JP6172152B2 - 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 are still problems in terms of environmental impact, 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 studies on such a production method, the present inventors have an iodine anion as a counter anion in a reaction of epoxide (oxirane) and carbon dioxide, and can hydrogen bond with an oxygen atom of epoxide. It has been found that the above-described object can be achieved by using a phosphonium salt having a hydrogen atom, and the present invention has been completed.

  The present invention relates to a process 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 having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide. It is invention of this.

  In producing a cyclic carbonate by the reaction of epoxide (oxirane) and carbon dioxide, by using a phosphonium salt having an iodine anion as a counter anion and 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 having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide is used, the reason why the above-described effect can be obtained is as follows. Conceivable. That is, a hydrogen atom capable of hydrogen bonding to an oxygen atom of an epoxide in a phosphonium salt is coordinated to an oxygen atom of the epoxide (oxirane), and the phosphonium salt (hereinafter referred to as phosphonium salt) with respect to the epoxide (oxirane) coordinated with a hydrogen atom. The phosphonium salt according to the present invention may be abbreviated to be effective as a catalyst, so that it is considered that a cyclic carbonate can be produced in good yield even under mild conditions such as normal temperature and normal pressure. .

  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 an iodine anion and having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the 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 has an iodine anion and is capable of hydrogen bonding with an oxygen atom of an epoxide (oxirane) that is a raw material, and has a highly active hydrogen atom (positive for binding to a negative atom). A quaternary phosphonium salt having a hydrogen atom), 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], (2) a polymer containing a monomer unit derived from a compound represented by the following general formula [2] as a constituent unit, And (3) Copolymer containing a monomer unit derived from a compound represented by the following general formula [3] and a monomer unit derived from a compound having a hydroxyl group, a carboxyl group, a thiol group, or a thiocarboxyl group in the molecule as constituent units. The thing chosen from coalescence is mentioned.

（式中、Ｒ^１は、ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有する炭素数１〜１０のアルキル基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有する炭素数６〜１０のアリール基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有する炭素数７〜１２のアラルキル基；あるいはヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリ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；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有していてもよい炭素数１〜１０のアルキル基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有していてもよい炭素数６〜１０のアリール基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有していてもよい炭素数７〜１２のアラルキル基；あるいはヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリ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す。）

(Wherein R ¹ represents a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group, or a hydroxyboryl group. An alkyl group having 1 to 10 carbon atoms; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group, or hydroxyboryl A C6-C10 aryl group having a group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group, or A C7-12 aralkyl group having a hydroxyboryl group; 2 to 10 carbon atoms having a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group, or a hydroxyboryl group N, N-dialkylamino group, R ² , R ³ and R ⁴ are each independently a hydrogen atom; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary Or a secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group, which may have a C 1-10 alkyl group; a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or Secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene Or an aryl group having 6 to 10 carbon atoms which may have a hydroxyboryl group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo Group, ureylene group, thioureylene group or hydroxyboryl group optionally having 7 to 12 carbon atoms; or hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, 1 And represents an N, N-dialkylamino group having 2 to 10 carbon atoms which may have a secondary or secondary amide group, sulfo group, ureylene group, thioureylene group or hydroxyboryl group.)

（式中、Ｒ^５は、ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有する炭素数１〜１０のアルキル基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有する炭素数６〜１０のアリール基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有する炭素数７〜１２のアラルキル基；あるいはヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリ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^６、Ｒ^７及びＲ^８はそれぞれ独立して、水素原子；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有していてもよい炭素数１〜１０のアルキル基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有していてもよい炭素数６〜１０のアリール基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリル基を有していてもよい炭素数７〜１２のアラルキル基；ヒドロキシル基、カルボキシル基、チオール基、チオカルボキシル基、１級もしくは２級アミノ基、１級もしくは２級アミド基、スルホ基、ウレイレン基、チオウレイレン基又はヒドロキシボリ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；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；あるい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す。ただし、Ｒ^６、Ｒ^７及びＲ^８のいずれか１つは、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である。）

(Wherein R ⁵ represents a hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group or hydroxyboryl group. An alkyl group having 1 to 10 carbon atoms; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group, or hydroxyboryl A C6-C10 aryl group having a group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group, or A C7-12 aralkyl group having a hydroxyboryl group; 2 to 10 carbon atoms having a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group, or a hydroxyboryl group N, N-dialkylamino group, R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary Or a secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group, which may have a C 1-10 alkyl group; a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or Secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene Or an aryl group having 6 to 10 carbon atoms which may have a hydroxyboryl group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo Group, ureylene group, thioureylene group or hydroxyboryl group optionally having 7 to 12 carbon atoms; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary Or a secondary amide group, a sulfo group, a ureylene group, a thioureylene group, or a hydroxyboryl group, which may have a C 2-10 N, N-dialkylamino group; a C 1-10 alkyl having a vinyl group Group: aryl group having 6 to 10 carbon atoms having vinyl group; aralkyl group having 7 to 12 carbon atoms having vinyl group Or it represents a carbon number 2 to 10 of N, N-dialkylamino group having a vinyl group. However, any one of R ⁶ , R ⁷ and R ⁸ 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, and 7 carbon atoms having a vinyl group. It is a C2-C10 N, N-dialkylamino group having a -12 aralkyl group or a vinyl group. )

（式中、Ｒ^９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^１０、Ｒ^１１及びＲ^１２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 ⁹ represents 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 a vinyl group. Represents an N, N-dialkylamino group having 2 to 10 carbon atoms, and each of R ¹⁰ , R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms. Group, 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 represented by R ^{1 to} R ¹² in the general formulas [1] to [3] may be linear, branched or cyclic, specifically 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 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- Ptyl group, neoheptyl group, cycloheptyl group, n-octyl group, 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, n-decyl group, isodecyl group, s-decyl group, t-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group, menthyl group, adamantyl group, A decahydronaphthyl group etc. are mentioned. 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 represented by R ^{1 to} R ¹² in the general formulas [1] to [3] may be either monocyclic or condensed polycyclic, specifically, For example, a phenyl group, a naphthyl group, an azulenyl group and the like can be mentioned. Among them, an aryl group having 6 carbon atoms such as a phenyl group is preferable.

The aralkyl group having 7 to 12 carbon atoms represented by R ^{1 to} R ¹² in the general formulas [1] to [3] may be monocyclic or condensed polycyclic, specifically, Examples include benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, tetrahydronaphthyl group, naphthylmethyl group, naphthylethyl group, etc. However, 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 represented by R ^{1 to} R ¹² in the general formulas [1] to [3] 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-pentylamino group, N, N-dineopentylamino Group, N, N-di-2-methylbutylamino group, N, N-bis (1,2-dimethylpropyl) amino group, N, N-di- -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- Butylethylamino group, N, N-ethylpentylamino group, N, N-ethylhexylamino group, N, N-ethylheptylamino group, N, N-ethyloctylamino group, N, N-butylpropylamino group, N , N-pentylpropylamino group, N, N-hexylpropylamino group, N, N-heptylpropylamino group, N, N-butylpentylamino group, N, N-butylhexylamino Among them, for example, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N, N-diisopropylamino group, N, N-ethylmethyl Carbon such as amino group, N, N-methylpropylamino group, N, N-butylmethylamino group, N, N-methylpentylamino group, N, N-ethylpropylamino group, N, N-butylethylamino group, etc. A linear, branched or cyclic N, N-dialkylamino group having 2 to 6 carbon atoms 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 the general formula [1], when one of R ² , R ³ and R ⁴ is a hydrogen atom, the remaining two R are a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary group Or a secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group, which may have a C 1-10 alkyl group; a hydroxyl group, a carboxyl group, a thiol group , A thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group, an aryl group having 6 to 10 carbon atoms; hydroxyl Group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group An aralkyl group having 7 to 12 carbon atoms which may have a fo group, a ureylene group, a thioureylene group or a hydroxyboryl group; or a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, An N, N-dialkylamino group having 2 to 10 carbon atoms which may have a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group is preferred.

In the general formula [2], when one of R ⁶ , R ⁷ and R ⁸ is a hydrogen atom, the remaining two R are a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary Or a secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group, which may have a C 1-10 alkyl group; a hydroxyl group, a carboxyl group, a thiol group , A thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group, an aryl group having 6 to 10 carbon atoms; hydroxyl Group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group An aralkyl group having 7 to 12 carbon atoms which may have a fo group, a ureylene group, a thioureylene group or a hydroxyboryl group; a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, 1 N, N-dialkylamino group having 2 to 10 carbon atoms which may have a secondary or secondary amide group, sulfo group, ureylene group, thioureylene group or hydroxyboryl group; 1 to 10 carbon atoms having a vinyl group An alkyl 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 an N, N-dialkylamino group having 2 to 10 carbon atoms having a vinyl group is preferable.

In General Formula [2], one of R ⁶ , R ⁷ and R ⁸ 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, or a vinyl group. In the case of the aralkyl group having 7 to 12 carbon atoms or the N, N-dialkylamino group having 2 to 10 carbon atoms having a vinyl group, the remaining two R are other groups (carbon having a vinyl group). An alkyl group having 1 to 10 carbon atoms, 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, and an N, N-dialkylamino having 2 to 10 carbon atoms having a vinyl group A group other than a group), among which a hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene An alkyl group having 1 to 10 carbon atoms which may have a thioureylene group or a hydroxyboryl group; a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide Aryl group having 6 to 10 carbon atoms which may have a group, sulfo group, ureylene group, thioureylene group or hydroxyboryl group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group A primary or secondary amide group, sulfo group, ureylene group, thioureylene group or hydroxyboryl group optionally having 7 to 12 carbon atoms; or hydroxyl group, carboxyl group, thiol group, thiocarboxyl group Primary or secondary amino group, primary or secondary amide group, sulfo Group, ureylene group, thioureylene group or a hydroxy boryl group and has optionally also good number from 2 to 10 carbon N, N-dialkylamino group is more preferable.

In General Formula [3], when one of R ¹⁰ , R ^11, and R ¹² is a hydrogen atom, the remaining two R's are an alkyl group having 1 to 10 carbon atoms and a carbon atom having 6 to 10 carbon atoms. An aryl group, an aralkyl group having 7 to 12 carbon atoms, or an N, N-dialkylamino group having 2 to 10 carbon atoms is preferable.

In R ^{1 to} R ⁸ in the general formulas [1] and [2], a hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group bonded to an alkyl group , Sulfo group, ureylene group, thioureylene group or hydroxyboryl group may be bonded to the carbon atom at the terminal of the alkyl group, or bonded to the carbon atom so as to be branched from the carbon atom in the chain of the alkyl group. You may do it. Moreover, the number of these groups is 1-5 normally, Preferably it is 1-3, More preferably, it is one. In addition, the carbon atom which comprises these groups shall not be included in the number of carbon atoms (C1-C10) which comprises the alkyl group to which it couple | bonds.

In R ^{1 to} R ⁸ in the general formulas [1] and [2], a hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group bonded to an aryl group , Sulfo group, ureylene group, thioureylene group or hydroxyboryl 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 these groups 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 bonding position of these groups is in the ortho-position relative to the bond with the phosphorus atom (phosphorus cation) bonded to the phenyl group is preferable. Moreover, the number of these groups is 1-5 normally, Preferably it is 1-3, More preferably, it is one. The carbon atoms constituting these groups are not included in the number of carbon atoms (6 to 10 carbon atoms) constituting the aryl group to which they are bonded.

In R ^{1 to} R ⁸ in the general formulas [1] and [2], a hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group bonded to an aralkyl group , Sulfo group, ureylene group, thioureylene group or hydroxyboryl group may be bonded to any carbon atom of the aryl group (phenyl group or naphthyl group) constituting the aralkyl group. For example, when the aryl group constituting the aralkyl group is a phenyl group, the bonding position of these groups is any of the ortho position, the meta position, and the para position with respect to the bond with the alkyl group bonded to the phenyl group. Of these, a phenyl group in which the bonding position of these groups is in the ortho-position relative to the bond with the alkyl group bonded to the phenyl group is preferable. Moreover, the number of these groups is 1-5 normally, Preferably it is 1-3, More preferably, it is one. Note that the carbon atoms constituting these groups are not included in the number of carbon atoms (7 to 12 carbon atoms) constituting the aralkyl group to which they are bonded.

When R ^{6 to} R ⁹ in the general formulas [2] and [3] are a C 1-10 alkyl group having a vinyl group, the vinyl group is bonded to the terminal carbon atom of the alkyl group. Alternatively, it may be bonded to the carbon atom so as to be branched from the carbon atom in the chain of the alkyl group. 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 ^{6 to} R ⁹ in the general formulas [2] and [3] are aryl groups having 6 to 10 carbon atoms having a vinyl group, the vinyl group is any carbon atom of the aromatic ring constituting the aryl group May be bonded to. 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 ^{6 to} R ⁹ in the general formulas [2] and [3] are a C 7-12 aralkyl group having a vinyl group, the vinyl group is an aryl group (phenyl group or naphthyl) constituting the aralkyl group. It may be bonded to any carbon atom of the group). 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) a compound represented by the general formula [1] include (1 ′) a compound represented by the following general formula [1 ′].

（式中、Ｒ^１'は、ヒドロキシル基を有する炭素数７〜１２のアラルキル基を表し、Ｒ^２'、Ｒ^３'及びＲ^４'はそれぞれ独立して、ヒドロキシル基を有していてもよい炭素数１〜１０のアルキル基、ヒドロキシル基を有していてもよい炭素数６〜１０のアリール基又はヒドロキシル基を有していてもよい炭素数７〜１２のアラルキル基を表す。）

(In the formula, R ^{1 ′} represents a C 7-12 aralkyl group having a hydroxyl group, and R ^{2 ′} , R ^{3 ′} and R ^{4 ′} may each independently have a hydroxyl group. This represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 12 carbon atoms which may have a hydroxyl group.

The alkyl group having 1 to 10 carbon atoms represented by R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the general formula [1 ′] is represented by R ^{1 to} R ¹² in the general formulas [1] to [3]. The same thing as a C1-C10 alkyl group is mentioned, Especially, a C2-C6 linear, branched or cyclic alkyl group is preferable.

The aryl group having 6 to 10 carbon atoms represented by R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the general formula [1 ′] is represented by R ^{1 to} R ¹² in the general formulas [1] to [3]. The same thing as a C6-C10 aryl group is mentioned, A preferable aryl group is 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 to} R in the general formulas [1] to [3]. It includes the same aralkyl group having 7 to 12 carbon atoms represented by ¹² include those preferred aralkyl group similar.

The hydroxyl group represented by R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} in the general formula [1 ′] is bonded to any carbon atom of the alkyl group, aryl group or aralkyl group to which the hydroxyl group is bonded. It may be. Specifically, when a hydroxyl group is bonded to an alkyl group, the hydroxyl group may be bonded to a carbon atom at the terminal of the alkyl group, or may be branched from a carbon atom in the chain of the alkyl group. May be bonded to the carbon atom. Further, when a hydroxyl group is bonded to an aryl group, the hydroxyl group may be bonded to any carbon atom of an aromatic ring constituting the aryl group. For example, when the aryl group is a phenyl group, The bonding position of the hydroxyl group may be ortho, meta, or para with respect to the bond with the phosphorus atom (phosphorus cation) bonded to the phenyl group. Among them, the bonding position of the hydroxyl group is A phenyl group having a positional relationship in the ortho position with respect to a bond with a phosphorus atom (phosphorus cation) bonded to the phenyl group is preferable. Furthermore, when a hydroxyl group is bonded to an aralkyl group, the hydroxyl group may be bonded to any carbon atom of an aryl group (phenyl group or naphthyl group) constituting the aralkyl group. For example, when the aryl group constituting the aralkyl group is a phenyl group, the bonding position of the hydroxyl group may be any of the ortho position, the meta position, and the para position with respect to the bond with the alkyl group bonded to the phenyl group. Of these, a phenyl group in which the bonding position of the hydroxyl group is in the ortho-position relative to the bond with the alkyl group bonded to the phenyl group is preferable. Moreover, the number of hydroxyl groups is 1-5 normally, Preferably it is 1-3, More preferably, it is one.

In the general formula [1 ′], R ^{2 ′} , R ^{3 ′} and R ^{4 ′} are an alkyl group having 1 to 10 carbon atoms having no hydroxyl group, and an aryl group having 6 to 10 carbon atoms having no hydroxyl group. And a C 7-12 aralkyl group having a hydroxyl group.

  More preferable specific examples of the compound represented by (1 ′) the general formula [1 ′] include (1 ″) a compound represented by the general formula [1 ″].

（式中、Ｒ^１''は、２-ヒドロキシルベンジル基を表し、Ｒ^２''は、２-ヒドロキシルベンジル基、炭素数２〜６のアルキル基又はフェニル基を表し、Ｒ^３''及びＲ^４''はそれぞれ独立して、炭素数２〜６のアルキル基又はフェニル基を表す。）

Wherein R ^{1 ″} represents a 2-hydroxylbenzyl group, R ^{2 ″} represents a ² -hydroxylbenzyl group, an alkyl group having 2 to 6 carbon atoms, or a phenyl group, and R ^{3 ″} and R ^{3 4 ″} each independently represents an alkyl group having 2 to 6 carbon atoms or a phenyl group.)

The alkyl group having 2 to 6 carbon atoms represented by R ^{2 ″} , R ^{3 ″} and R ⁴ ″ in the general formula [1 ″] may be linear, branched or cyclic. Specifically, for example, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, s -Pentyl, t-pentyl, neopentyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, cyclopentyl, n-hexyl, isohexyl, s-hexyl, t-hexyl Group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group and the like. In the specific examples described above, n- represents a normal isomer, s- represents a sec isomer, and t- represents a tert isomer.

  Specific examples of the compound represented by the general formula [1 ′] and the compound represented by the general formula [1 ″] include those represented by the formulas (1-1) to (1-5). 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.

  These compounds represented by the general formula [1], the compound represented by the general formula [1 ′], and the compound represented by the general formula [1 ″] (phosphonium salt according to the present invention) are commercially available. Alternatively, those appropriately synthesized by a general method performed in this field may be used. Among them, in particular, the compounds represented by the above formulas (1-1) to (1-3) are obtained by reacting, for example, commercially available triphenylphosphine with hydroiodic acid to obtain a triphenylphosphine hydroiodide salt. What is necessary is just to synthesize | combine by making 2-, 3- or 4-hydroxybenzyl alcohol react. In addition, the compound represented by the above formula (1-4) is obtained by reacting, for example, commercially available tri-n-butylphosphine with hydroiodic acid to obtain a tri-n-butylphosphine hydroiodide salt. What is necessary is just to synthesize | combine by making hydroxybenzyl alcohol react. Furthermore, the compound represented by the above formula (1-5) may be synthesized, for example, by reacting commercially available diphenylphosphine hydrogen iodide with 2-hydroxybenzyl alcohol.

  As described above, the phosphonium salt according to the present invention includes not only (1) a monomer such as a compound represented by the general formula [1] but also (2) a compound represented by the general formula [2]. A polymer containing a monomer unit as a constituent unit, or (3) a compound having a hydroxyl group, a carboxyl group, a thiol group or a thiocarboxyl group in the molecule and a monomer unit derived from a compound represented by the general formula [3] It may be a copolymer contained as a derived structural unit. 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 and a hydrogen atom capable of hydrogen bonding to the oxygen atom of the epoxide, A polymer (polymer) can also be used as the phosphonium salt according to the present invention.

  (2) As a polymer containing a monomer unit derived from the compound represented by the general formula [2] as a constituent unit, a homopolymer comprising a monomer unit derived from the compound represented by the general formula [2] (homopolymer) Or a copolymer (heteropolymer) comprising a monomer unit derived from the compound represented by the general formula [2] and a monomer unit derived from a vinyl monomer other than the compound represented by the general formula [2]. It may be.

  When the phosphonium salt according to the present invention is a polymer containing, as a constituent unit, a monomer unit derived from the compound represented by (2) the general formula [2], the compound (derived from the monomer unit constituting the polymer). Preferable specific examples of the compound) include those represented by the following general formula [2 ′].

（式中、Ｒ^５'は、ヒドロキシル基又はチオウレイレン基を有する炭素数７〜１２のアラルキル基を表し、Ｒ^６'は、ビニル基を有する炭素数６〜１０のアリール基を表し、Ｒ^７'及びＲ^８'はそれぞれ独立して、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基又は炭素数７〜１２のアラルキル基を表す。）

(In the formula, R ^{5 ′} represents a C 7-12 aralkyl group having a hydroxyl group or a thioureylene group, R ^{6 ′} represents a C 6-10 aryl group having a vinyl group, and R ^{7 ′.} And R ^{8 ′} each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{7 ′} and R ^{8 ′} in the general formula [2 ′] include 1 to C carbon atoms represented by R ^{1 to} R ¹² in the general formulas [1] to [3]. The same thing as the 10 alkyl group is mentioned.

The aryl group having 6 to 10 carbon atoms represented by R ^{6 ′} , R ^{7 ′} and R ^{8 ′} in the general formula [2 ′] is represented by R ^{1 to} R ¹² in the general formulas [1] to [3]. The same thing as a C6-C10 aryl group is mentioned, A preferable aryl group is also the same.

The aralkyl group having 7 to 12 carbon atoms represented by R ^{5 ′} , R ^{7 ′} and R ^{8 ′} in the general formula [2 ′] is represented by R ^{1 to} R ¹² in the general formulas [1] to [3]. The same thing as a C7-C12 aralkyl group is mentioned, A preferable aralkyl group is also the same.

The hydroxyl group or thioureylene group represented by R ^{5 ′} in the general formula [2 ′] may be bonded to any carbon atom of the aralkyl group to which the hydroxyl group or thioureylene group is bonded. Specifically, when a hydroxyl group or thioureylene group is bonded to an aralkyl group, the hydroxyl group or thioureylene group is bonded to any carbon atom of an aryl group (phenyl group or naphthyl group) constituting the aralkyl group. It may be. For example, when the aryl group constituting the aralkyl group is a phenyl group, the bonding position of the hydroxyl group or thioureylene group is the ortho position, meta position, para position with respect to the bond with the alkyl group bonded to the phenyl group. In particular, a phenyl group in which the bonding position of the hydroxyl group or thioureylene group is in a para-position relative to the bond with the alkyl group bonded to the phenyl group is preferable. Moreover, the number of a hydroxyl group or a thioureylene group is 1-5 normally, Preferably it is 1-3, More preferably, it is one. In addition, the carbon atom which comprises the group containing a thioureylene group shall not be contained in the number of carbon atoms (7-12 carbon atoms) which comprises the aralkyl group to which it couple | bonds.

The bonding position of the vinyl group in the aryl group having 6 to 10 carbon atoms having the vinyl group represented by R ^{6 ′} in the general formula [2 ′] is as follows: R ^{6 to} R ⁹ in the general formulas [2] and [3] Examples similar to the bonding position of the vinyl group in the case of an aryl group having 6 to 10 carbon atoms having a vinyl group are given. 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 ^{6 to} R ⁹ in the general formulas [2] and [3].

In General Formula [2 ′], R ^{7 ′} and R ^{8 ′} are preferably selected from aryl groups having 6 to 10 carbon atoms.

  More preferred specific examples of the compound represented by the general formula [2 ′] include, for example, a compound represented by the general formula [2 ″].

（式中、Ｒ^５''は、２-ヒドロキシルベンジル基又は３，５-ジトリフルオロメチルフェニルチオウレイレニルプロピル基を表し、Ｒ^６''は、４-ビニルフェニル基を表し、Ｒ^７''及びＲ^８''は、フェニル基を表す。）

(Wherein R ^{5 ″} represents a 2-hydroxylbenzyl group or 3,5-ditrifluoromethylphenylthioureylenylpropyl group, R ^{6 ″} represents a 4-vinylphenyl group, R ^{7 ′ 'And} R ^8'' represent a phenyl group.)

  The vinyl monomer other than the compound represented by the general formula [2] 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 [2]. 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.

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

  In the polymer containing a monomer unit derived from the compound represented by the general formula [2] as a constituent unit, a monomer unit derived from the compound represented by the general formula [2] and a compound other than the compound represented by the general formula [2] The polymerization ratio of the monomer unit derived from the vinyl monomer is not particularly limited as long as the polymer functions as a phosphonium salt. For example, the monomer unit derived from the compound represented by the general formula [2]: General formula Monomer units derived from vinyl monomers other than the compound represented by [2] = 10: 0.1 to 1:10.

  (3) As a copolymer containing a monomer unit derived from the compound represented by the general formula [3] and a monomer unit derived from a compound having a hydroxyl group, a carboxyl group, a thiol group or a thiocarboxyl group in the molecule as constituent units If these include monomer units derived from the compound represented by the general formula [3] and monomer units derived from compounds having a hydroxyl group, a carboxyl group, a thiol group or a thiocarboxyl group in the molecule, these monomers A monomer unit other than the unit may be included.

  The phosphonium salt according to the present invention comprises (3) a monomer unit derived from a compound represented by the general formula [3] and a monomer unit derived from a compound having a hydroxyl group, carboxyl group, thiol group or thiocarboxyl group in the molecule. As a preferred specific example of the compound represented by the general formula [3] (a compound derived from the monomer unit constituting the polymer) in the case of a copolymer contained as a structural unit, for example, the following general formula [3 ′] The thing shown by is mentioned.

（式中、Ｒ^９'は、ビニル基を有する炭素数６〜１０のアリール基を表し、Ｒ^１０'、Ｒ^１１'及びＲ^１２'はそれぞれ独立して、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基又は炭素数７〜１２のアラルキル基を表す。）

(Wherein R ^{9 ′} represents an aryl group having 6 to 10 carbon atoms having a vinyl group, and R ^{10 ′} , R ^{11 ′} and R ^{12 ′} are each independently an alkyl group having 1 to 10 carbon atoms, Represents an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 12 carbon atoms.)

The alkyl group having 1 to 10 carbon atoms represented by R ^{10 ′} , R ^{11 ′} and R ^{12 ′} in the general formula [3 ′] is represented by R ^{1 to} R ¹² in the general formulas [1] to [3]. The same thing as a C1-C10 alkyl group is mentioned, Especially, a C1-C4 linear, branched or cyclic alkyl group is preferable.

Examples of the aryl group having 6 to 10 carbon atoms represented by R ^{9 ′} , R ^{10 ′} , R ^{11 ′} and R ^{12 ′} in the general formula [3 ′] include R ^{1 to} R in the general formulas [1] to [3]. The same thing as the C6-C10 aryl group shown by ¹² is mentioned, A preferable aryl group is also the same.

The aralkyl group having 7 to 12 carbon atoms represented by R ^{10 ′} , R ^{11 ′} and R ^{12 ′} in the general formula [3 ′] is represented by R ^{1 to} R ¹² in the general formulas [1] to [3]. The same thing as a C7-C12 aralkyl group is mentioned, A preferable aralkyl group is also the same.

The bonding position of the vinyl group in the aryl group having 6 to 10 carbon atoms having the vinyl group represented by R ^{9 ′} in the general formula [3 ′] is such that R ^{6 to} R ⁹ in the general formulas [2] and [3] are Examples similar to the bonding position of the vinyl group in the case of an aryl group having 6 to 10 carbon atoms having a vinyl group are given. 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 ^{6 to} R ⁹ in the general formulas [2] and [3].

In the general formula [3 ′], R ^{10 ′} is preferably selected from an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and among them, an alkyl group having 1 to 10 carbon atoms. More preferably, is selected.

In the general formula [3 ′], R ^{11 ′} and R ^{12 ′} are preferably selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms. More preferably, 10 aryl groups are selected.

  More preferable specific examples of the compound represented by the general formula [3 ′] include, for example, a compound represented by the general formula [3 ″].

（式中、Ｒ^９''は、４-ビニルフェニル基を表し、Ｒ^１０''は、炭素数１〜４のアルキル基を表し、Ｒ^１１''及びＲ^１２''は、フェニル基を表す。）

(Wherein R ^{9 ″} represents a 4-vinylphenyl group, R ^{10 ″} represents an alkyl group having 1 to 4 carbon atoms, and R ^{11 ″} and R ^{12 ″} represent a phenyl group. .)

The alkyl group having 1 to 4 carbon atoms represented by R ¹⁰ ″ in the general formula [3 ″] may be linear, branched or cyclic, and specifically includes, for example, methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group and the like. In the specific examples described above, n- represents a normal isomer, s- represents a sec isomer, and t- represents a tert isomer.

  Specific examples of the compound represented by the general formula [3 ′] (the compound derived from the monomer unit constituting the polymer) include those represented by the formulas (3-1) to (3-4), Of these, the compound represented by the formula (3-1) 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 compound having a hydroxyl group, carboxyl group, thiol group or thiocarboxyl group in the molecule has a vinyl group polymerizable with the vinyl group in the compound represented by the general formula [3] in the molecule, and the hydroxyl group. As long as it is a compound having at least one carboxyl group, thiol group or thiocarboxyl group, there is no particular limitation. Specific examples of the compound include a compound having a hydroxyl group in a molecule such as a hydroxystyrene derivative such as 2-hydroxystyrene, 3-hydroxystyrene, and 4-hydroxystyrene, for example, a molecule such as (meth) acrylic acid. Compounds having a carboxyl group, such as mercaptostyrene derivatives such as 2-mercaptostyrene, 3-mercaptostyrene, 4-mercaptostyrene, etc. Compounds having a thiol group in the molecule, such as (meth) thioacrylic acid Examples include compounds having a carboxyl group, and among them, compounds having a hydroxyl group in the molecule such as hydroxystyrene derivatives such as 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, etc. are preferable. For example, 2-hydroxystyrene, 3 Hydroxystyrene derivatives such as -hydroxystyrene and 4-hydroxystyrene are more preferable, and 4-hydroxystyrene is particularly preferable among them. In addition, (meth) acrylic acid in the above-mentioned specific examples means acrylic acid or methacrylic acid.

  As the monomer unit other than the monomer unit derived from the compound represented by the general formula [3] and the monomer unit derived from the compound having a hydroxyl group, a carboxyl group, a thiol group or a thiocarboxyl group in the molecule, the general formula [2 ] The monomer unit similar to the monomer unit derived from vinyl monomers other than the compound shown by these is mentioned, A preferable monomer unit also includes the monomer unit derived from the same vinyl monomer.

  As a specific example of a copolymer containing a monomer unit derived from the compound represented by the general formula [3] and a monomer unit derived from a compound having a hydroxyl group, a carboxyl group, a thiol group, or a thiocarboxyl group in the molecule as constituent units Examples include 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.

  Weight average molecular weight of a copolymer comprising a monomer unit derived from the compound represented by the general formula [3] and a monomer unit derived from a compound having a hydroxyl group, carboxyl group, thiol group or thiocarboxyl group in the molecule as a constituent unit As long as the said polymer is in the range which functions as a phosphonium salt, it will not restrict | limit, For example, it is usually 2,000-50,000, Preferably it is 3,000-30,000.

  In a copolymer containing a monomer unit derived from the compound represented by the general formula [3] and a monomer unit derived from a compound having a hydroxyl group, carboxyl group, thiol group or thiocarboxyl group in the molecule as a constituent unit, As a polymerization ratio of the monomer unit derived from the compound represented by [3] and the monomer unit derived from the compound having a hydroxyl group, a carboxyl group, a thiol group, or a thiocarboxyl group in the molecule, the polymer is a phosphonium salt. The monomer unit is not particularly limited as long as it is within a functioning range. For example, a monomer unit derived from a compound represented by the general formula [3]: a monomer derived from a compound having a hydroxyl group, a carboxyl group, a thiol group, or a thiocarboxyl group in the molecule Unit = 10: 1 to 1:10. For example, taking the formula (A) as an example, x and y in the formula (A) are x: y = 10: 1 to 1:10.

  The compound represented by the above general formulas [2] and [3] (a compound derived from the monomer unit constituting the polymer) may be present as a monomer unit in the polymer, and the polymer is not necessarily synthesized. It is not necessary to be a raw material. That is, the compounds represented by the general formulas [2] and [3] may be polymerized to form a polymer, or a tertiary phosphine that is a precursor of the compound is polymerized and then a quaternary phosphonium with an iodide. A polymer may be synthesized by chlorination. As a more specific method for synthesizing a polymer, for example, a commercially available tertiary phosphine having a vinyl group such as diphenyl (4-vinylphenyl) phosphine and a hydroxystyrene derivative such as 4-hydroxystyrene are copolymerized. For example, there is a method of reacting an iodide such as hydroiodic acid, methyl iodide, benzyl iodide or the like to form 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 hydroxyl group, a carboxyl group, a thiol group, or a thiocarboxyl group is contained in the monomer unit derived from the compound represented by the general formula [1] and the compound represented by the general formula [3]. A copolymer containing a monomer unit derived from the compound as a constituent unit is preferred, and among them, the monomer unit derived from the compound represented by the general formula [3] and the hydroxyl group, carboxyl group, thiol group or thiol in the molecule A copolymer containing a monomer unit derived from a compound having a carboxyl group as a constituent unit is more preferred. 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.

  In the phosphonium salt according to the present invention, the phosphorus atom (phosphorus cation) and the hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide are represented by mol of phosphorus atom (phosphorus cation) in the phosphonium salt according to the present invention. The number of hydrogen atoms is usually 1 to 30 times that of the number, and it is particularly preferable that the number of hydrogen atoms is 10 to 15 times that of the hydrogen atom. The phosphonium salt in which hydrogen atoms capable of hydrogen bonding with oxygen atoms of the epoxide are usually present in an amount of 1 to 30 times mol, preferably 10 to 15 times mol of the number of mols of phosphorus atoms (phosphorus cations) in the phosphonium salt { When the compound (monomer) or polymer} is used, the yield of the product cyclic carbonate tends to increase.

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

  There are no particular restrictions on the order of charging the raw material epoxide (oxirane) and carbon dioxide, and the phosphonium salt according to the present invention, which acts as a catalyst, into the reaction system. For example, there may be mentioned a method in which epoxide (oxirane) and the phosphonium salt according to the present invention are sequentially charged into the reaction system, and carbon dioxide gas is blown into the reaction system into which these are charged.

  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 epoxide (oxirane) as a raw material and the cyclic carbonate as a product also serve as a solvent, such an organic solvent 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 includes the epoxide (oxirane), the kind of the phosphonium salt according to the present invention, the amount of carbon dioxide used for the epoxide (oxirane), the amount of the phosphonium salt according to the present invention for the epoxide (oxirane), The presence or absence of the organic solvent, its type and amount used, reaction temperature, and pressure during the reaction may be affected. 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, after distilling off the organic solvent in the reaction system, the resulting residue is subjected to recrystallization, distillation, column chromatography, etc. It can be isolated. 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 (2-hydroxybenzyl) triphenylphosphonium iodide [Formula (1-1)] Dry acetonitrile of 390 mg (1 mmol) of triphenylphosphine hydrogen iodide and 130 mg (1.05 mmol) of 2-hydroxybenzyl alcohol The 10 mL solution was stirred at 90 ° 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 give (2-hydroxybenzyl) triphenylphosphonium iodide as a pale yellow solid. 468 mg (yield 94%) was obtained. The structure of (2-hydroxybenzyl) triphenylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 4.91 (d, 2H, J = 14.8 Hz, PC H ₂ ), 6.63 (t, 1H, J = 7) .6 Hz, Ar H ), 6.72 (d, 1 H, J = 7.6 Hz, Ar H ), 6.85 (dt, 1 H, J = 7.6, 2.0 Hz, Ar H ), 7.12 (tt, 1H, J = 7.6,2.0Hz , Ar H), 7.63-7.76 (m, 12H, ArH), 7.87-7.92 (m, 3H, Ar H), 9.76 (s, 1H, O H ).
¹³ C-NHR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 23.22 (d, J = 48.6 Hz, P C H ₂ ), 113.66 (d, J = 7.6 Hz, Ar ), 115.34 (d, J = 2.0 Hz, Ar ), 118.29 (d, J = 84.8 Hz, Ar ), 119.08 (d, J = 2.0 Hz, Ar ), 129. 91 (d, J = 12.4 Hz, Ar ), 131.52 (d, J = 4.8 Hz, Ar ), 133.86 (d, J = 9.5 Hz, Ar ), 134.88 (d, J = 1.9 Hz, Ar ), 155.98 (d, J = 5.8 Hz, Ar ).

Synthesis Example 2 Synthesis of (3-hydroxybenzyl) triphenylphosphonium iodide [Formula (1-2)] Dry acetonitrile of 390 mg (1 mmol) of triphenylphosphine hydrogen iodide salt and 130 mg (1.05 mmol) of 3-hydroxybenzyl alcohol The 10 mL solution was stirred at 90 ° 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 (3-hydroxybenzyl) triphenylphosphonium iodide as a light gray powder. 471 mg (yield 95%) was obtained. The structure of (3-hydroxybenzyl) triphenylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 5.08 (d, 2H, J = 15.6 Hz, PC H ₂ ), 6.39 (d, 1H, J = 7) .2Hz, Ar H), 6.43 ( q, 1H, J = 2.0Hz, Ar H), 6.69 (dt, 1H, J = 7.2,2.0Hz, Ar H), 7.02 (T, 1H, J = 7.6 Hz, Ar H ), 7.63-7.71 (m, 6H, Ar H ), 7.75 (ddd, 6H, J = 8.0, 8.0, 3 .6 Hz, Ar H ), 7.88-7.94 (m, 3 H, Ar H ), 9.52 (s, 1 H, O H ).
¹³ C-NHR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 28.13 (d, J = 46.8 Hz, P C H ₂ ), 115.27 (d, J = 3.0 Hz, Ar ), 117.76 (d, J = 5.7 Hz, Ar ), 117.89 (d, J = 84.9 Hz, Ar ), 121.33 (d, J = 5.7 Hz, Ar ), 128. 96 (d, J = 8.6 Hz, Ar ), 129.69 (d, J = 3.0 Hz, Ar ), 130.03 (d, J = 12.4 Hz, Ar ), 133.95 (d, J = 9.5 Hz, Ar ), 135.03 (d, J = 1.9 Hz, Ar ), 157.46 (d, J = 2.8 Hz, Ar ).

Synthesis Example 3 Synthesis of (4-hydroxybenzyl) triphenylphosphonium iodide [Formula (1-3)] Dry acetonitrile of 390 mg (1 mmol) of triphenylphosphine hydrogen iodide salt and 130 mg (1.05 mmol) of 4-hydroxybenzyl alcohol The 10 mL solution was stirred at 90 ° 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 give (4-hydroxybenzyl) triphenylphosphonium iodide as a white solid. 479 mg (yield 97%) was obtained. The structure of (4-hydroxybenzyl) triphenylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 5.07 (d, 2H, J = 15.2 Hz, PC H ₂ ), 6.62 (d, 2H, J = 8) .4 Hz, Ar H ), 6.79 (dd, 2 H, J = 8.8, 2.8 Hz, Ar H ), 7.64-7.72 (m, 6 H , Ar H ), 7.75 (ddd , 6H, J = 8.0,8.0,4.0Hz, Ar H), 7.89-7.95 (m, 3H, Ar H), 9.62 (s, 1H, O H).
¹³ C-NHR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 27.57 (d, J = 46.7 Hz, P C H ₂ ), 115.55 (d, J = 1.8 Hz, Ar ), 117.02 (d, J = 8.6 Hz, Ar ), 117.95 (d, J = 83.9 Hz, Ar ), 130.01 (d, J = 12.4 Hz, Ar ), 131. 97 (d, J = 4.8 Hz, Ar ), 133.99 (d, J = 9.5 Hz, Ar ), 134.95 (d, J = 2.0 Hz, Ar ), 157.34 (d, J = 2.9 Hz, Ar ).

Synthesis Example 4 Synthesis of diphenylphosphine hydrogen iodide salt A solution of diphenylphosphine 745 mg (4 mmol) in dioxane 8 mL was stirred at room temperature, 55% hydroiodic acid 1 mL (ca. 7.3 mmol) was added to the solution, Stir 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 1.14 g of diphenylphosphine hydrogen iodide salt as a pale yellow solid ( Yield 91%) was obtained. The structure of diphenylphosphine hydrogen iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 6.18 (brs, 2H, P H ₂ ), 7.44-7.56 (m, 6H, Ar H ), 7 70-7.77 (m, 4H, Ar H ).
¹³ C-NHR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 128.45 (d, J = 12.4 Hz, Ar ), 130.91 (d, J = 10.5 Hz, Ar ), 131.48 (d, J = 2.8 Hz, Ar ), 134.90 (d, J = 134 Hz, Ar ).

Synthesis Example 5 Synthesis of bis (2-hydroxybenzyl) diphenylphosphonium iodide [formula (1-5)] 314 mg (1 mmol) of diphenylphosphine hydrogen iodide obtained in Synthesis Example 4 and 497 mg (4 mmol) of 2-hydroxybenzyl alcohol ) Was stirred at 90 ° C. for 24 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 12 hours to give white powder of bis (2-hydroxybenzyl) diphenylphosphonium. 525 mg (> 99% yield) of iodide was obtained. The structure of bis (2-hydroxybenzyl) diphenylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 4.44 (d, 4H, J = 14.4 Hz, PC H ₂ ), 6.60 (t, 2H, J = 7) .6 Hz, Ar H ), 6.72 (d, 2 H, J = 8.0 Hz, Ar H ), 6.82 (dt, 2 H, J = 7.6, 2.0 Hz, Ar H ), 7.06 (Tt, 2H, J = 7.6, 2.0 Hz, Ar H ), 7.54-7.69 (m, 8H, Ar H ), 7.75-7.81 (m, 2H, Ar H ) , 9.93 (s, 2H, O H).
¹³ C-NHR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 23.22 (d, J = 45.8 Hz, P C H ₂ ), 114.34 (d, J = 8.6 Hz, Ar ), 115.21 (d, J = 2.9 Hz, Ar ), 117.95 (d, J = 81.9 Hz, Ar ), 119.05 (d, J = 2.9 Hz, Ar ), 129. 06 (d, J = 11.4 Hz, Ar ), 129.44 (d, J = 2.8 Hz, Ar ), 131.47 (d, J = 4.7 Hz, Ar ), 133.69 (d, J = 9.6 Hz, Ar ), 134.38 (d, J = 2.8 Hz, Ar ), 155.48 (d, J = 4.7 Hz, Ar ).

Synthesis Example 6 Synthesis of (2-hydroxybenzyl) tri-n-butylphosphonium iodide [formula (1-4)] 1.32 g (4 mmol) of tri-n-butylphosphine hydrogen iodide salt and 521 mg of 2-hydroxybenzyl alcohol A solution of (4.2 mmol) in 40 mL of dry acetonitrile was stirred at 90 ° C. 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 give (2-hydroxybenzyl) tri-n as a white solid. 1.72 g (99% yield) of butylphosphonium iodide was obtained. The structure of (2-hydroxybenzyl) tri-n-butylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 0.88 (t, 9H, J = 7.2 Hz, C H ₃ ), 1.31-1.49 (m, 12H) _{, C H 2 C H 2 CH} 3), 2.10-2.20 (m, 6H, PC H 2 CH 2), 3.64 (d, 2H, J = 15.2Hz, PC H 2), 6 .84 (t, 1H, J = 7.6 Hz, Ar H ), 6.91 (d, 1H, J = 8.0 Hz, Ar H ), 7.19 (tt, 1H, J = 7.6, 2 0.0 Hz, Ar H ), 7.26 (dt, 1 H, J = 7.6, 2.0 Hz, Ar H ), 10.11 (s, 1 H, O H ).
¹³ C—NHR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 13.19 ( C H ₃ ), 17.89 (d, J = 45.7 Hz, P C H ₂ CH ₂ ), 20 .50 (d, J = 46.7 Hz, P C H ₂ Ar), 22.53 (d, J = 3.9 Hz, C H ₂ CH ₃ ), 23.36 (d, J = 15.2 Hz, PCH ₂ C H ₂ ), 115.35 (d, J = 5.7 Hz, Ar ), 115.41 ( Ar ), 119.55 (d, J = 2.7 Hz, Ar ), 129.42 (d, J = 2.9 Hz, Ar ), 131.55 (d, J = 4.7 Hz, Ar ), 155.44 (d, J = 3.9 Hz, Ar ).

Synthesis Example 7 Synthesis of poly [(4-t-butoxystyrene)-(4-vinyltriphenylphosphine)] copolymer (P-1A) using 1 equivalent of 4-t-butoxystyrene 4-vinyltriphenylphosphine 721 mg (2.5 mmol), 4-t-butoxystyrene 441 mg (2.5 mmol) and 2,2′-azobis (isobutyronitrile) (AIBN) 25 mg (0.15 mmol) were dissolved in 10 mL of dry toluene. The mixture was stirred at 80 ° C. for 48 hours after the second freeze degassing. After completion of the reaction, the solution was concentrated to about 1/3, 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 a white powder of poly [(4-t-butoxystyrene)-(4-vinyltriphenylphosphine)] copolymer (P-1A) 1 0.09 g (94% yield) was obtained. 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): 0.89-2.52 (m, 6H, C H ₂ C H ), 1.13-1.38 (brs, 9H) , C (C H ₃ ) ₃ ), 6.23-7.84 (m, 19H, Ar H ).
x (4-vinyltriphenylphosphine): y (4-t-butoxystyrene) = 1: 0.95.
GPC (DMF, 40 ° C.): M _n = 5,250, M _w / M _n = 2.12.

Synthesis Example 8 Synthesis of poly [(4-t-butoxystyrene)-(4-vinyltriphenylphosphine)] copolymer (P-2A) using 5 equivalents of 4-t-butoxystyrene 4-vinyltriphenylphosphine 1.44 g (5 mmol), 4.41 g (25 mmol) of 4-t-butoxystyrene and 148 mg (0.9 mmol) of 2,2′-azobis (isobutyronitrile) (AIBN) were dissolved in 60 mL of dry toluene. The mixture was stirred at 80 ° C. for 48 hours after the second freeze degassing. After completion of the reaction, the solution was concentrated to about 1/3, and then reprecipitated with 300 mL of methanol. The residue was washed with methanol and then vacuum-dried at 40 ° C. for 12 hours to obtain a white powder of poly [(4-t-butoxystyrene)-(4-vinyltriphenylphosphine)] copolymer (P-2A) 4 0.22 g (72% yield) was obtained. 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): 0.43-2.31 (m, 63H, C H ₂ C H , C (C H ₃ ) ₃ ), 6.12 -7.73 (m, 34.6H, Ar H ).
x (4-vinyltriphenylphosphine): y (4-t-butoxystyrene) = 1: 4.8.
GPC (DMF, 40 ° C.): M _n = 4,840, M _w / M _n = 1.96.

Synthesis Example 9 Synthesis of poly [(4-hydroxystyrene)-(4-vinyltriphenylphosphine)] copolymer (P-1B) Poly [(4-t-butoxystyrene)-( 4-vinyltriphenylphosphine)] copolymer (P-1A) 684 mg (1.5 mmol, -Ot-Bu group) in 12 mL of dry dichloromethane was stirred at room temperature, and 3 mL of trifluoroacetic acid 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 dissolved in a mixed solution of 1 mL of tetrahydrofuran / N, N-dimethylformamide and added dropwise to 50 mL of 10% aqueous sodium carbonate solution for reprecipitation. The suspension was stirred at room temperature for 1 hour and then filtered. The obtained residue was washed with water and then vacuum-dried at 25 ° C. for 4 hours and at 50 ° C. for 20 hours to give a pale orange powder of poly [(4- 593 mg (yield> 99%) of hydroxystyrene)-(4-vinyltriphenylphosphine)] copolymer (P-1B) were 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 = 5,250).
¹ H-NMR (400 MHz, DMF-d ₇ , 25 ° C.) δ (ppm): 0.76-2.42 (m, 6H, C H ₂ C H ), 6.03-7.81 (m, 18H , Ar H), 8.99-9.66 (brs , 1H, O H).
M _n = 4,640 (calculated value).

Synthesis Example 10 Synthesis of Poly [(4-hydroxystyrene)-(4-vinyltriphenylphosphine)] Copolymer (P-2B) Poly [(4-t-butoxystyrene)-( 4-vinyltriphenylphosphine)] copolymer (P-2A) 3.40 g (16.3 mmol, -Ot-Bu group) in 120 mL of dry dichloromethane was stirred at room temperature, and 30 mL of trifluoroacetic acid was added to the solution. Then, 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 dissolved in a mixed solution of 5 mL of tetrahydrofuran / 5 mL of N, N-dimethylformamide and added dropwise to 300 mL of 10% aqueous sodium carbonate solution for reprecipitation. The suspension was stirred at room temperature for 1 hour and then filtered. The obtained residue was washed with water and then vacuum-dried at 25 ° C. for 4 hours and at 50 ° C. for 20 hours to give a white powder of poly [(4-hydroxy Styrene)-(4-vinyltriphenylphosphine)] copolymer (P-2B) 2.58 g (yield 98%) 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 = 4,840).
¹ H-NMR (400 MHz, DMF-d ₇ , 25 ° C.) δ (ppm): 0.80-2.36 (m, 17.4H, C H ₂ C H ), 6.17-7.85 (m , 33.2H, Ar H), 9.03-9.42 (brs, 4.8H, O H).
M _n = 3,730 (calculated value).

Synthesis Example 11 Synthesis of poly [(4-hydroxystyrene) -methyldiphenyl (4-vinylphenyl) phosphonium iodide] copolymer (P-1) Poly [(4-hydroxystyrene)-obtained in Synthesis Example 9 A mixed solution of (4-vinyltriphenylphosphine)] copolymer (P-1B) 402 mg (1 mmol, -PPh ₂ groups) in dry tetrahydrofuran 8 mL / dry dichloromethane 2 mL was stirred at room temperature, and methyl iodide 710 mg was added to the solution. (5 mmol) was added, and the mixture was further stirred at 50 ° C. for 48 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 a pale yellow solid poly [(4-hydroxystyrene) -methyldiphenyl (4-vinylphenyl) phosphonium iodide. DO] copolymer (P-1) (525 mg, yield 97%) 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 = 4,640).
¹ H-NMR (400 MHz, DMF-d ₇ , 25 ° C.) δ (ppm): 0.85 to 2.50 (m, 6H, C H ₂ C H ), 3.14-3.47 (brs, 3H _{, PC H 3), 6.29-8.01 (} m, 18H, Ar H), 9.12-9.57 (brs, 1H, O H).
M _n = 6,280 (calculated value).

Synthesis Example 12 Synthesis of poly [(4-hydroxystyrene) -methyldiphenyl (4-vinylphenyl) phosphonium iodide] copolymer (P-2) Poly [(4-hydroxystyrene)-obtained in Synthesis Example 10 (4-vinyltriphenylphosphine)] copolymer (P-2B) 1.75 g (2 mmol, -PPh ₂ groups) of dry tetrahydrofuran 32 mL / dry dichloromethane 8 mL was stirred at room temperature, and the solution was iodinated. After adding 1.42 g (10 mmol) of methyl, the mixture was further stirred at 50 ° C. for 48 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 a pale yellow solid poly [(4-hydroxystyrene) -methyl. Diphenyl (4-vinylphenyl) phosphonium iodide] copolymer (P-2) 2.03 g (yield> 99%) 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 = 3,730).
¹ H-NMR (400 MHz, DMF-d ₇ , 25 ° C.) δ (ppm): 1.10-2.61 (m, 17.4 H , C H ₂ C H ), 3.11-3.45 (brs _{, 3H, PC H 3),} 6.15-8.26 (m, 33.2H, Ar H), 8.95-9.69 (brs, 4.8H, O H).
M _n = 4,350 (calculated value).

Comparative Synthesis Example 1 Synthesis of benzyl iodide A solution of 1.27 g (10 mmol) of benzyl chloride in 15 mL of dry acetone was stirred at room temperature. Stir. After completion of the reaction, the solution was concentrated to about 1/3, then 50 mL of water was added and extracted twice with 20 mL of hexane. The extracted hexane solution was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 2.17 g (yield> 99%) of benzyl iodide as a pale yellow oily substance. The structure of benzyl iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 4.45 (s, 2H, C H ₂ ), 7.21-7.32 (m, 3H, Ar H ), 7.36 -7.39 (m, 2H, Ar H ).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 5.73 ( C H ₂ ), 127.86 ( Ar ), 128.71 ( Ar ), 128.79 ( Ar ), 139. 25 ( Ar ).

Comparative Synthesis Example 2 Synthesis of benzyltriphenylphosphonium iodide A solution of 1.05 g (4 mmol) of triphenylphosphine in 16 mL of dry dichloromethane was stirred at room temperature, and 1.31 g (6 mmol) of benzyl iodide was added to the solution. Stir 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 1.87 g (yield of yellow solid benzyltriphenylphosphonium iodide). 97%). The structure of benzyltriphenylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 5.47 (d, 2H, J = 15, 6 Hz, PC H ₂ ), 6.96-7.01 (m, 2H) , Ar H ), 7.20-7.32 (m, 3H, Ar H ), 7.67 (dd, 2H, J = 12.2, 1.6 Hz, Ar H ), 7.69 (dd, 4H , J = 11.6, 0.8 Hz, Ar H ), 7.75 (ddd, 6H, J = 8.0, 8.0, 3.6 Hz, Ar H ), 7.88-7.94 (m , 3H, Ar H).
¹³ C-NMR (100 MHz, DMSO-d ₆ , 25 ° C.) δ (ppm): 28.09 (d, J = 46.7 Hz, P C H ₂ ), 117.73 (d, J = 84.9 Hz, Ar ), 127.82 (d, J = 8.5 Hz, Ar ), 128.15-128.45 (m, Ar ), 128.53-128.91 (m, Ar ), 130.05 (d, J = 12.4 Hz, Ar ), 130.61-130.96 (m, Ar ), 133.96 (d, J = 9.6 Hz, Ar ), 135.06 (d, J = 1.9 Hz, Ar) ).

Comparative Synthesis Example 3 Synthesis of benzyltri-n-butylphosphonium iodide A solution of 870 mg (4 mmol) of 93% tri-n-butylphosphine in 16 mL of dry dichloromethane was stirred at room temperature, and 1.31 g (6 mmol) of benzyl iodide was added to the solution. After the addition, 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. (Yield 96%) was obtained. The structure of benzyltri-n-butylphosphonium iodide was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 0.93 (t, 9H, J = 7.2 Hz, C H ₃ ), 1.42-1.57 (m, 12H, C _{H 2 C H 2 CH 3)} , 2.37-2.49 (m, 6H, PC H 2 CH 2), 4.20 (d, 2H, J = 14.4Hz, PC H 2), 7.32 -7.39 (m, 3H, Ar H ), 7.47-7.52 (m, 2H, Ar H).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 12.97 ( C H ₃ ), 18.28 (d, J = 46.7 Hz, P C H ₂ CH ₂ ), 23.12 (D, J = 4.7 Hz, C H ₂ CH ₃ ), 23.35 (d, J = 15.2 Hz, PCH ₂ C H ₂ ), 26.30 (d, J = 43.8 Hz, P C H _{2 Ar), 127.80 (d,} J = 8.5Hz, Ar), 127.86 (d, J = 4.8Hz, Ar), 128.84 (d, J = 2.9Hz, Ar), 129 .57 (d, J = 4.8 Hz, Ar ).

Example 1 and Comparative Example 1 Synthesis of (phenoxymethyl) ethylene carbonate using various phosphonium salts A solution (or suspension) of various phosphonium salts 0.05 mmol shown in Table 1 in 0.2 mL of tetrahydrofuran was stirred at room temperature. After adding 1 mmol of phenyl glycidyl ether, 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 1.

Examples 2 and 3 and Comparative Example 2 Synthesis of n-butylethylene carbonate using various phosphonium salts 0.05-mL N-methylpyrrolidone solution (or suspension) of 0.05 mmol of various phosphonium salts shown in Table 2 The mixture was stirred at room temperature, 1 mmol of n-hexene oxide was added, the reaction system was sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa), and 24 under the conditions shown in Table 2. Stir for 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 2.

Examples 4 and 5 Synthesis of carbonate using bis (2-hydroxybenzyl) diphenylphosphonium iodide as phosphonium salt 0.05 mmol of N-methyl bis (2-hydroxybenzyl) diphenylphosphonium iodide obtained in Synthesis Example 5 The pyrrolidone 0.2 mL solution (or suspension) was stirred at room temperature, and after adding 1 mmol of various epoxides shown in Table 3, the reaction system was sealed with a balloon filled with carbon dioxide gas, and 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 3.

Examples 6 to 10 and Comparative Examples 3 and 4 Synthesis of carbonate using (2-hydroxybenzyl) tri-n-butylphosphonium iodide as a phosphonium salt (2-hydroxybenzyl) tri-- obtained in Synthesis Example 6 0.05 mmol of n-butylphosphonium iodide or 0.05 mmol of benzyltri-n-butylphosphonium iodide obtained in Comparative Synthesis Example 3 dissolved (or suspended) in 0.2 mL of various solvents shown in Table 4 Was stirred at room temperature, 1 mmol of various epoxides shown in Table 4 were added to the solution (or suspension), the reaction system was sealed with a balloon filled with carbon dioxide gas, and 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 4. In Examples 9 and 10 and Comparative Example 4, experiments were conducted in bulk using a system to which no solvent was added.

Example 11 Isolation and synthesis of propylene carbonate using (2-hydroxybenzyl) tri-n-butylphosphonium iodide as a phosphonium salt 21.8 mg (0.05 mmol) of (2-hydroxybenzyl) tri-n-butylphosphonium iodide ), 209 mg (5 mmol) of propylene oxide was 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) and further stirred at room temperature for 24 hours ( ¹ H -95% conversion by NMR). After completion of the reaction, hexane / ethyl acetate was added to the reaction solution to precipitate and remove (2-hydroxybenzyl) tri-n-butylphosphonium iodide, and then the solvent was distilled off. Was dried under reduced pressure (5 mmHg) for 3 hours to obtain 368 mg (yield 72%) of propylene carbonate as a colorless oily substance. The structure of propylene carbonate was confirmed by ¹ H- and ¹³ C-NMR analysis.
¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 1.50 (d, 3H, J = 6.0 Hz, C H ₃ ), 4.04 (t, 1H, J = 8.0 Hz) , C H H), 4.57 (t, 1 H, J = 8.0 Hz, CH H ), 4.82-4.92 (m, 1 H, C H ).
¹³ C-NMR (100 MHz, CDCl ₃ , 25 ° C.) δ (ppm): 19.37 ( C H ₃ ), 70.60 (CH C H ₂ ), 73.50 ( C HCH ₂ ), 155.00 ( C = O).

Examples 12 to 15 Synthesis of (phenoxymethyl) ethylene carbonate using a polymer (copolymer P-1 or P-2) as a phosphonium salt Phosphonium salt (P-1 or P) obtained in Synthesis Example 11 or 12 -2) A solution obtained by dissolving (or suspending) 0.05 mmol in 0.2 mL of various solvents shown in Table 5 was stirred at room temperature, and 1 mmol of phenylglycidyl ether was added to the solution (or suspension). 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 5.

Examples 16 and 17 Synthesis of n-butylethylene carbonate using a polymer (copolymer P-2) as a phosphonium salt 0.05 mmol of the phosphonium salt (P-2) obtained in Synthesis Example 12 was added to n-hexene. After adding 1 mmol of 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 for 24 hours under the conditions shown in Table 6. 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.

  From the results of Tables 1 to 4 and Example 11, by using a phosphonium salt having an iodine anion and having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide, mild conditions such as normal temperature and normal pressure are used. However, it was found that the reaction between epoxide (oxirane) and carbon dioxide proceeds efficiently. 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. In addition, since the phosphonium salt according to the present invention is a metal-free (metal-free) catalyst, the production method of the present invention using these catalysts is also useful from the viewpoint of green chemistry, and considers reducing the environmental burden. It turned out to be a practical manufacturing method.

  Further, from the results of Tables 5 and 6, even when the polymer is used as a phosphonium salt having an iodine anion and having a hydrogen atom capable of hydrogen bonding with the oxygen atom of the epoxide, the cyclic carbonate is obtained in a high yield. It turns out that it is obtained. The phosphonium salts according to the present invention comprising these polymers were found to be useful from the viewpoint of green chemistry because they can be easily recovered and reused.

  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 (9)

A method for producing a cyclic carbonate, comprising reacting an epoxide and carbon dioxide in the presence of a phosphonium salt having an iodine anion and having a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide. The phosphonium salt comprises (1) a compound represented by the general formula [1], (2) a polymer containing a monomer unit derived from the compound represented by the general formula [2] as a constituent unit, and (3) a general formula [ 3] and a monomer unit derived from a compound having a hydroxyl group, a carboxyl group, a thiol group, or a thiocarboxyl group in the molecule and a copolymer containing a monomer unit derived from the compound represented by the formula (3) as a constituent unit. The manufacturing method according to claim 1.

(Wherein R ¹ represents a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group, or a hydroxyboryl group. An alkyl group having 1 to 10 carbon atoms; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group, or hydroxyboryl A C6-C10 aryl group having a group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group, or A C7-12 aralkyl group having a hydroxyboryl group; 2 to 10 carbon atoms having a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group, or a hydroxyboryl group N, N-dialkylamino group, R ² , R ³ and R ⁴ are each independently a hydrogen atom; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary Or a secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group, which may have a C 1-10 alkyl group; a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or Secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene Or an aryl group having 6 to 10 carbon atoms which may have a hydroxyboryl group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo Group, ureylene group, thioureylene group or hydroxyboryl group optionally having 7 to 12 carbon atoms; or hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, 1 And represents an N, N-dialkylamino group having 2 to 10 carbon atoms which may have a secondary or secondary amide group, sulfo group, ureylene group, thioureylene group or hydroxyboryl group.)

(Wherein R ⁵ represents a hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group or hydroxyboryl group. An alkyl group having 1 to 10 carbon atoms; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group, or hydroxyboryl A C6-C10 aryl group having a group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene group, or A C7-12 aralkyl group having a hydroxyboryl group; 2 to 10 carbon atoms having a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or secondary amino group, a primary or secondary amide group, a sulfo group, a ureylene group, a thioureylene group, or a hydroxyboryl group N, N-dialkylamino group, R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary Or a secondary amide group, a sulfo group, a ureylene group, a thioureylene group or a hydroxyboryl group, which may have a C 1-10 alkyl group; a hydroxyl group, a carboxyl group, a thiol group, a thiocarboxyl group, a primary or Secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene Or an aryl group having 6 to 10 carbon atoms which may have a hydroxyboryl group; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo Group, ureylene group, thioureylene group or hydroxyboryl group optionally having 7 to 12 carbon atoms; hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary Or a secondary amide group, a sulfo group, a ureylene group, a thioureylene group, or a hydroxyboryl group, which may have a C 2-10 N, N-dialkylamino group; a C 1-10 alkyl having a vinyl group Group: aryl group having 6 to 10 carbon atoms having vinyl group; aralkyl group having 7 to 12 carbon atoms having vinyl group Or it represents a carbon number 2 to 10 of N, N-dialkylamino group having a vinyl group. However, any one of R ⁶ , R ⁷ and R ⁸ 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, and 7 carbon atoms having a vinyl group. It is a C2-C10 N, N-dialkylamino group having a -12 aralkyl group or a vinyl group. )

(In the formula, R ⁹ represents 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 a vinyl group. Represents an N, N-dialkylamino group having 2 to 10 carbon atoms, and each of R ¹⁰ , R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or an N, N-dialkylamino group having 2 to 10 carbon atoms.) The phosphonium salt comprises (1 ′) a compound represented by the general formula [1 ′], (2 ′) a polymer containing a monomer unit derived from the compound represented by the general formula [2 ′] as a constituent unit, and (3 ') A monomer unit derived from a compound represented by the general formula [3'] and a copolymer containing monomer units derived from a compound having a hydroxyl group in the molecule as constituent units. The manufacturing method as described.

(In the formula, R ^{1 ′} represents a C 7-12 aralkyl group having a hydroxyl group, and R ^{2 ′} , R ^{3 ′} and R ^{4 ′} may each independently have a hydroxyl group. This represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 12 carbon atoms which may have a hydroxyl group.

(In the formula, R ^{5 ′} represents a C 7-12 aralkyl group having a hydroxyl group or a thioureylene group, R ^{6 ′} represents a C 6-10 aryl group having a vinyl group, and R ^{7 ′.} And R ^{8 ′} each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

(Wherein R ^{9 ′} represents an aryl group having 6 to 10 carbon atoms having a vinyl group, and R ^{10 ′} , R ^{11 ′} and R ^{12 ′} are each independently an alkyl group having 1 to 10 carbon atoms, Represents an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 12 carbon atoms.) The phosphonium salt is (1 ″) a compound represented by the general formula [1 ″], (2 ″) a monomer unit derived from the compound represented by the general formula [2 ″], and a monomer derived from a styrene derivative. A copolymer composed of units, and a copolymer composed of monomer units derived from a compound represented by (3 ″) the general formula [3 ″] and a monomer unit derived from a hydroxystyrene derivative, The manufacturing method according to claim 1.

Wherein R ^{1 ″} represents a 2-hydroxylbenzyl group, R ^{2 ″} represents a ² -hydroxylbenzyl group, an alkyl group having 2 to 6 carbon atoms, or a phenyl group, and R ^{3 ″} and R ^{3 4 ″} each independently represents an alkyl group having 2 to 6 carbon atoms or a phenyl group.)

(Wherein R ^{5 ″} represents a 2-hydroxylbenzyl group or 3,5-ditrifluoromethylphenylthioureylenylpropyl group, R ^{6 ″} represents a 4-vinylphenyl group, R ^{7 ′ 'And} R ^8'' represent a phenyl group.)

(Wherein R ^{9 ″} represents a 4-vinylphenyl group, R ^{10 ″} represents an alkyl group having 1 to 4 carbon atoms, and R ^{11 ″} and R ^{12 ″} represent a phenyl group. .) 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 4. The production method according to claim 4, wherein the hydroxystyrene derivative is selected from 2-hydroxystyrene, 3-hydroxystyrene, and 4-hydroxystyrene. The phosphonium salt is 2-hydroxybenzyltriphenylphosphonium iodide, 3-hydroxybenzyltriphenylphosphonium iodide, 4-hydroxybenzyltriphenylphosphonium iodide, bis (2-hydroxybenzyl) diphenylphosphonium iodide, 2-hydroxy The production method according to claim 1, wherein the production method is selected from benzyltri-n-butylphosphonium iodide and a copolymer of methyl (4-vinylphenyl) diphenylphosphonium iodide and 4-hydroxystyrene. 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.