracenyl group) and the like. -14 aryl groups are mentioned, and among them, for example, aryl groups having 6 carbon atoms such as phenyl groups are preferred. Specific examples of the aryl group having a hetero atom include a perfluorophenyl group, a perfluoronaphthyl group, a perfluoroazurenyl group, a perfluorobiphenylyl group, a perfluoroindacenyl group, and a perfluoroacena group. Examples include aryl groups having 6 to 14 carbon atoms having a fluoro group (fluorine atom) such as a phthalenyl group, a perfluorophenanthryl group, and a perfluoroanthryl group (perfluoroanthracenyl group). An aryl group having 6 carbon atoms having a fluoro group (fluorine atom) such as a perfluorophenyl group is preferable.

The monovalent hydrocarbon groups represented by A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II] are aralkyl. Specific examples in the case of a group, that is, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ in the general formulas [I] and [II] The aralkyl group which may have a hetero atom shown may be either monocyclic or condensed polycyclic. Specific examples of the case where the aralkyl group has no hetero atom include, for example, benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, Examples thereof include aralkyl groups having 7 to 20 carbon atoms such as a tetrahydronaphthyl group, a naphthylmethyl group, a naphthylethyl group, an indenyl group, and a fluorenyl group. Among them, for example, a benzyl group, a phenethyl group, a methylbenzyl group, a phenylpropyl group, 1 Aralkyl groups having 7 to 14 carbon atoms such as -methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, tetrahydronaphthyl group, naphthylmethyl group, naphthylethyl group, indenyl group and fluorenyl group are preferred. Specific examples of the case where the aralkyl group has a hetero atom include, for example, a phenyloxymethyl group, a phenyloxyethyl group, a phenyloxypropyl group, a benzyloxymethyl group, a benzyloxyethyl group, a benzyloxypropyl group, a phenethyloxy group. Methyl group, phenethyloxyethyl group, phenethyloxypropyl group, naphthyloxymethyl group, naphthyloxyethyl group, naphthyloxypropyl group, furyl group, pyranyl group, thienyl group, chromenyl group, chromanyl group, xanthenyl group, phenoxathinyl group And an aralkyl group having 7 to 20 carbon atoms having a hetero atom such as an oxygen atom such as a sulfur group, and the like, among them, for example, phenyloxymethyl group, phenyloxyethyl group, phenyloxypropyl group, benzyloxymethyl, etc. Benzyloxyethyl group, benzyloxypropyl group, phenethyloxymethyl group, phenethyloxyethyl group, phenethyloxypropyl group, naphthyloxymethyl group, naphthyloxyethyl group, naphthyloxypropyl group, furyl group, pyranyl group, thienyl group, A C7-14 aralkyl group having a hetero atom such as an oxygen atom or sulfur atom such as a chromenyl group, a chromanyl group, a xanthenyl group or a phenoxathiinyl group is preferred.

  Specific examples of the divalent hydrocarbon group represented by T in the general formula [II] include an alkylene group (alkanediyl group), an alkenylene group, an arylene group, and an aralkylene group.

  Specific examples of the hetero atom in the divalent hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom represented by T in the general formula [II] include, for example, an oxygen atom, a sulfur atom, such as fluorine Examples thereof include halogen atoms such as atoms and chlorine atoms.

  Specific examples when the divalent hydrocarbon group represented by T in the general formula [II] is an alkylene group (alkanediyl group), that is, having a heteroatom represented by T in the general formula [II] The alkylene group (alkanediyl group) may be linear, branched or cyclic. Specific examples of the alkylene group (alkanediyl group) having no hetero atom include, for example, a methylene group (methanediyl group), an ethylene group (ethane-1,2-diyl group), a propylene group (propane-1, 2-diyl group), trimethylene group (propane-1,3-diyl group), tetramethylene group (butane-1,4-diyl group), pentamethylene group (pentane-1,5-diyl group), hexamethylene group (Hexane-1,6-diyl group), heptamethylene group (heptane-1,7-diyl group), octamethylene group (octane-1,8-diyl group), nonamethylene group (nonane-1,9-diyl group) ), Decamethylene group (decane-1,10-diyl group), undecane methylene group (undecane-1,11-diyl group), dodecane methylene group (dodecane-1,12-diyl group), tridecamethylene group ( Ridecane-1,13-diyl group), tetradecane methylene group (tetradecane-1,14-diyl group), pentadecane methylene group (pentadecane-1,15-diyl group), hexadecane methylene group (hexadecane-1,16) -Diyl group), heptadecane group (heptadecane-1,17-diyl group), octadecamethylene group (octadecane-1,18-diyl group), nonadecamethylene group (nonadecane-1,19-diyl group), Examples thereof include an alkylene group (alkanediyl group) having 1 to 20 carbon atoms such as an icosamethylene group (icosane-1,20-diyl group). Specific examples of the alkylene group (alkanediyl group) having a hetero atom include, for example, a methylene bis (oxymethyl) group, a methylene bis (oxyethyl) group, a methylene bis (oxypropyl) group, a methylene bis (oxybutyl) group, and a methylene bis. (Oxypentyl) group, ethylenebis (oxymethyl) group, ethylenebis (oxyethyl) group, ethylenebis (oxypropyl) group, ethylenebis (oxybutyl) group, ethylenebis (oxypentyl) group, trimethylenebis (oxymethyl) ) Group, trimethylenebis (oxyethyl) group, trimethylenebis (oxypropyl) group, trimethylenebis (oxybutyl) group, trimethylenebis (oxypentyl) group, tetramethylenebis (oxymethyl) group, tetramethylenebis ( Oxy Til) group, tetramethylene bis (oxypropyl) group, tetramethylene bis (oxybutyl) group, tetramethylene bis (oxypentyl) group, pentamethylene bis (oxymethyl) group, pentamethylene bis (oxyethyl) group, pentamethylene bis Examples thereof include C3-C20 alkylene groups (alkanediyl groups) having an ether group (oxygen atom) such as (oxypropyl) group, pentamethylenebis (oxybutyl) group, pentamethylenebis (oxypentyl) group, and the like. In the above specific examples, the alkylene group (alkanediyl group) is not limited to the normal-form, but is branched such as sec-form, tert-form, iso-form, neo-form, or cyclic form such as cyclo-form. May be an alkylene group (alkanediyl group).

  Specific examples when the divalent hydrocarbon group represented by T in the general formula [II] is an alkenylene group, that is, the alkenylene group optionally having a heteroatom represented by T in the general formula [II] May be linear, branched or cyclic. Specific examples of the case where the alkenylene group has no hetero atom include, for example, vinylene group, propenylene group, butenylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, nonenylene group, decenylene group, undecenylene group, dodecenylene group And aldecylene groups having 2 to 20 carbon atoms such as tridecenylene group, tetradecenylene group, pentadecenylene group, hexadecenylene group, heptadecenylene group, octadecenylene group, nonadecenylene group, icosenylene group and the like. Specific examples of the case where the alkenylene group has a hetero atom include, for example, a perfluorovinylene group, a perfluoropropenylene group, a perfluorobutenylene group, a perfluoropentenylene group, a perfluorohexenylene group, Perfluoroheptenylene group, perfluorooctenylene group, perfluorononenylene group, perfluorodecenylene group, perfluoroundecenylene group, perfluorododecenylene group, perfluorotridecenylene group, perfluoro Tetradecenylene group, perfluoropentadecenylene group, perfluorohexadecenylene group, perfluoroheptadecenylene group, perfluorooctadecenylene group, perfluorononadecenylene group, perfluoroicoseni group C2-C2 having a fluoro group (fluorine atom) such as a len group And the like of the alkenylene group. In the above specific examples, the alkenylene group is not limited to a normal-form, but is a branched alkenylene group such as a sec-form, tert-form, iso-form, or neo-form, or a cyclo-form. May be. Further, the position of the double bond in the alkenylene group is not limited to the 1-position, and may be an alkenylene group having a double bond at a position different from the 1-position such as the 2-position, the 3-position, and the ω-position.

  Specific examples when the divalent hydrocarbon group represented by T in the general formula [II] is an arylene group, that is, as the arylene group optionally having a heteroatom represented by T in the general formula [II] May be monocyclic or condensed polycyclic. Specific examples of the arylene group having no hetero atom include C6-C12 arylene groups such as a phenylene group, a naphthylene group, and a biphenylene group. Moreover, as a specific example in case the said arylene group has a hetero atom, it is C6-C12 arylene which has fluoro groups (fluorine atoms), such as a perfluorophenylene group, a perfluoro naphthylene group, a perfluoro biphenylene group, for example. Groups and the like.

  Specific examples when the divalent hydrocarbon group represented by T in the general formula [II] is an aralkylene group, that is, the aralkylene group optionally having a hetero atom represented by T in the general formula [II] May be monocyclic or condensed polycyclic. Specific examples of the case where the aralkylene group does not have a hetero atom include, for example, benzylene group, phenethylene group, phenylpropylene group, phenylbutylene group, tetrahydronaphthylene group, naphthylmethylene group, naphthylethylene group, etc. There are 20 aralkylene groups. Specific examples of the aralkylene group having a hetero atom include, for example, a methylene bis (phenoxymethyl) group, a methylene bis (phenoxyethyl) group, a methylene bis (phenoxypropyl) group, an ethylene bis (phenoxymethyl) group, an ethylene bis ( Phenoxyethyl) group, ethylenebis (phenoxypropyl) group, trimethylenebis (phenoxymethyl) group, trimethylenebis (phenoxyethyl) group, dimethylmethylenebis (phenoxymethyl) group, dimethylmethylenebis (phenoxyethyl) group, di Perfluoromethylmethylenebis (phenoxymethyl) group, diperfluoromethylmethylenebis (phenoxyethyl) group, tetramethylenebis (phenoxymethyl) group, tetramethylenebis (phenoxyethyl) group, ethylmethyl Methylenebis (phenoxymethyl) group, ethylmethylmethylenebis (phenoxyethyl) group, pentamethylenebis (phenoxymethyl) group, cyclopentanediylbis (phenoxymethyl) group, hexamethylenebis (phenoxyethyl) group, cyclohexanediylbis (phenoxy) And a C 15-20 aralkylene group having a hetero atom such as a fluorine atom or an oxygen atom such as a methyl group.

A ₁ and A ₂ , A ₁ and A ₄ , A ₃ and A ₄ , A ₅ and A ₆ , A ₅ and A ₇ , A ₈ and A ₁₀ , A ₉ and A in the general formulas [I] and [II] _{The fact that 10} may form a cyclic structure means that a cyclic structure having 5 to 10 carbon atoms may be formed together with the carbon atoms via these two A's. Among such cyclic structures, those in which a cyclic structure is formed by A ₁ and A ₄ , A ₅ and A ₇ , A ₈ and A ₁₀ are preferable. Specific examples of the cyclic structure in the case of forming a cyclic structure include, for example, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, etc., among them, a cyclopentane ring, a cyclohexane A cyclic structure having 5 to 7 carbon atoms such as a ring and a cycloheptane ring is preferable. In addition, the specific example of the cyclic structure described above is merely an example, and is not limited to the specific example illustrated here. A condensed ring, a spiro ring, a bridged ring, or a substituent such as an alkyl group is further substituted on these rings. Also included.

  Specific examples of the epoxide (oxirane) represented by the general formula [I] include those represented by the formulas (I-I) to (I-XIII). The epoxide (oxirane) represented by the following formula is merely an example of a specific example, and is not limited to the specific example illustrated here.

  Specific examples of the epoxide (oxirane) represented by the general formula [II] include those represented by the formulas (II-I) to (II-IX). The epoxide (oxirane) represented by the following formula is merely an example of a specific example, and is not limited to the specific example illustrated here.

  The epoxides (oxiranes) represented by the general formulas [I] and [II] may be commercially available products or those appropriately synthesized by general methods performed in this field.

  In the production method of the present invention, carbon dioxide is used as a raw material for producing a cyclic carbonate, similarly to the epoxide (oxirane) described above. The carbon dioxide is industrially produced by collecting, purifying, etc., carbon dioxide produced as a by-product in the production of electric power, gas, etc., but there is no particular limitation on the supply form, origin, and the like. Further, the purity of carbon dioxide is not necessarily high and may be diluted with an inert gas such as nitrogen gas or argon gas. However, since the reaction volume tends to increase if the purity of carbon dioxide is low, the carbon dioxide is preferably highly pure. The purity of carbon dioxide is preferably 95% or more, particularly 99% or more.

  The amount of carbon dioxide used in the present invention is not particularly limited as long as it is a practical amount. For example, it is usually 0.9 equivalent or more, preferably 0.95 equivalent or more, relative to the number of moles of epoxide (oxirane). Preferably it is 1.0 equivalent or more. Moreover, as an upper limit, it is 10,000 equivalent, for example.

  The phosphonium salt according to the present invention is a quaternary phosphonium salt having an iodine anion, which may be a monomer or a polymer. Specific examples of the phosphonium salt include, for example, (1) a compound represented by the following general formula [1] and (2) a compound represented by the following general formula [1] and having a vinyl group Selected from polymers containing a monomer unit as a constituent unit.

（式中、Ｒ^１は、ビニル基を有していてもよい炭素数１〜１０のアルキル基、ビニル基を有していてもよい炭素数６〜１０のアリール基、ビニル基を有していてもよい炭素数７〜１２のアラルキル基又はビニル基を有していてもよい炭素数２〜１０のＮ，Ｎ-ジアルキルアミノ基を表し、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ独立して、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、炭素数７〜１２のアラルキル基又は炭素数２〜１０のＮ，Ｎ-ジアルキルアミノ基を表す。）

(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a vinyl group, an aryl group having 6 to 10 carbon atoms which may have a vinyl group, have a vinyl group Represents an optionally substituted aralkyl group having 7 to 12 carbon atoms or an N, N-dialkylamino group having 2 to 10 carbon atoms which may have a vinyl group, and R ² , R ³ and R ⁴ are each independently , A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an N, N-dialkylamino group having 2 to 10 carbon atoms.

The alkyl group having 1 to 10 carbon atoms in the alkyl group having 1 to 10 carbon atoms which may have the vinyl group represented by R ¹ in the general formula [1], and R ² , R ³ and R ⁴ The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specifically includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n- Butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, n-pentyl, isopentyl, s-pentyl, t-pentyl, neopentyl, 2-methylbutyl, 1,2-dimethyl Propyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2 3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, n-heptyl group, isoheptyl group, s-heptyl group, t-heptyl group, neoheptyl group, cycloheptyl group, n-octyl group, isooctyl group, s-octyl group Group, t-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, s-nonyl group, t-nonyl group, neononyl group, cyclononyl group, n-decyl group, isodecyl group , S-decyl group, t-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group, menthyl group, adamantyl group, decahydronaphthyl group, etc., among them, for example, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl , Isopentyl group, s-pentyl group, t-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, s-hexyl Straight chain having 1 to 6 carbon atoms such as a group, t-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, etc. A branched or cyclic alkyl group is preferred. In the specific examples described above, n- represents a normal isomer, s- represents a sec isomer, and t- represents a tert isomer.

The aryl group having 6 to 10 carbon atoms in the aryl group having 6 to 10 carbon atoms which may have the vinyl group represented by R ¹ in the general formula [1], and R ² , R ³ and R ⁴ The aryl group having 6 to 10 carbon atoms may be monocyclic or condensed polycyclic, and specifically includes, for example, phenyl group, naphthyl group, azulenyl group, etc. An aryl group having 6 carbon atoms such as a phenyl group is preferred.

7 to 12 aralkyl groups in the aralkyl group having 7 to 12 carbon atoms which may have the vinyl group represented by R ¹ in the general formula [1], and R ² , R ³ and R ⁴ The aralkyl group having 7 to 12 carbon atoms may be monocyclic or condensed polycyclic, and specifically includes, for example, benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methyl group. Examples thereof include a phenylethyl group, a phenylbutyl group, a 2-methylphenylpropyl group, a tetrahydronaphthyl group, a naphthylmethyl group, and a naphthylethyl group. Among them, an aryl group having 7 carbon atoms such as a benzyl group is preferable.

The N, N-dialkylamino group having 2 to 10 carbon atoms in the N, N-dialkylamino group having 2 to 10 carbon atoms which may have the vinyl group represented by R ¹ in the general formula [1], and R The N, N-dialkylamino group having 2 to 10 carbon atoms represented by ² , R ³ and R ⁴ may be linear, branched or cyclic. Specifically, for example, N , N-dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N, N-diisopropylamino group, N, N-di-n-butylamino group, N, N- Diisobutylamino group, N, N-di-s-butylamino group, N, N-di-t-butylamino group, N, N-dicyclobutylamino group, N, N-di-n-pentylamino group, N, N-diisopentylamino group, N, N-di-s-pentylamino group, N, N-di-t-pe Tylamino group, N, N-dineopentylamino group, N, N-di-2-methylbutylamino group, N, N-bis (1,2-dimethylpropyl) amino group, N, N-di-1- Ethylpropylamino group, N, N-dicyclopentylamino group, N, N-ethylmethylamino group, N, N-methylpropylamino group, N, N-butylmethylamino group, N, N-methylpentylamino group, N, N-hexylmethylamino group, N, N-heptylmethylamino group, N, N-methyloctylamino group, N, N-methylnonylamino group, N, N-ethylpropylamino group, N, N-butyl Ethylamino group, N, N-ethylpentylamino group, N, N-ethylhexylamino group, N, N-ethylheptylamino group, N, N-ethyloctylamino group, N, N-butylpropylamino group, N, N-pentylpro A ruamino group, an N, N-hexylpropylamino group, an N, N-heptylpropylamino group, an N, N-butylpentylamino group, an N, N-butylhexylamino group, and the like. -Dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N, N-diisopropylamino group, N, N-ethylmethylamino group, N, N-methylpropylamino group, C 2-6 linear or branched, such as N, N-butylmethylamino group, N, N-methylpentylamino group, N, N-ethylpropylamino group, N, N-butylethylamino group Alternatively, a cyclic N, N-dialkylamino group is preferable, and among them, for example, an N, N-dialkylamino group having 2 carbon atoms such as an N, N-dimethylamino group is more preferable. In the specific examples described above, n- represents a normal isomer, s- represents a sec isomer, and t- represents a tert isomer.

In General Formula [1], when one of R ² , R ^3, and R ⁴ is a hydrogen atom, the remaining two R are an alkyl group having 1 to 10 carbon atoms and a carbon atom having 6 to 10 carbon atoms. It is preferably selected from an aryl group, an aralkyl group having 7 to 12 carbon atoms, and an N, N-dialkylamino group having 2 to 10 carbon atoms.

When R ¹ in the general formula [1] is a C 1-10 alkyl group having a vinyl group, the vinyl group may be bonded to the terminal carbon atom of the alkyl group, or the alkyl group You may couple | bond with the said carbon atom so that it may branch from the carbon atom in a chain | strand. The number of vinyl groups is usually one. Two carbon atoms constituting the vinyl group are not included in the number of carbon atoms (1 to 10 carbon atoms) constituting the alkyl group to which the vinyl group is bonded. In other words, the alkyl group having a vinyl group has 3 to 12 carbon atoms.

When R ¹ in the general formula [1] is a C 6-10 aryl group having a vinyl group, the vinyl group may be bonded to any carbon atom of the aromatic ring constituting the aryl group. . For example, when the aryl group is a phenyl group, the bonding position of the vinyl group may be any of the ortho position, the meta position, and the para position with respect to the bond with the phosphorus atom (phosphorus cation) bonded to the phenyl group. Of these, a phenyl group in which the vinyl group is bonded to the phosphorus atom (phosphorus cation) bonded to the phenyl group in a para-position is preferable. The number of vinyl groups is usually one. Two carbon atoms constituting the vinyl group are not included in the number of carbon atoms (6 to 10 carbon atoms) constituting the aryl group to which the vinyl group is bonded. In other words, the aryl group having a vinyl group has 8 to 12 carbon atoms.

When R ¹ in the general formula [1] is a C 7-12 aralkyl group having a vinyl group, the vinyl group is any carbon atom of the aryl group (phenyl group or naphthyl group) constituting the aralkyl group. May be bonded to. The number of vinyl groups is usually one. Note that the two carbon atoms constituting the vinyl group are not included in the number of carbon atoms (7 to 12 carbon atoms) constituting the aralkyl group to which the vinyl group is bonded. In other words, the carbon number of the aralkyl group in the case of having a vinyl group is 9-14.

  Preferable specific examples when the phosphonium salt according to the present invention is (1) the compound represented by the general formula [1] include, for example, a compound represented by the following general formula [1 ′].

（式中、Ｒ^１'は、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、炭素数７〜１２のアラルキル基又は炭素数２〜１０のＮ，Ｎ-ジアルキルアミノ基を表し、Ｒ^２'、Ｒ^３'及びＲ^４'はそれぞれ独立して、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、炭素数７〜１２のアラルキル基又は炭素数２〜１０のＮ，Ｎ-ジアルキルアミノ基を表す。）

(In the formula, R ^{1 ′} represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an N, N-dialkylamino group having 2 to 10 carbon atoms. R ^{2 ′} , R ^{3 ′} and R ^{4 ′} each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or carbon. Represents an N, N-dialkylamino group of formula 2 to 10.)

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the general formula [1 ′] include R ¹ , R ² and R ³ in the general formula [1]. And the same thing as a C1-C10 alkyl group shown by R < ⁴ > is mentioned, A preferable alkyl group is also the same.

Examples of the aryl group having 6 to 10 carbon atoms represented by R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the general formula [1 ′] include R ¹ , R ² and R ³ in the general formula [1]. And the same aryl group having 6 to 10 carbon atoms as R ⁴ , and preferable aryl groups are also the same.

Examples of the aralkyl group having 7 to 12 carbon atoms represented by R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the general formula [1 ′] include R ¹ , R ² and R ³ in the general formula [1]. And the same thing as the C7-C12 aralkyl group shown by R < ⁴ > is mentioned, A preferable aralkyl group is also the same.

Examples of the N, N-dialkylamino group having 2 to 10 carbon atoms represented by R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the general formula [1 ′] include R ¹ in the general formula [1], R ^{2, R 3} and a carbon number of 2-10 represented by ^{R 4} N, N-include the same dialkylamino group, preferably N, N-dialkylamino group include those similar.

In the general formula [1 ′], when one of R ^{2 ′} , R ^{3 ′} and R ^{4 ′} is a hydrogen atom, the remaining two R ^′ are an alkyl group having 1 to 10 carbon atoms, carbon It is preferably selected from an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an N, N-dialkylamino group having 2 to 10 carbon atoms.

  Specific examples of the compound represented by the general formula [1 ′] include those represented by the formulas (1′-1) to (1′-12). In addition, the compound shown by a following formula is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.

  As the compound represented by the general formula [1] and the compound represented by the general formula [1 ′] (phosphonium salt according to the present invention), commercially available products may be used, and general compounds used in this field may be used. You may use what was synthesize | combined suitably by the method. Among them, in particular, the compounds represented by the above formulas (1′-1) to (1′-3) are obtained by, for example, reacting commercially available triphenylphosphine with hydroiodic acid, methyl iodide or benzyl iodide. What is necessary is just to synthesize. The compounds represented by the above formulas (1′-4) to (1′-6) can be synthesized, for example, by reacting commercially available dicyclohexylphenylphosphine with hydroiodic acid, methyl iodide or benzyl iodide. Good. Furthermore, the compounds represented by the above formulas (1′-7) to (1′-9) may be synthesized, for example, by reacting commercially available tributylphosphine with hydroiodic acid, methyl iodide or benzyl iodide. . Furthermore, the compounds represented by the above formulas (1′-10) to (1′-12) are obtained by, for example, reacting commercially available tris (dimethylamino) phosphine with hydroiodic acid, methyl iodide or benzyl iodide. Can be synthesized.

  As described above, the phosphonium salt according to the present invention is derived not only from a monomer such as a compound represented by the general formula [1 ′] but also from a compound represented by the general formula [1] having a vinyl group. The polymer which contains the monomer unit to perform as a structural unit may be sufficient. That is, in the production method of the present invention, as long as the structure of the quaternary phosphonium salt has an iodine anion as a counter ion of the phosphonium cation, the polymer (polymer) is also used as the phosphonium salt according to the present invention. Can be used.

  As a polymer containing a monomer unit derived from a compound represented by the general formula [1] having a vinyl group as a constituent unit, a single weight composed of a monomer unit derived from a compound represented by the general formula [1] having a vinyl group is used. A monomer unit derived from the compound represented by the general formula [1] having a vinyl group and a vinyl monomer other than the compound represented by the general formula [1] having a vinyl group. It may be a copolymer (heteropolymer) composed of derived monomer units.

  When the phosphonium salt according to the present invention is a polymer containing a monomer unit derived from the compound represented by the general formula [1] having a vinyl group as a constituent unit, the compound (derived from the monomer unit constituting the polymer) Preferable specific examples of the compound) include those represented by the following general formula [1 ″].

（式中、Ｒ^１''は、ビニル基を有する炭素数１〜１０のアルキル基、ビニル基を有する炭素数６〜１０のアリール基、ビニル基を有する炭素数７〜１２のアラルキル基又はビニル基を有する炭素数２〜１０のＮ，Ｎ-ジアルキルアミノ基を表し、Ｒ^２''、Ｒ^３''及びＲ^４''はそれぞれ独立して、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、炭素数７〜１２のアラルキル基又は炭素数２〜１０のＮ，Ｎ-ジアルキルアミノ基を表す。）

(Wherein R ^{1 ″} is an alkyl group having 1 to 10 carbon atoms having a vinyl group, an aryl group having 6 to 10 carbon atoms having a vinyl group, an aralkyl group having 7 to 12 carbon atoms having a vinyl group, or vinyl. Represents an N, N-dialkylamino group having 2 to 10 carbon atoms and R ^{2 ″} , R ^{3 ″} and R ^{4 ″} each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Represents an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an N, N-dialkylamino group having 2 to 10 carbon atoms.)

  In other words, the polymer containing the monomer unit derived from the compound represented by the general formula [1 ″] as a constituent unit is (2) the compound represented by the general formula [1] and having a vinyl group. It corresponds to a polymer containing monomer units derived from those as constituent units.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{1 ″} , R ^{2 ″} , R ^{3 ″} and R ^{4 ″} in the general formula [1 ″] include R ¹ in the general formula [1], the same alkyl group having 1 to 10 carbon atoms represented by R ^2, R ³ and R ⁴ can be mentioned include those preferred alkyl group similar.

Examples of the aryl group having 6 to 10 carbon atoms represented by R ^{1 ″} , R ^{2 ″} , R ^{3 ″} and R ^{4 ″} in the general formula [1 ″] include R ¹ in the general formula [1], the same as the aryl group having 6 to 10 carbon atoms represented by R ^2, R ³ and R ⁴ can be mentioned include those preferred aryl group same.

Examples of the aralkyl group having 7 to 12 carbon atoms represented by R ^{1 ″} , R ^{2 ″} , R ^{3 ″} and R ^{4 ″} in the general formula [1 ″] include R ¹ in the general formula [1], the same as the aralkyl group having 7 to 12 carbon atoms represented by R ^2, R ³ and R ⁴ can be mentioned include those preferred aralkyl group similar.

As the N, N-dialkylamino group having 2 to 10 carbon atoms represented by R ^{1 ″} , R ^{2 ″} , R ^{3 ″} and R ^{4 ″} in the general formula [1 ″], the general formula [1 ] The same thing as a C2-C10 N, N- dialkylamino group shown by R < ¹ >, R < ² >, R < ³ > and R < ⁴ > is mentioned, The preferable N, N-dialkylamino group is also the same. Can be mentioned.

In the general formula [1 ″], when one of R ^{2 ″} , R ^{3 ″} and R ^{4 ″} is a hydrogen atom, the remaining two R ^″ have 1 to 10 carbon atoms. And an alkyl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an N, N-dialkylamino group having 2 to 10 carbon atoms.

General formula ^'' R ¹ in [1 ^']', the bonding position of the vinyl group when it is an alkyl group having 1 to 10 carbon atoms having a vinyl group is R ¹ in the general formula [1], a vinyl group Examples similar to the bonding position of the vinyl group in the case of the alkyl group having 1 to 10 carbon atoms are included. Further, the number of vinyl groups and the range of the carbon number of the alkyl group in the case of having a vinyl group are the same as in the case of R ¹ in the general formula [1].

When R ¹ ″ in the general formula [1 ″] is an aryl group having 6 to 10 carbon atoms having a vinyl group, the bonding position of the vinyl group is that R ¹ in the general formula [1] represents a vinyl group. Examples similar to the bonding position of the vinyl group in the case of an aryl group having 6 to 10 carbon atoms are included. Further, the number of vinyl groups and the range of the carbon number of the aryl group in the case of having a vinyl group are the same as in the case of R ¹ in the general formula [1].

General formula [1 ''] R ¹ in ^'' is the bonding position of the vinyl group when it is aralkyl group having 7 to 12 carbon atoms having a vinyl group is R ¹ in the general formula [1], a vinyl group Examples similar to the bonding position of the vinyl group in the case of the aralkyl group having 7 to 12 carbon atoms are included. Further, the number of vinyl groups and the range of the carbon number of the aralkyl group in the case of having a vinyl group are the same as in the case of R ¹ in the general formula [1].

  Specific examples of the compound represented by the general formula [1 ″] (the compound derived from the monomer unit constituting the polymer) include, for example, those represented by the formulas (1 ″ -1) to (1 ″ -6). Among them, the compound represented by the formula (1 ″ -2) is preferable. In addition, the compound (compound derived from the monomer unit which comprises a polymer) shown by a following formula is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.

  The vinyl monomer other than the compound represented by the general formula [1 ″] is not particularly limited as long as it is a compound having a vinyl group polymerizable with the vinyl group in the compound represented by the general formula [1 ″]. Specific examples of the vinyl monomer include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 4-isopropylstyrene, and the like. Styrene derivatives such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) acrylic acid (Meth) acrylic acid esters such as isobutyl, (meth) acrylic acid-s-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid cyclobutyl, (meth) acrylic acid phenyl, for example, N, N-dimethyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide (Meth) acrylamide derivatives such as N, N-diisopropyl (meth) acrylamide, such as acrylonitrile, and the like, among them, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 4 Styrene derivatives such as -ethylstyrene, 4-n-propylstyrene, 4-isopropylstyrene and the like are preferable, and among them, styrene is more preferable. In addition, (meth) acrylic acid in the above-mentioned specific examples means acrylic acid or methacrylic acid. In addition, (meth) acrylamide in the above specific examples means acrylamide or methacrylamide.

  Specific examples of the polymer containing a monomer unit derived from the compound represented by the general formula [1 ″] as a constituent unit include, for example, those represented by the formula (A). In addition, the polymer shown by a following formula is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.

  The weight average molecular weight of the polymer containing a monomer unit derived from the compound represented by the general formula [1 ″] as a constituent unit is not particularly limited as long as the polymer functions as a phosphonium salt. Usually, it is 2,000 to 50,000, preferably 3,000 to 30,000.

  In a polymer including a monomer unit derived from a compound represented by the general formula [1 ″] as a constituent unit, a monomer unit derived from a compound represented by the general formula [1 ″] and a general formula [1 ″] The polymerization ratio of the monomer unit derived from the vinyl monomer other than the compound represented by the formula is not particularly limited as long as the polymer functions as a phosphonium salt. For example, the compound represented by the general formula [1 ″] Monomer unit derived from: Monomer unit derived from a vinyl monomer other than the compound represented by the general formula [1 ″] = 10: 0.1 to 1:10. For example, taking the formula (A) as an example, x and y in the formula (A) are x: y = 10: 0.1 to 1:10.

  The compound represented by the above general formula [1 ″] (a compound derived from the monomer unit constituting the polymer) may be present as a monomer unit in the polymer, and is not necessarily used when the polymer is synthesized. It does not have to be a raw material. That is, these compounds represented by the general formula [1 ″] may be polymerized to form a polymer, or a tertiary phosphine that is a precursor of the compound is polymerized and then quaternary phosphonium chloride is formed with an iodide. Thus, a polymer may be synthesized. As a more specific synthesis method of the polymer, for example, a commercially available tertiary phosphine having a vinyl group such as diphenyl (4-vinylphenyl) phosphine is homopolymerized by a general polymerization method performed in this field, or For example, a commercially available tertiary phosphine having a vinyl group such as diphenyl (4-vinylphenyl) phosphine and a vinyl monomer such as styrene are copolymerized, and then iodine such as hydroiodic acid, methyl iodide, benzyl iodide or the like is copolymerized. There is a method of reacting a compound with a quaternary phosphonium chloride.

  Among the phosphonium salts according to the present invention, one of them may be used alone, or two or more thereof may be used in combination.

  As the phosphonium salt according to the present invention, a polymer containing a monomer unit derived from a compound represented by the general formula [1 ″] as a constituent unit is preferable, and among them, a compound represented by the general formula [1 ″] More preferred is a copolymer comprising a monomer unit derived from the above and a monomer unit derived from a vinyl monomer other than the compound represented by the general formula [1 ″], and among them, the above formula (1 ″ -2) More preferred is a copolymer (a copolymer represented by the formula (A)) comprising a monomer unit derived from the compound represented by formula (I) and a monomer unit derived from a styrene derivative. These polymers are preferable in that they can be easily separated from the product cyclic carbonate, unreacted epoxide (oxirane), by-products and the like, and can be recovered and reused.

  The amount of the phosphonium salt according to the present invention is usually 0.1 to 30 mol%, preferably 0.5 to 20 mol%, in terms of phosphorus atom in the phosphonium salt, per 1 mol of epoxide (oxirane). In addition, when the usage-amount of the said phosphonium salt is very small, it exists in the tendency for the yield of a cyclic carbonate to fall.

  The compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide according to the present invention is a highly active hydrogen atom that can form a hydrogen bond with the oxygen atom of the epoxide (oxirane) that is a raw material. It means a compound having a positively bonded hydrogen atom). More specifically, the compound has a hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene in the molecule. Having at least one group selected from a group and a hydroxyboryl group.

  Specific examples of the compound having a hydroxyl group in the molecule include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, perfluoromethanol, perfluoroethanol, perfluoro. aliphatic alcohols such as n-propanol, hexafluoroisopropanol, perfluoroisopropanol, methoxymethanol, methoxyethanol, ethoxymethanol, ethoxyethanol, such as phenol, 4-methylphenol, 4-methoxyphenol, 4-nitrophenol, 2, Aromatic alcohols such as 2′-biphenol, 2-hydroxypyridine, and 3-hydroxypyridine are exemplified.

  Specific examples of the compound having a carboxyl group in the molecule include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid and lauric acid. Acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids such as lactic acid, malic acid, tartaric acid and citric acid An aliphatic tricarboxylic acid such as aconitic acid, an aliphatic oxocarboxylic acid such as pyruvic acid, an aromatic monocarboxylic acid such as benzoic acid, an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, etc. Aromatic hydroxycarboxylic acids such as salicylic acid and gallic acid, for example aromatic hexacarboxylic acids such as melittic acid Such as carboxylic acid, and the like. In the present invention, a carboxylic acid having one or more hydroxyl groups in the molecule is referred to as a hydroxycarboxylic acid regardless of the number of carboxyl groups.

  Specific examples of the compound having a thiol group in the molecule include fats such as methanethiol, ethanethiol, n-propanethiol, isopropanethiol, n-butanethiol, isobutanethiol, s-butanethiol, and t-butanethiol. Group thiols, for example, aromatic thiols such as thiophenol.

  Specific examples of the compound having a thiocarboxyl group in the molecule include aliphatic thiocarboxylic acids such as thioformic acid, thioacetic acid, thiopropionic acid, thiobutyric acid, thiovaleric acid, and thiocaproic acid, and aromatics such as thiobenzoic acid. Examples thereof include thiocarboxylic acid.

  Specific examples of the compound having a primary or secondary amino group in the molecule include aliphatic primary amines such as methylamine, ethylamine, propylamine, butylamine and ethanolamine, for example, aromatic primary amines such as aniline, Examples thereof include aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine and diethanolamine, and aromatic secondary amines such as diphenylamine.

  Specific examples of the compound having a primary or secondary amide group in the molecule include primary amides such as formamide, acetamide, and propanamide, such as N-methylformamide, N-ethylformamide, N-methylacetamide, N- Secondary amides such as ethylacetamide, N-methylpropanamide, N-ethylpropanamide and the like can be mentioned.

  Specific examples of the compound having a sulfo group in the molecule include aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and trifluoromethanesulfonic acid, such as benzenesulfonic acid and toluenesulfonic acid. And aromatic sulfonic acids such as

  Specific examples of the compound having a ureylene group in the molecule include 1- [3,5-bis (trifluoromethyl) phenyl] -3-phenyl-2-urea.

  Specific examples of the compound having a thioureylene group in the molecule include 1- [3,5-bis (trifluoromethyl) phenyl] -3-phenyl-2-thiourea.

  Specific examples of the compound having a hydroxyboryl group in the molecule include methyl boronic acid, ethyl boronic acid, propyl boronic acid, butyl boronic acid, propenyl boronic acid, phenyl boronic acid, 2-thiophene boronic acid and the like.

  As the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide according to the present invention, not only a monomer but also a polymer (polymer) can be used. Such a polymer has a structure (functional group) containing a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide in the structure.

  Specific examples of such a polymer include, for example, a structure containing a hydrogen atom capable of hydrogen bonding with a vinyl group and an oxygen atom of an epoxide in the molecule, such as 4-hydroxystyrene, (meth) acrylic acid, and (meth) acrylamide. A homopolymer composed of monomer units derived from a compound having (functional group) or a copolymer thereof, for example, a copolymer composed of monomer units derived from 4-hydroxystyrene and monomer units derived from styrene, (meth) A structure (functional group) containing a hydrogen atom capable of hydrogen bonding with a vinyl group and an oxygen atom of an epoxide in the molecule, such as a copolymer comprising a monomer unit derived from acrylic acid and a monomer unit derived from a methacrylic acid ester Hydrogen derived from a monomer unit having a vinyl group in the molecule and capable of hydrogen bonding to an oxygen atom of the epoxide Structure (functional group) to have no compound copolymer comprising monomer units derived from including the child and the like.

  A specific example of a compound having a vinyl group in the molecule and not having a structure (functional group) containing a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide is represented by the above general formula [1 ″]. The thing similar to the specific example of vinyl monomers other than a compound is mentioned.

  Specific examples in the case where the compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide is a polymer include those represented by the formulas (B) to (D). In addition, the polymer shown by a following formula is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.

  When the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide is a polymer (polymer), the weight average molecular weight of the polymer is a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide. If it is in the range which functions as a compound which has this, it will not restrict | limit in particular, For example, it is 2,000-50,000 normally, Preferably it is 3,000-30,000.

  When the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of epoxide is a polymer (polymer), it has a structure (functional group) containing a vinyl atom and a hydrogen atom capable of hydrogen bonding with the oxygen atom of epoxide in the molecule. As a polymerization ratio of a monomer unit derived from a compound and a monomer unit derived from a compound having a vinyl group in the molecule and a structure (functional group) containing a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide. Is not particularly limited as long as the polymer functions as a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide, for example, hydrogen capable of hydrogen bonding with a vinyl group and an oxygen atom of epoxide in the molecule. Monomer unit derived from a compound having an atom-containing structure (functional group): has a vinyl group in the molecule and can hydrogen bond with an oxygen atom of epoxide Monomer units = 10 derived from a compound having no structure (functional group) containing a hydrogen atom: 0.1 to 1: 10. For example, taking the above formulas (C) to (D) as examples, x and y in the above formula (C) are x: y = 10: 0.1 to 1:10, and the formula (D) X, y, and z in it are x: (y + z) = 10: 0.1 to 1:10.

  The compound which has a hydrogen atom which can be hydrogen-bonded with the oxygen atom of epoxide concerning this invention may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide according to the present invention is a homopolymer consisting of monomer units derived from isopropanol, phenol, 4-methoxyphenol, 4-hydroxystyrene, and 4-hydroxystyrene. Copolymer comprising a monomer unit derived from a monomer unit derived from 4-t-butoxystyrene, a monomer unit derived from 4-hydroxystyrene, and a copolymer comprising a monomer unit derived from 4-t-butoxystyrene and styrene Among them, a copolymer composed of a monomer unit derived from 4-hydroxystyrene and a monomer unit derived from 4-t-butoxystyrene, and a monomer unit derived from 4-hydroxystyrene and 4-t-butoxystyrene From monomer units derived from styrene and monomer units derived from styrene That the copolymer is more preferable. When the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide is a polymer, the product can be easily separated from the cyclic carbonate, unreacted epoxide (oxirane), by-product, etc., and recovered. It is preferable in that it can be reused.

  As the usage-amount of the compound which has a hydrogen atom which can hydrogen-bond with the oxygen atom of an epoxide concerning this invention, it is 1-30 normally in conversion of the hydrogen atom in the said compound with respect to mol number of the phosphonium salt concerning this invention. Equivalent, preferably 10 to 15 equivalent. When a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide is usually used in an amount of 1 to 30 equivalents, preferably 10 to 15 equivalents, relative to the number of moles of the phosphonium salt according to the present invention, the product is a cyclic carbonate. Tends to increase the yield.

  In the production method of the present invention, the reason for using the phosphonium salt according to the present invention and the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide is as follows. That is, as a result of intensive studies on a method for producing a cyclic carbonate using carbon dioxide, the present inventors have found that a phosphonium salt having an iodine anion and a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide. It has been found that it acts effectively as a catalyst in the reaction of epoxide (oxirane) with carbon dioxide. A compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide has a coordination action similar to that of a metal ligand to the oxygen atom of the epoxide (oxirane), and a phosphonium salt having an iodine anion is an epoxide ( It is considered that the cyclic carbonate can be produced with good yield even under mild conditions such as normal temperature and normal pressure.

  There is a particular restriction on the order of introduction of the epoxide (oxirane) and carbon dioxide as raw materials, and the phosphonium salt having iodine anion acting as a catalyst and the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide into the reaction system. Absent. For example, an epoxide (oxirane), a phosphonium salt according to the present invention, and a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide are sequentially charged into the reaction system, and carbon dioxide gas is introduced into the reaction system into which these are charged. The method of blowing in is mentioned.

  You may perform the manufacturing method of this invention in the organic solvent which added the organic solvent in the reaction system. In addition, when the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of epoxide, or the raw material epoxide (oxirane) and the product cyclic carbonate also serve as a solvent, such an organic solvent is used. May not be used.

  Specific examples of the organic solvent may be any solvent that does not adversely affect the raw material epoxide (oxirane) and carbon dioxide, and the product cyclic carbonate. For example, aliphatic carbonization such as hexane, heptane, and octane. Hydrogen solvents such as aromatic hydrocarbon solvents such as benzene, toluene and xylene, halogen solvents such as dichloromethane, trichloromethane (chloroform) and tetrachloromethane (carbon tetrachloride) such as diethyl ether, diisopropyl ether and methyl ether solvents such as 2-t-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, such as 2-propanone (acetone), 2-butanone (ethyl methyl ketone), 4-methyl-2- Pentanone (methyl Ketone solvents, such as ethyl acetate, acetic acid-n-propyl, isopropyl acetate, isobutyl acetate, acetic acid-s-butyl, acetic acid-t-butyl, ethyl butyrate, isoamyl butyrate, for example, N, Amide solvents such as N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidinone (N-methylpyrrolidone), 1,3-dimethyl-2-imidazolidinone (dimethylethyleneurea), for example acetonitrile And nitrile solvents such as In the specific examples described above, n- represents a normal isomer, s- represents a sec isomer, and t- represents a tert isomer.

  Of these organic solvents, one of them may be used alone, or two or more thereof may be used in combination.

  The usage-amount of the said organic solvent will not be restrict | limited especially if it is a practical quantity, For example, it is 0.01-500 mL normally with respect to 1 mmol of epoxides (oxirane), Preferably it is 0.1-100 mL.

  The production method of the present invention is desirably performed under the following conditions (reaction temperature, pressure, reaction time).

  The temperature (reaction temperature) during the reaction in the production method of the present invention is desirably set to a temperature at which the epoxide (oxirane) as a raw material and carbon dioxide react efficiently and yield a cyclic carbonate in good yield. The production method of the present invention is characterized in that a cyclic carbonate can be obtained in good yield even under mild conditions such as normal temperature and normal pressure. It is desirable to perform the reaction at ˜65 ° C., preferably 40˜60 ° C.

  The pressure during the reaction in the production method of the present invention is desirably set to a pressure at which the raw material epoxide (oxirane) and carbon dioxide react efficiently and yield a cyclic carbonate in good yield. The production method of the present invention is characterized in that a cyclic carbonate can be obtained with good yield even under mild conditions such as normal temperature and normal pressure. It is desirable to perform the reaction at ˜0.11 MPa.

  The reaction temperature and pressure described above are reaction conditions that have been difficult to achieve with conventional production methods. Since the manufacturing method of the present invention does not require the high temperature and high pressure conditions required by the conventional manufacturing method, compared with the conventional manufacturing method, it requires less heat energy to maintain the temperature and has a high strength. There is an advantageous effect suitable for production on an industrial scale such that a pressure vessel is not required.

  The reaction time in the production method of the present invention is the epoxide (oxirane), the phosphonium salt according to the present invention, the kind of the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide, the amount of carbon dioxide used relative to the epoxide (oxirane), The amount of the phosphonium salt according to the present invention for the epoxide (oxirane) and the amount of the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide, the presence or absence of addition of an organic solvent, the type and amount of use, the reaction temperature, and the reaction time It may be affected by the pressure. For this reason, the desired reaction time cannot be generally stated, but is usually 0.1 to 120 hours, preferably 1 to 72 hours, for example.

  Various cyclic carbonates can be obtained with high yields by the production method of the present invention described above in detail. Since the production method of the present invention can be applied to various epoxides (oxiranes), the structure of the product cyclic carbonate is not particularly limited. Specific examples of the cyclic carbonate include, for example, those represented by the following general formula [III] or the general formula [II] as cyclic carbonates formed from the epoxide (oxirane) represented by the general formula [I]. Examples of the cyclic carbonate generated from the epoxide (oxirane) include those represented by the following general formula [IV].

（式中、Ａ_１、Ａ_２、Ａ_３及びＡ_４は上記に同じ。）

(In the formula, A ₁ , A ₂ , A ₃ and A ₄ are the same as above.)

（式中、Ａ_５、Ａ_６、Ａ_７、Ａ_８、Ａ_９、Ａ_１０及びＴは上記に同じ。）

(In the formula, A ₅ , A ₆ , A ₇ , A ₈ , A ₉ , A ₁₀ and T are the same as above.)

  Specific examples of the cyclic carbonate represented by the general formula [III] include those represented by the formulas (III-I) to (III-XIII). In addition, the cyclic carbonate shown by a following formula is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.

  Specific examples of the cyclic carbonate represented by the general formula [IV] include those represented by the formulas (IV-I) to (IV-IX). In addition, the cyclic carbonate shown by a following formula is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.

  The cyclic carbonate obtained by the production method of the present invention can be isolated by general post-treatment operations and purification operations usually performed in this field. As a specific example of the isolation method, for example, if necessary, the residue obtained by distilling off the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide and / or the organic solvent in the reaction system is obtained. The cyclic carbonate can be isolated by performing recrystallization, distillation, column chromatography or the like. In addition, if necessary, the cyclic residue can be isolated by performing an extraction operation on the obtained residue and removing impurities, followed by recrystallization, distillation, column chromatography, or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited at all by these examples. In the following examples, “%” is based on weight (w / w%) unless otherwise specified.

Synthesis Example 1 Synthesis of triphenylphosphine hydrogen iodide [formula (1′-1)] A solution of 1.05 g (4 mmol) of triphenylphosphine in 8 mL of 1,4-dioxane was stirred at room temperature, and 55% iodine was added to the solution. Hydrochloric acid 1 mL (ca. 7.3 mmol) was added, and the mixture was further stirred at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether, and the residue was vacuum-dried at 40 ° C. for 12 hours to obtain 1.56 g of a light yellow solid triphenylphosphine hydrogen iodide salt. (Yield> 99%) was obtained. The structure of triphenylphosphine hydrogen iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 5.33 (d, 1H, J = 5.6 Hz, P H ), 7.52 to 7.58 (m, 6H, Ar H ), 7.59-7.66 (m, 9H, Ar H ).
¹³ C-NHR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 128.74 (d, J = 11.5 Hz, Ar ), 131.46 (d, J = 9.6 Hz, Ar ), 132.02 (d, J = 1.9 Hz, Ar ), 132.69 (d, J = 102 Hz, Ar ).

Synthesis Example 2 Synthesis of methyltriphenylphosphonium iodide [formula (1′-2)] A solution of 1.05 g (4 mmol) of triphenylphosphine in 16 mL of dry tetrahydrofuran was stirred at room temperature, and 1.14 g of methyl iodide ( 8 mmol) was added, and the mixture was further stirred at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether, and the residue was vacuum-dried at 40 ° C. for 12 hours to obtain 1.59 g of a white powder of methyltriphenylphosphonium iodide (recovery). 98%) was obtained. The structure of triphenylphosphine hydrogen iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 3.18 (d, 3H, J = 13.6 Hz, PC H ₃ ), 7.63-7.86 (m, 15H, Ar H ).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 11.45 (d, J = 57.2 Hz, P C H ₃ ), 118.68 (d, J = 88.7 Hz, Ar ) , 130.41 (d, J = 13.3 Hz, Ar ), 133.16 (d, J = 10.5 Hz, Ar ), 135.14 (d, J = 2.8 Hz, Ar ).

Synthesis Example 3 Synthesis of dicyclohexylphenylphosphine hydrogen iodide [formula (1′-4)] A solution of 274 mg (1 mmol) of dicyclohexylphenylphosphine in 4 mL of 1,4-dioxane was stirred at room temperature, and 55% hydrogen iodide was added to the solution. After adding 0.25 mL (ca.1.8 mmol) of acid, the mixture was further stirred at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether / tetrahydrofuran, and the residue was vacuum-dried at 40 ° C. for 12 hours to obtain 386 mg of dicyclohexylphenylphosphine hydrogen iodide as a pale yellow powder. (Yield 96%) was obtained. The structure of dicyclohexylphenylphosphine hydrogen iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 1.13-2.33 (m, 20H, 2 (C H ₂ ) ₅ ), 2.88-3.02 (m, 2H , 2 (C H )), 7.61-8.05 (m, 5H, Ar H ), 9.07 (dt, 1H, J = 489.2, 6.4 Hz, P H ).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 24.86 ( C H ₂ ), 25.55 ( C H ₂ ), 25.68 (d, J = 1.9 Hz, C H ₂ ), 26.04 (d, J = 2.9 Hz, C H ₂ ), 26.80 (d, J = 1.9 Hz, C H ₂ ), 28.76 (d, J = 41.0 Hz, C H), 113.14 (d, J = 74.4 Hz, Ar ), 130.15 (d, J = 11.4 Hz, Ar ), 134.09 (d, J = 8.6 Hz, Ar ), 134. 71 (d, J = 2.8 Hz, Ar ).

Synthesis Example 4 Synthesis of methyldicyclohexylphenylphosphonium iodide [formula (1′-5)] A solution of 549 mg (2 mmol) of dicyclohexylphenylphosphine in 8 mL of dry tetrahydrofuran was stirred at room temperature, and 568 mg (4 mmol) of methyl iodide was added to the solution. After that, the mixture was further stirred at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether, and the residue was vacuum-dried at 40 ° C. for 12 hours to give 818 mg (yield 98%) of white powder of methyldicyclohexylphenylphosphonium iodide. %). The structure of methyldicyclohexylphenylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 1.13-2.18 (m, 20H, 2 (C H ₂ ) ₅ ), 2.36 (d, 3H, J = 12 .4 Hz, PC H ₃ ), 3.04-3.17 (m, 2H, 2 (C H )), 7.69-7.82 (m, 3H, Ar H ), 7.87-7.94 ( M , 2H, ArH).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 0.74 (d, J = 51.5 Hz, P C H ₃ ), 25.08 ( C H ₂ ), 25.39-25 .62 (m, C H ₂ ), 29.83 (d, J = 45.7 Hz, C H), 115.57 (d, J = 77.2 Hz, Ar ), 130.21 (d, J = 11 .5 Hz, Ar ), 132.56 (d, J = 7.6 Hz, Ar ), 134.39 (d, J = 3.0 Hz, Ar ).

Synthesis Example 5 Synthesis of tri-n-butylphosphine hydrogen iodide [formula (1′-7)] A solution of 3.92 g (18 mmol) of 93% tributylphosphine in 24 mL of 1,4-dioxane was stirred at room temperature. After adding 3 mL (ca. 21.9 mmol) of 55% hydroiodic acid over 5 minutes, the mixture was further stirred at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether / tetrahydrofuran, and the residue was vacuum-dried at 50 ° C. for 24 hours to obtain a white solid of tri-n-butylphosphine hydrogen iodide. 6.11 g (yield> 99%) of salt was obtained. The structure of tri-n-butylphosphine hydrogen iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 0.98 (t, 9H, J = 7.2 Hz, 3 (C H ₃ )), 1.54 (sext, 6H, J = _{7.6Hz, 3 (C H 2 CH} 3)), 1.64-1.74 (m, 6H, 3 (CH 2 C H 2 CH 2)), 2.44-2.53 (m, 6H, 3 (PC H ₂ )), 7.40 (dsep, 1H, J = 486.0, 5.2 Hz, P H ).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 13.33 ( C H ₃ ), 17.00 (d, J = 46.7 Hz, P C H ₂ ), 23.64 (d _{, J = 14.3Hz, PCH 2 C} H 2), 24.67 (d, J = 4.7Hz, C H 2 CH 3).

Synthesis Example 6 Synthesis of methyltri-n-butylphosphonium iodide [formula (1′-8)] A solution of 870 mg (4 mmol) of 93% tributylphosphine in 16 mL of dry tetrahydrofuran was stirred at room temperature, and 1.14 g of methyl iodide was added to the solution. (8 mmol) was added, and the mixture was further stirred at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether, and the residue was vacuum-dried at 40 ° C. for 12 hours to obtain 1.24 g of white powder of methyltri-n-butylphosphonium iodide. (Yield 90%) was obtained. The structure of methyltri-n-butylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 0.98 (t, 9H, J = 7.2 Hz, 3 (C H ₃ )), 1.49-1.64 (m, 12H, 3 (C H ₂ C H ₂ CH ₃ )), 2.10 (d, 3H, J = 13.2 Hz, PC H ₃ ), 2.43-2.53 (m, 6H, 3 (PC H ₂ )).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 5.19 (d, J = 51.5 Hz, P C H ₃ ), 13.10 ( C H ₃ ), 20.09 (d , J = 48.6 Hz, P C H ₂ ), 23.18 (d, J = 4.8 Hz, C H ₂ CH ₃ ), 23.31 (d, J = 15.2 Hz, PCH ₂ C H ₂ ) .

Synthesis Example 7 Synthesis of methyltris (dimethylamino) phosphonium iodide [formula (1′-11)] A solution of 816 mg (5 mmol) of tris (dimethylamino) phosphine in 10 mL of dry tetrahydrofuran was stirred at room temperature, and methyl iodide 1 was added to the solution. After adding .42 g (10 mmol), the mixture was further stirred at room temperature for 6 hours. After completion of the reaction, the residue obtained by distilling off the solvent was vacuum-dried at 40 ° C. for 12 hours to obtain 1.54 g (yield 100%) of methyltris (dimethylamino) phosphonium iodide as a white powder. . The structure of methyltris (dimethylamino) phosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 2.25 (d, 3H, J = 14.0 Hz, PC H ₃ ), 2.84 (d, 18H, J = 10.4 Hz) , 6 (C H ₃ )).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 9.92 (d, J = 111.5 Hz, P C H ₃ ), 36.88 (d, J = 3.9 Hz, N C H _3).

Synthesis Example 8 Synthesis of poly [styrene- (4-vinyltriphenylphosphine)] copolymer (P-1A) using 3 mol% of 2,2′-azobis (isobutyronitrile) (AIBN) 4-vinyltri 1.44 g (5 mmol) of phenylphosphine, 1.56 g (15 mmol) of styrene and 99 mg (0.6 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) are dissolved in 20 mL of dry toluene, and freeze-dried three times. After stirring, the mixture was stirred at 80 ° C. for 24 hours. After completion of the reaction, the solution was concentrated to about half and then reprecipitated with 100 mL of methanol. The residue was washed with methanol and vacuum-dried at 40 ° C. for 12 hours to obtain 2.50 g of a white powdered poly [styrene- (4-vinyltriphenylphosphine)] copolymer (P-1A) (yield 83%). ) The structure (unit ratio) of the copolymer was confirmed by ¹ H-NMR analysis. Moreover, molecular weight and molecular weight distribution were confirmed by GPC analysis.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ , 25 ° C.) δ (ppm): 0.76-2.65 (m, 12 H , C H ₂ C H ), 6.16-7.65 (m, 29 .6H, Ar H).
x (4-vinyltriphenylphosphine): y (styrene) = 1: 3.0.
GPC (DMF, 40 ° C.): M _n = 4,230, M _w / M _n = 2.07.

Synthesis Example 9 Synthesis of poly [styrene- (4-vinyltriphenylphosphine)] copolymer (P-2A) using 1 mol% of 2,2′-azobis (isobutyronitrile) (AIBN) 4-vinyltri 1.44 g (5 mmol) of phenylphosphine, 1.56 g (15 mmol) of styrene and 33 mg (0.2 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) are dissolved in 20 mL of dry toluene, and freeze-dried three times. After stirring, the mixture was stirred at 80 ° C. for 48 hours. After completion of the reaction, the solution was concentrated to about half and then reprecipitated with 100 mL of methanol. The residue was washed with methanol and vacuum-dried at 40 ° C. for 12 hours to obtain 2.43 g of a white powdered poly [styrene- (4-vinyltriphenylphosphine)] copolymer (P-2A) (yield 81%). ) The structure (unit ratio) of the copolymer was confirmed by ¹ H-NMR analysis. Moreover, molecular weight and molecular weight distribution were confirmed by GPC analysis.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ , 25 ° C.) δ (ppm): 0.87-2.41 (m, 12H, C H ₂ C H ), 6.24-7.71 (m, 31H , Ar H ).
x (4-vinyltriphenylphosphine): y (styrene) = 1: 2.7.
GPC (DMF, 40 ° C.): M _n = 13,100, M _w / M _n = 2.03.

Synthesis Example 10 Synthesis of poly [styrene-methyldiphenyl (4-vinylphenyl) phosphonium iodide] copolymer (P-1) Poly [styrene- (4-vinyltriphenylphosphine)] copolymer obtained in Synthesis Example 8 A solution of polymer (P-1A) 901 mg (1.5 mmol, -PPh ₂ groups) in dry dichloromethane 7.5 mL was stirred at room temperature, methyl iodide 1.06 g (7.5 mmol) was added to the solution, Furthermore, it stirred at 50 degreeC for 24 hours. After completion of the reaction, the residue obtained by distilling off the solvent was vacuum-dried at 50 ° C. for 12 hours to give a yellow solid poly [styrene-methyldiphenyl (4-vinylphenyl) phosphonium iodide] copolymer ( P-1) 1.10 g (99% yield) was obtained. The structure of the copolymer was confirmed by ¹ H-NMR analysis. The molecular weight was calculated based on the number average molecular weight (M _n = 4,230) of the raw material.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ , 25 ° C.) δ (ppm): 0.71-2.49 (m, 12 H , C H ₂ C H ), 2.85-3.28 (brs, 3H , PC H ₃ ), 6.09-8.08 (m, 29H, Ar H ).
M _n = 5,230 (calculated value).

Synthesis Example 11 Synthesis of poly [styrene-methyldiphenyl (4-vinylphenyl) phosphonium iodide] copolymer (P-2) Poly [styrene- (4-vinyltriphenylphosphine)] copolymer obtained in Synthesis Example 9 A solution of 854 mg (1.5 mmol, -PPh ₂ groups) of polymer (P-2A) in 7.5 mL of dry dichloromethane was stirred at room temperature, and 1.06 g (7.5 mmol) of methyl iodide was added to the solution. Furthermore, it stirred at 50 degreeC for 24 hours. After completion of the reaction, the residue obtained by distilling off the solvent was vacuum-dried at 50 ° C. for 12 hours to give a yellow solid poly [styrene-methyldiphenyl (4-vinylphenyl) phosphonium iodide] copolymer ( P-2) 1.08 g (yield 100%) was obtained. The structure of the copolymer was confirmed by ¹ H-NMR analysis. The molecular weight was calculated based on the number average molecular weight of the raw material (M _n = 13,100).
¹ H-NMR (400 MHz, CD ₂ Cl ₂ , 25 ° C.) δ (ppm): 0.81 to 2.88 (m, 11.1 H , C H ₂ C H ), 2.95 to 3.36 (brs _{, 3H, PC H 3),} 6.30-8.39 (m, 27.5H, Ar H).
M _n = 16,400 (calculated value).

Comparative Synthesis Example 1 Synthesis of triphenylphosphine hydrobromide A solution of 1.05 g (4 mmol) of triphenylphosphine in 8 mL of 1,4-dioxane was stirred at room temperature, and 1 mL (ca.8) of 48% hydrobromic acid was added to the solution. 0.8 mmol), and the mixture was further stirred at 70 ° C. for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether, and the residue was vacuum-dried at 40 ° C. for 12 hours to obtain 1.34 g of triphenylphosphine hydrobromide as a white solid ( Yield 98%). The structure of triphenylphosphine hydrobromide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 7.53-7.59 (m, 6H, Ar H ), 7.60-7.67 (m, 9H, Ar H ), 10.60 (brs, 1H, P H).
¹³ C-NMR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 128.77 (d, J = 11.4 Hz, Ar ), 131.48 (d, J = 9.6 Hz, Ar ), 132.05 (d, J = 1.9 Hz, Ar ), 132.70 (d, J = 102 Hz, Ar ).

Synthesis Example 12 Synthesis of 1- [3,5-bis (trifluoromethyl) phenyl] -3-phenyl-2-thiourea (compound having a hydrogen atom capable of hydrogen bonding to an oxygen atom of epoxide) 3,5 isothiocyanic acid A solution of 814 mg (3 mmol) of bis (trifluoromethyl) phenyl in 15 mL of dry dichloromethane was stirred at room temperature, 293 mg (3.15 mmol) of aniline was added to the solution, and the mixture was further stirred at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with hexane / t-butyl methyl ether, and the residue was vacuum-dried at 40 ° C. for 12 hours to give 1- [3,5 of white solid. There was obtained 1.01 g (yield 92%) of -bis (trifluoromethyl) phenyl] -3-phenyl-2-thiourea. The structure of 1- [3,5-bis (trifluoromethyl) phenyl] -3-phenyl-2-thiourea was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ , 25 ° C.) δ (ppm): 7.33-7.41 (m, 3H, Ar H ), 7.47-7.53 (m, 2H, Ar H ), 7.71 (s, 1H, Ar H), 7.87 (brs, 1H, N H), 8.01 (s, 1H, Ar H), 8.59 (brs, 1H, N H).
¹³ C-NMR (100 MHz, CD ₂ Cl ₂ , 25 ° C.) δ (ppm): 119.80 ( Ar ), 122.22 ( Ar ), 124.93 ( Ar ), 125.30 ( Ar ), 126. 07 (Ar), 128.58 (Ar ), 130.89 (Ar), 132.11 (q, J = 33.4Hz, C F 3), 136.23 (Ar), 140.34 (Ar), 180.21 ( C = S).

Synthesis Example 13 Synthesis of poly (4-t-butoxystyrene) Drying 4.29 g (30 mmol) of 4-t-butoxystyrene and 148 mg (0.9 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) It melt | dissolved in 30 mL of toluene, and it stirred at 80 degreeC for 48 hours after freeze deaeration 3 times. After completion of the reaction, the solution was concentrated to about 1/3, and then reprecipitated with 150 mL of methanol. The residue was washed with methanol and then vacuum-dried at 40 ° C. for 12 hours to obtain 2.23 g (yield 42%) of white powder poly (4-t-butoxystyrene). The structure of the polymer was confirmed by ¹ H-NMR analysis. Moreover, molecular weight and molecular weight distribution were confirmed by GPC analysis.
¹ H-NMR (400 MHz, DMF-d ₇ , 25 ° C.) δ (ppm): 0.85-2.00 (m, 12H, C H ₂ C H , C (C H ₃ ) ₃ ), 6.16 -6.87 (m, 4H, Ar H ).
GPC (DMF, 40 ° C.): M _n = 10,600, M _w / M _n = 2.03.

Synthesis Example 14 Synthesis of poly [(4-t-butoxystyrene)-(4-hydroxystyrene)] polymer (P-3) (a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide) In Synthesis Example 13 A solution of the obtained poly (4-t-butoxystyrene) 1.76 g (10 mmol, -Ot-Bu group) in 80 mL of dry dichloromethane was stirred at room temperature, and 20 mL of trifluoroacetic acid was added to the solution. Stir at room temperature for 12 hours. After completion of the reaction, 50 mL of 10% aqueous sodium carbonate solution was added to the residue obtained by distilling off the solvent, and the mixture was stirred at room temperature for 1 hour. The suspension was filtered, and the residue was washed with water and then vacuum-dried at 40 ° C. for 24 hours to obtain a light pink solid poly [(4-t-butoxystyrene)-(4-hydroxystyrene)] polymer. 1.42 g (yield 98%) of (P-3) was obtained. The conversion rate of the butoxy group into a hydroxyl group was 88%. The structure (unit ratio) of the polymer was confirmed by ¹ H-NMR analysis. Moreover, molecular weight and molecular weight distribution were confirmed by GPC analysis.
¹ H-NMR (400 MHz, DMF-d ₇ , 25 ° C.) δ (ppm): 0.76-2.46 (m, 4.7H, C H ₂ C H , C (C H ₃ ) ₃ ), 5 .84-7.21 (m, 4.6H, Ar H ), 8.15-10.2 (brs, 1H, O H).
x (4-t-butoxystyrene): z (4-hydroxystyrene) = 0.14: 1.
GPC (DMF, 40 ° C.): M _n = 7,040, M _w / M _n = 1.98.

Synthesis Example 15 Synthesis of poly [styrene- (4-t-butoxystyrene)] copolymer 1.76 g (10 mmol) of 4-t-butoxystyrene, 3.12 g (30 mmol) of styrene and 2,2′-azobis (iso 197 mg (1.2 mmol) of butyronitrile) (AIBN) was dissolved in 40 mL of dry toluene, and after freeze degassing three times, the mixture was stirred at 80 ° C. for 48 hours. After completion of the reaction, the solution was concentrated to about 1/3 and then reprecipitated with 200 mL of methanol. The residue was washed with methanol and then vacuum-dried at 40 ° C. for 12 hours to obtain 3.03 g (yield 62%) of a white powder of poly [styrene- (4-t-butoxystyrene)] copolymer. The structure (unit ratio) of the copolymer was confirmed by ¹ H-NMR analysis. Moreover, molecular weight and molecular weight distribution were confirmed by GPC analysis.
¹ H-NMR (400 MHz, DMF-d ₇ , 25 ° C.) δ (ppm): 0.83 to 2.45 (m, 12 H , C H ₂ C H ), 1.12 to 1.41 (brs, 9H) , C (C H ₃ ) ₃ ), 6.24-7.42 (m, 19H, Ar H ).
x (4-t-butoxystyrene): y (styrene) = 1: 2.9.
GPC (DMF, 40 ° C.): M _n = 5,080, M _w / M _n = 2.05.

Synthesis Example 16 Synthesis of poly [styrene- (4-t-butoxystyrene)-(4-hydroxystyrene)] copolymer (P-4) (a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide) Synthesis A solution of 2.40 g (5 mmol, -Ot-Bu group) of the poly [styrene- (4-t-butoxystyrene)] copolymer obtained in Example 15 in 40 mL of dry dichloromethane was stirred at room temperature. After adding 10 mL of trifluoroacetic acid, the mixture was further stirred at room temperature for 12 hours. After completion of the reaction, 50 mL of 10% aqueous sodium carbonate solution was added to the residue obtained by distilling off the solvent, and the mixture was stirred at room temperature for 1 hour. The suspension was filtered, and the residue was washed with water and then vacuum-dried at 40 ° C. for 24 hours to obtain a light gray solid poly [styrene- (4-t-butoxystyrene)-(4-hydroxystyrene)]. 2.15 g (99% yield) of copolymer (P-4) was obtained. The conversion rate of the butoxy group into a hydroxyl group was 81%. The structure (unit ratio) of the target product was confirmed by ¹ H-NMR analysis. Moreover, molecular weight and molecular weight distribution were confirmed by GPC analysis.
¹ H-NMR (400 MHz, DMF-d ₇ , 25 ° C.) δ (ppm): 0.59-2.63 (m, 16.6H, C H ₂ C H , C (C H ₃ ) ₃ ), 6 .15-7.74 (m, 22.9H, Ar H ), 8.81-9.80 (brs, 1H, O H).
x (4-t-butoxystyrene): y (styrene): z (4-hydroxystyrene) = 0.23: 3.6: 1.
GPC (DMF, 40 ° C.): M _n = 5,230, M _w / M _n = 2.28.

Examples 1 to 9 and Comparative Examples 1 to 6 Synthesis of (phenoxymethyl) ethylene carbonate using various phosphonium salts or phosphines Various phosphonium salts or phosphine 0.05 mmol solutions shown in Table 1 in 0.2 mL of isopropanol (or The suspension was stirred at room temperature, 1 mmol of phenylglycidyl ether was added to the solution, the reaction system was sealed with a balloon filled with carbon dioxide gas to make a carbon dioxide gas atmosphere (0.1 MPa), and room temperature For 24 hours. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed with reference to tetramethylsilane contained in deuterated chloroform, and the produced (phenoxymethyl) ethylene carbonate Yield was calculated. These results are shown in Table 1.

Examples 10 and 11 and Comparative Examples 7 to 10 Synthesis of (phenoxymethyl) ethylene carbonate in the presence or absence of a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide Triphenylphosphine hydroiodide salt A solution obtained by dissolving (or suspending) 0.05 mmol in 0.2 mL of various organic solvents shown in Table 2 was stirred at room temperature, 1 mmol of phenylglycidyl ether was added to the solution (or suspension), The reaction system was sealed with a balloon filled with carbon gas to form a carbon dioxide gas atmosphere (0.1 MPa), and further stirred at room temperature for 24 hours. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed with reference to tetramethylsilane contained in deuterated chloroform, and the produced (phenoxymethyl) ethylene carbonate Yield was calculated. These results are shown in Table 2. In these experimental examples, experiments were performed in the presence or absence of a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide. That is, among the above organic solvents, examples using the solvents of Examples 10 and 11 that function as compounds having hydrogen atoms capable of hydrogen bonding with oxygen atoms are compounds having hydrogen atoms capable of hydrogen bonding with oxygen atoms of epoxides. Is a compound having a hydrogen atom capable of hydrogen bonding to an oxygen atom, in which an example using the solvent of Comparative Examples 7 to 10 that does not function as a compound having a hydrogen atom capable of hydrogen bonding to an oxygen atom is an experimental example in the presence of It is an experimental example in the absence of.

Examples 12 to 18 and Comparative Examples 11 and 12 Synthesis of (phenoxymethyl) ethylene carbonate using a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide as a co-solvent 0.05 mmol of methyltriphenylphosphonium iodide A 0.2 mL solution (or suspension) of isopropanol was stirred at room temperature, and 0.05 mmol of a compound having hydrogen atoms capable of hydrogen bonding with oxygen atoms of epoxides and 1 mmol of phenylglycidyl ether shown in Table 3 were added to the solution. After the addition, the reaction system was sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa), and further stirred at room temperature for 24 hours. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed on the basis of tetramethylsilane contained in deuterated chloroform, and the produced (phenoxymethyl) ethylene carbonate Yield was calculated. These results are shown in Table 3. In Comparative Example 11, an experiment was performed using a system in which a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide was not added. In Comparative Example 12, an experiment was conducted using a system in which methyltriphenylphosphonium iodide was not added. .

Examples 19 to 22 Synthesis of n-butylethylene carbonate using various phosphonium salts After adding 0.05 mmol of phenol and 1 mmol of n-hexene oxide to 0.05 mmol of various phosphonium salts shown in Table 4, carbon dioxide gas The reaction system was sealed with a balloon filled with a carbon dioxide gas atmosphere (0.1 MPa) and further stirred at room temperature for 24 hours. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed on the basis of tetramethylsilane contained in deuterated chloroform, and the produced n-butylethylene carbonate was recovered. The rate was calculated. These results are shown in Table 4.

Examples 23 to 27 and Comparative Examples 13 and 14 Synthesis of n-butylethylene carbonate using various compounds having a hydrogen atom capable of hydrogen bonding with the oxygen atom of epoxide To 0.05 mmol of methyltriphenylphosphonium iodide, After adding 0.05 mmol of various compounds having hydrogen atoms capable of hydrogen bonding with oxygen atoms of epoxide and 1 mmol of n-hexene oxide shown in Table 5, the reaction system was sealed with a balloon filled with carbon dioxide gas, Under a carbon gas atmosphere (0.1 MPa), the mixture was further stirred at room temperature for 24 hours. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed on the basis of tetramethylsilane contained in deuterated chloroform, and the produced n-butylethylene carbonate was recovered. The rate was calculated. These results are shown in Table 5. In Comparative Example 13, an experiment was performed using a system in which a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide was not added. In Comparative Example 14, an experiment was conducted using a system in which methyltriphenylphosphonium iodide was not added. .

Examples 28-34 Examination of addition amount of compound having hydrogen atom capable of hydrogen bonding with oxygen atom of epoxide with respect to phosphonium salt 0.01 mmol of methyltriphenylphosphonium iodide, and 4-methoxyphenol and n in the amounts shown in Table 6 -After adding 1 mmol of hexene oxide, the reaction system was sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa), and further stirred at room temperature for 24 hours. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed on the basis of tetramethylsilane contained in deuterated chloroform, and the produced n-butylethylene carbonate was recovered. The rate was calculated. These results are shown in Table 6.

Examples 35 to 40 Synthesis of (phenoxymethyl) ethylene carbonate using a polymer (copolymer P-1 or P-2) as a phosphonium salt The phosphonium salt (P-1 or P) obtained in Synthesis Example 10 or 11 -2) A solution obtained by dissolving (or suspending) 0.05 mmol in 0.2 mL of various solvents shown in Table 7 is stirred at room temperature, and 0.05 mmol of phenol and phenylglycidyl ether are added to the solution (or suspension). After 1 mmol was added, the reaction system was sealed with a balloon filled with carbon dioxide gas to create a carbon dioxide gas atmosphere (0.1 MPa), and further stirred at room temperature for 24 hours. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed with reference to tetramethylsilane contained in deuterated chloroform, and the produced (phenoxymethyl) ethylene carbonate Yield was calculated. These results are shown in Table 7. Examples 35 and 36 correspond to compounds having hydrogen atoms in which an experiment using a system in which no phenol is added and isopropanol as a solvent can form a hydrogen bond with an oxygen atom of the epoxide.

Examples 41 and 42 Synthesis of n-butylethylene carbonate using polymer (copolymer P-1 or P-2) as phosphonium salt Phosphonium salt (P-1 or P-) obtained in Synthesis Example 10 or 11 2) After adding 0.05 mmol of phenol and 1 mmol of n-hexene oxide to 0.05 mmol, the reaction system is sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa), and further at room temperature. For 24 hours. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed on the basis of tetramethylsilane contained in deuterated chloroform, and the produced n-butylethylene carbonate was recovered. The rate was calculated. These results are shown in Table 8.

Examples 43 to 45 Synthesis of carbonate using a polymer (polymer P-3 or copolymer P-4) as a compound having a hydrogen atom capable of hydrogen bonding to an oxygen atom of epoxide Methyltriphenylphosphonium iodide The compound having a hydrogen atom capable of hydrogen bonding to the oxygen atom of epoxide (P-3 or P-4) obtained in Synthesis Example 14 or 16 in 05 mmol, 0.2 mL of tetrahydrofuran, and Table 9 After adding 1 mmol of epoxide, the reaction system was sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa), and further stirred at room temperature for 24 hours. After extracting a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, the reaction solution was analyzed with reference to tetramethylsilane contained in deuterated chloroform, and the yield of the produced carbonate was calculated. . These results are shown in Table 9. In Examples 43 and 44, bulk experiments using a system to which tetrahydrofuran was not added were conducted.

Examples 46 to 48 A polymer (copolymer P-1) was used as a phosphonium salt, and a polymer (copolymer P-4) was used as a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide. Synthesis of carbonate Compound (P-4) 0 having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide obtained in Synthesis Example 16 to 0.05 mmol of the phosphonium salt (P-1) obtained in Synthesis Example 10 .05 mmol, 0.2 mL of tetrahydrofuran and 1 mmol of epoxide shown in Table 10 were added, and the reaction system was sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa). The mixture was stirred for 24 hours under the conditions shown. After extracting a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, the reaction solution was analyzed with reference to tetramethylsilane contained in deuterated chloroform, and the yield of the produced carbonate was calculated. . These results are shown in Table 10. In Example 48, a bulk experiment using a system to which tetrahydrofuran was not added was performed.

Example 49 Using a polymer (copolymer P-1) as a phosphonium salt and a polymer (copolymer P-4) as a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide The compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide obtained in Synthesis Example 16 is added to 0.05 mmol of the phosphonium salt (P-1) obtained in Synthesis Example 10 ( P-4) After adding 0.05 mmol and 1 mmol of n-hexene oxide, the reaction system is sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa), and further at room temperature for 24 hours. Stir. After removing a small amount of the reaction solution after stirring for 24 hours, the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed on the basis of tetramethylsilane contained in deuterated chloroform, and the produced n-butylethylene carbonate was recovered. The rate was calculated.
Further, from the solution after completion of the reaction, the phosphonium salt (P-1) and the compound (P-4) having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide are recovered, and the experiment is repeated four times under the same conditions. (5 experiments were performed in total), and the yield of the produced n-butylethylene carbonate was calculated. These results are shown in Table 11.

  From the results of Tables 1 to 5, in the reaction of epoxide (oxirane) and carbon dioxide, a combination of a quaternary phosphonium salt having iodine anion and a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of epoxide is used. Thus, it was found that the reaction of epoxide (oxirane) and carbon dioxide proceeds efficiently even under mild conditions such as normal temperature and normal pressure. That is, when phenyl glycidyl ether, which is a highly reactive epoxide, is used as a raw material, the reaction proceeds efficiently, and even when n-hexene oxide, which is a low reactive epoxide, is used, in bulk. The reaction proceeds efficiently by the reaction, and a cyclic carbonate can be obtained in a high yield regardless of which epoxide (oxirane) is used. Further, the phosphonium salt according to the present invention is a metal-free (metal-free) catalyst, and further, a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide can be easily procured from a commercial product. The production method of the present invention using these catalysts was useful from the viewpoint of green chemistry, and was found to be a practical production method considering reduction of environmental load.

  In addition, from the results in Table 6, it was found that the cyclic carbonate can be obtained with high yield by adjusting the amount of the compound having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide. That is, when a compound having 2 to 30 equivalents of a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide is used with respect to the number of moles of the phosphonium salt, a cyclic carbonate can be obtained with a high yield. It was found that when a compound having 10 to 15 equivalents of hydrogen atom capable of hydrogen bonding with the oxygen atom of epoxide was used with respect to the number of moles, a cyclic carbonate was obtained with higher yield.

  Furthermore, from the results of Tables 7 to 11, even when the polymer is used as a quaternary phosphonium salt having an iodine anion and / or a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide, the yield is obtained. It was found that a cyclic carbonate can be obtained well. It was also found that even when these polymers were recovered and repeatedly used, a cyclic carbonate was obtained without a decrease in yield. A quaternary phosphonium salt having an iodine anion or a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide comprising these polymers is useful from the viewpoint of green chemistry because it can be easily recovered and reused. I found out.

  In the production method of the present invention, for example, in producing a cyclic carbonate widely used in various applications such as an electrolyte of a lithium ion secondary battery, a plastic raw material, etc. by reaction of epoxide (oxirane) with carbon dioxide, This makes it possible to produce the cyclic carbonate with high yield under mild conditions such as normal pressure. Furthermore, the production method of the present invention makes it possible to practically produce a cyclic carbonate in consideration of reducing the environmental load.

Claims (6)

A phosphonium salt comprising a polymer containing epoxide and carbon dioxide as a constituent unit and a monomer unit derived from the compound represented by the general formula [1 ″], and a homopolymer comprising a monomer unit derived from 4-hydroxystyrene A copolymer comprising a monomer unit derived from 4-hydroxystyrene and a monomer unit derived from 4-t-butoxystyrene; a monomer unit derived from 4-hydroxystyrene; and a monomer unit derived from 4-t-butoxystyrene; A method for producing a cyclic carbonate, characterized by reacting in the presence of a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide selected from a copolymer comprising monomer units derived from styrene .

(Wherein R ^{1 ″} is an alkyl group having 1 to 10 carbon atoms having a vinyl group, an aryl group having 6 to 10 carbon atoms having a vinyl group, an aralkyl group having 7 to 12 carbon atoms having a vinyl group, or vinyl. Represents an N, N-dialkylamino group having 2 to 10 carbon atoms and R ^{2 ″} , R ^{3 ″} and R ^{4 ″} each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Represents an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an N, N-dialkylamino group having 2 to 10 carbon atoms.) The phosphonium salt is a monomer unit derived from the compound represented by the general formula [1 ″] and a monomer unit derived from a vinyl monomer selected from a styrene derivative, (meth) acrylic acid ester, (meth) acrylamide and acrylonitrile. The manufacturing method of Claim 1 which is a copolymer which consists of. The styrene derivative is selected from styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 4-ethylstyrene, 4-n-propylstyrene, and 4-isopropylstyrene. The manufacturing method according to claim 2. The production method according to claim 1, wherein the phosphonium salt is a copolymer composed of a monomer unit derived from a compound represented by the general formula (1 ''-2) and a monomer unit derived from a styrene derivative.

The manufacturing method of Claim 1 made to react at 40-60 degreeC. The manufacturing method of Claim 1 made to react by 0.09-0.11 MPa.