JP2012024765A - Catalyst for manufacturing cyclic carbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid catalyst which gives a cyclic carbonate at a high yield and a high selectivity, excels in stability and facilitates catalyst separation after reaction; and an inexpensive and safe synthesis method of a cyclic carbonate of a continuous distribution method industrially advantageous by the use of the same.SOLUTION: As a catalyst, a catalyst containing silica having a surface modified by binding (tributylphosphonium bromide)-2C-8C alkylene group (-CHPBuBr, n=2 to 8), (triethylphosphonium bromide)-2C-8C alkylene group (-CHPEtBr, n=2 to 8), or (tributylphosphonium iodide)-2C-8C alkylene group (-CHPBuI, n=2 to 8) is used.

Description

  The present invention relates to a catalyst used when synthesizing a cyclic carbonate from epoxide and carbon dioxide, and a method for synthesizing a cyclic carbonate using the catalyst.

Cyclic carbonate is one of the important compounds used in a wide range of applications as organic solvents, synthetic fiber processing agents, pharmaceutical raw materials, cosmetic additives, electrolyte solvents for lithium batteries, and intermediates for the synthesis of alkylene glycols and dialkyl carbonates. It is.
Conventionally, this cyclic carbonate is produced by reacting an epoxide and carbon dioxide under appropriate pressure conditions in the presence of a homogeneous catalyst. As such homogeneous catalysts, halides such as alkali metals (Patent Document 1 etc.) and onium salts such as quaternary ammonium salts (Patent Document 2 etc.) have been known for a long time and are used industrially. ing.
Recently, a cyclic carbonate using carbon dioxide in a supercritical state as a reaction medium as well as a reagent in the presence of an alkali metal halide or a fluorinated alkylphosphonium salt, which is a method discovered by the present inventors. Has been proposed (Patent Document 3).
More recently, it has been reported that an ionic fluid such as octylmethylimidazolium tetrafluoroborate exhibits good catalytic ability (Non-patent Document 1).
However, when using a homogeneous catalyst, it is usually necessary to separate the reaction mixture from the catalyst by distillation, etc., which not only complicates the production process, but also decomposes and produces by-products during the separation process. There is a problem of the generation of things.

On the other hand, the use of a solid catalyst for the purpose of simplifying the catalyst separation process has also been proposed, such as ion exchange resins (Patent Document 4 and the like), basic layered compounds such as hydrotalcite (Patent Document 5), rare earth compounds ( Patent Document 6), heteropoly acids mainly composed of tungsten oxide or molybdenum oxide (Patent Document 7) and the like are disclosed. Further, it has been reported that magnesia can be used as a solid catalyst (Non-patent Document 2).
However, many solid catalysts are generally not sufficient in terms of activity, yield and selectivity as compared with homogeneous catalysts, and ion exchange resins have not exhibited activity exceeding the performance of molecular catalysts. Moreover, much time and energy were required to prepare a highly active catalyst.

Japanese Patent Publication No.63-17072 JP 55-145623 A JP 11-335372 A Japanese Patent Laid-Open No. 3-120270 Japanese Patent Laid-Open No. 11-226413 JP 2002-363177 A Japanese Unexamined Patent Publication No. 7-206847

Chem.Commun., 2003,896 Chem. Commun., 1997, 1129

  The present invention overcomes the above-mentioned problems in the production of conventional cyclic carbonates, and its purpose is to provide cyclic carbonates with higher yield and higher selectivity, excellent stability, and catalyst separation after the reaction. An object of the present invention is to provide an easy solid catalyst and an industrially advantageous, inexpensive and safe method for synthesizing a cyclic carbonate using the catalyst.

  As a result of intensive studies in order to solve the above-described conventional problems, the present inventors have found that a catalyst containing an inorganic solid material whose surface is modified with an ionic material containing a Group 15 element has been developed. It has been found that it has high activity and high selectivity for the synthesis reaction of cyclic carbonate from carbon, and the present invention has been completed.

That is, according to this application, the following invention is provided.
(1) A catalyst used when synthesizing a cyclic carbonate from epoxide and carbon dioxide, characterized by containing an inorganic solid substance surface-modified with an ionic substance containing a Group 15 element.
(2) The ionic substance containing a Group 15 element is at least one substance selected from organic phosphonium salts, organic ammonium salts, organic arsonium salts, and organic antimonium salts, as described in (1) above Catalyst.
(3) The catalyst according to (2) above, wherein the salt selected from organic phosphonium salts, organic ammonium salts, organic arsonium salts, and organic antimonium salts is a halide.
(4) Anion of a salt selected from organic phosphonium salt, organic ammonium salt, organic arsonium salt and organic antimonium salt is sulfate ion, hydrogen sulfate ion, phosphate ion, hydrogen phosphate ion, dihydrogen phosphate ion, cyanide ion The catalyst according to (3) above, which is at least one selected from the group consisting of isothiocyanate ion, isocyanate ion, carbonate ion and hydrogencarbonate ion.
(5) The catalyst according to any one of (1) to (4) above, wherein the inorganic solid substance is a metal oxide.
(6) The catalyst according to (5) above, wherein the metal oxide is an oxide containing silicon.
(7) A catalyst used when synthesizing a cyclic carbonate from epoxide and carbon dioxide, which contains an ionic substance containing a Group 15 element and an inorganic solid substance.
(8) The ionic substance containing a Group 15 element is at least one substance selected from organic ammonium salts, organic phosphonium salts, organic arsonium salts, and organic antimonium salts, as described in (7) above Catalyst.
(9) The catalyst according to (8) above, wherein the salt selected from organic ammonium salts, organic phosphonium salts, organic arsonium salts and antimonium salts is a halide.
(10) Anions of salts selected from organic phosphonium salts, organic ammonium salts, organic arsonium salts, and organic antimonium salts are sulfate ions, hydrogen sulfate ions, phosphate ions, hydrogen phosphate ions, dihydrogen phosphate ions, cyanide ions. The catalyst according to (9) above, which is at least one selected from the group consisting of isothiocyanate ion, isocyanate ion, carbonate ion and hydrogencarbonate ion.
(11) The catalyst according to any one of (7) to (10) above, wherein the inorganic solid substance is a metal oxide.
(12) The catalyst according to (11) above, wherein the metal oxide is an oxide containing silicon.

  The catalyst of the present invention has an extremely high efficiency from an epoxide and carbon dioxide to an electrolyte solvent for lithium batteries, an organic solvent, a synthetic fiber processing agent, a pharmaceutical raw material, and a cyclic carbonate useful as an intermediate for synthesizing alkylene glycol and dialkyl carbonate. Can be obtained with high selectivity. It can be used in a flow reaction system, is safe and inexpensive, has a long life, and is easy to separate and recover.

FIG. 1 is an explanatory diagram of a flow reaction apparatus preferably used in the present invention.

The synthesis reaction of the cyclic carbonate from the epoxide of the present invention and carbon dioxide is represented by the following general formula (1).

In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, a substituted or unsubstituted organic group, and more specifically an alkyl group, an aryl group, an alkenyl group, a cyclo Represents an alkyl group or an arylalkyl group, and may be the same or different from each other; Substituents here are halogen atoms, halogenated alkyl groups, dialkylamino groups, nitro groups, carbonyl groups, carboxyl groups, alkoxy groups, acetoxy groups, cyano groups, hydroxyl groups, mercapto groups, sulfone groups, etc. It is not limited to the substituent. Any one or more of R _{1 to} R ₄ may be bonded in a cyclic manner, and may contain an unsaturated bond.

The epoxide used in the present invention is a compound represented by the following general formula (2).

In the general formula (2), R ₁ , R ₂ , R ₃ and R ₄ are the same as those in the general formula (1). Any one or a plurality of R _{1 to} R ₄ may be bonded cyclically, and may contain a hetero element or an unsaturated bond. Specifically, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, vinyl ethylene oxide, trifluoromethyl ethylene oxide, cyclohexene oxide, styrene oxide, butadiene monooxide, butadiene dioxide, chloral, 2-methyl-3-phenylbutene oxide, Examples include pinene oxide, tetracyanoethylene oxide, and the like, but the present invention is not limited to these epoxides, and includes at least one three-membered ring composed of two carbon atoms and one oxygen atom in the structural formula. Any so-called epoxy compound can be used.

The cyclic carbonate produced in the present invention is a compound represented by the following general formula (3).

In the general formula (3), R ₁ , R ₂ , R ₃ and R ₄ are the same as in the general formula (1). Any one or a plurality of R _{1 to} R ₄ may be bonded cyclically, and may contain a hetero element or an unsaturated bond. Specifically, ethylene carbonate, propylene carbonate, butylene carbonate, isobutylene carbonate, trifluoromethyl ethylene carbonate, vinyl ethylene carbonate, cyclohexene carbonate, styrene carbonate, butadiene monocarbonate, butadiene dicarbonate, chloromethyl carbonate, pinene carbonate, tetracyano Although ethylene carbonate etc. are illustrated, the cyclic carbonate produced in the present invention is not limited to these, and any so-called cyclic carbonate containing a 5-membered ring having an O—CO—O bond may be used.

  The catalyst of the first aspect used in the present invention contains an inorganic solid material whose surface is modified with an ionic material containing a Group 15 element. In this surface-modified inorganic solid substance, an ionic substance containing a Group 15 element and an inorganic solid substance are usually bonded by a chemical bond.

The ionic substance containing a Group 15 element means at least one substance selected from organic phosphonium salts, organic ammonium salts, organic arsonium salts, and organic antimonium salts. Those preferably used in the present invention are organic phosphonium salts, organic arsonium salts, and organic antimonium salts.
Ionic substances containing these Group 15 elements can generally be represented by the general formula ER ₅ R ₆ R ₇ R ₈ X.
Here, E represents one of group 15 elements (nitrogen, phosphorus, arsenic, antimony, bismuth), R _{5 to} R ₈ represent an organic group which may be substituted, and more specifically, an alkyl group, aryl Represents a group or the like, and 2 to 4 of them may be bonded in a ring shape. Or the ring in this case may include a double bond or a triple bond. Accordingly, nitrogen-containing heterocyclic salts such as imidazolinium, pyridinium, tetrazolinium and the like are also included.
X is an anion, halide ion, phosphate ion, hydrogen phosphate ion, dihydrogen phosphate ion, nitrate ion, sulfate ion, hydrogen sulfate ion, organic acid ion, carbonate ion, bicarbonate ion, borate ion, boric acid From hydrogen ion, alkyl or aryl sulfate ion, mono or dialkyl phosphate ion, mono or diaryl phosphate ion, mono or dialkyl borate ion, cyanide ion, thiocyanate ion, isocyanate ion, carboxylate ion, tetrafluoroborate ion, etc. One or more anions selected, preferably halide ions, sulfate ions, hydrogen sulfate ions, phosphate ions, hydrogen phosphate ions, dihydrogen phosphate ions, cyanide ions, isothiocyan ions, isocyanate ions, Carbonate ions and Hydrogen carbonate ions and the like, and halide ions such as chloride ions, bromide ions, and iodide ions are more preferable.

The inorganic solid substance used in the present invention may be a simple substance or a compound as long as it is an inorganic substance in a solid state. Specifically, carbon, silicon, aluminum, titanium, iron, copper, silver, gold, platinum, nickel, cobalt An alloy containing two or more metals, a metal oxide containing one or more metals, a metal nitride, a metal carbide, a metal sulfide, a metal halide, a metal boride, a metal phosphide , Metal oxyhalides, metal oxynitrides, metal oxysulfides, and mixtures thereof, but preferably contain Group 2-6 and Group 13, Group 14 element oxides, more preferably silicon An oxide (such as silica) is used.
Also, usually, it is preferable to use of about surface area 10m ² / g~2000m ² / g.
Examples of the silicon-containing oxide that is preferably used in the present invention include silica gel for separation and silica gel for drying.
Although there is no restriction | limiting in particular in the form of the inorganic solid substance used by this invention, Usually, it is a fine powder form, a thin film form, or a spherical or cylindrical particle | grain with an average particle diameter of about 0.1-10 mm.

The surface-modified inorganic solid material catalyst used in the present invention is represented by the model S-ER ₅ R ₆ R ₇ R ₈ X, and is represented by a schematic diagram such as the following chemical formula (4). Here, S represents the solid substance described in the previous section, E represents one of the Group 15 elements, R ₅ to R ₈ represent the same organic group as in the previous section, and may be the same or different from each other. Any one of an optionally substituted alkyl group, aryl group and aralkyl group, some or all of which may be cyclically bonded, and may contain a hetero atom. Actually, one or more of the substituents of R have a chemical bond with solid S. For example, a schematic diagram in the case where only R ₅ has a chemical bond with the solid surface is shown in chemical formula (5). In the case of the chemical formula (5), the R ₅ part is called a linker here, but as a candidate for the linker, a terminal composed of a carbon skeleton such as an alkylene group, an arylene group, an aralkylene group or the like having a terminal directly bonded to a solid substance or a polyethylene glycol chain In addition, it may be composed of a covalent bond containing a skeleton heteroelement such as a silicone chain, having a branch or ring in the middle, or having an unsaturated bond or a substituent containing a heteroelement. More specifically, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, phenylene, phenylmethylene, xylyl, alkylenephenylene, phenylenealkylene, polyethylene glycolyl A group having a trimethylene group is preferably used. Similarly, when the linker portion is limited to one, the three organic groups constituting ER ₆ R ₇ R ₈ of the remaining onium portion are alkyl, aryl, aralkyl, oxyalkyl, and oxyaryl. Arbitrary combinations selected from groups and the like can be used, and more specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopentadienyl group, ferrocenyl group, hexyl group, cyclohexyl group , Phenyl group, pentyl group, tolyl group, methoxyphenyl group, benzyl group, octyl group, naphthyl group and the like. In order to more specifically represent a solid, a linker, and an onium salt, a schematic diagram such as the chemical formula (6) is also used.

In the above formula, SiO ₂ is silica gel and L is a linker, which usually represents an alkylene group having 2 to 8 carbon atoms, preferably an alkylene group having 3 carbon atoms. R is a substituent on phosphorus and is an alkyl group or an aryl group. R _{5 to} R ₈ are as described above, and X represents the anion.

  Although there is no restriction | limiting in particular in the synthesis method of the surface modification silica catalyst etc. which are used by this invention, For example, it obtains by reaction with the substance containing a group 15 element and commercially available halogenated alkyl group or halogenated aryl group modified silica gel. In addition, the surface-modified silica or the like synthesized in this way can replace the anion which is a counter ion with various ones by an ion exchange reaction.

  Further, it is not always necessary to separately synthesize the surface-modified silica catalyst or the like, and in the cyclic carbonate synthesis reaction system from epoxide and carbon dioxide, a halogenated alkyl group or halogenated aralkyl group-modified silica gel and a substance containing a Group 15 element The same effect as the surface-modified silica catalyst or the like can be obtained also by coexisting with.

  Moreover, in this invention, you may use what carried | supported these surface modification silicas on arbitrary support | carriers. Examples of the carrier include silica, alumina, zeolite, silicon carbide, clay mineral (montmorillonite, etc.), silica-alumina, zirconia, titania, zinc oxide, cadmium sulfide, magnesia, and the like, but are not limited thereto. is not.

The catalyst of the second aspect used in the present invention is characterized by containing an ionic substance containing a Group 15 element (hereinafter also referred to as onium salt) and an inorganic solid substance.
As the ionic substance containing a Group 15 element, at least one substance selected from organic phosphonium salts, organic arsonium salts, organic antimonium salts, and organic ammonium salts shown in the first aspect is used.

Specific examples of such ionic substances containing Group 15 elements include tetramethylphosphonium iodide, tetramethylphosphonium bromide, tetramethylphosphonium chloride, tetraethylphosphonium iodide, tetraethylphosphonium bromide, tetraethylphosphonium chloride, tetra Propylphosphonium iodide, tetrapropylphosphonium bromide, tetrapropylphosphonium chloride, tetrabutylphosphonium iodide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrapentylphosphonium iodide, tetrapentylphosphonium bromide, tetrapentylphosphonium chloride, tetrahexylphosphonium Iodide, tetrahexylphosphonium bromide, tetrahex Ruphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraheptylphosphonium iodide, tetraheptylphosphonium bromide, tetraheptylphosphonium chloride, tetrabenzylphosphonium iodide, tetrabenzylphosphonium bromide, tetrabenzylphosphonium Chloride, tetraoctylphosphonium iodide, tetraoctylphosphonium bromide, tetraoctylphosphonium chloride, tetranonylphosphonium iodide, tetranonylphosphonium bromide, tetranonylphosphonium chloride, tetrakisdecylphosphonium iodide, tetrakisdecylphosphonium bromide, tetrakisdecylphosphonium chloride Lido, tetradodecylphosphonium iodide, tetradodecylphosphonium bromide, tetradodecylphosphonium chloride, tetrakistetradecylphosphonium iodide, tetrakistetradecylphosphonium bromide, tetrakistetradecylphosphonium chloride, tetrakishexadecylphosphonium iodide, tetrakishexadecylphosphonium bromide, Tetrakishexadecylphosphonium iodide, tetrakisoctadecylphosphonium iodide, tetrakisoctadecylphosphonium bromide, tetrakisoctadecylphosphonium chloride, trimethylpropylphosphonium iodide, trimethylpropylphosphonium bromide, trimethylpropylphosphonium chloride, butyltrimethylphosphonium iodide , Butyltrimethylphosphonium bromide, butyltrimethylphosphonium chloride, trimethylpentylphosphonium iodide, trimethylpentylphosphonium bromide, trimethylpentylphosphonium chloride, hexyltrimethylphosphonium iodide, hexyltrimethylphosphonium bromide, hexyltrimethylphosphonium chloride, trimethylphenyl Phosphonium iodide, trimethylphenylphosphonium bromide, trimethylphenylphosphonium chloride, heptyltrimethylphosphonium iodide, heptyltrimethylphosphonium bromide, heptyltrimethylphosphonium chloride, benzyltrimethylphosphonium iodide, benzyltrimethylphosphonium bromide, benzyltrimethylphosphine Nium chloride, trimethyloctylphosphonium iodide, trimethyloctylphosphonium bromide, trimethyloctylphosphonium chloride, trimethylnonylphosphonium iodide, trimethylnonylphosphonium bromide, trimethylnonylphosphonium chloride, decyltrimethylphosphonium iodide, decyltrimethylphosphonium bromide, Decyltrimethylphosphonium chloride, trimethylundecylphosphonium iodide, trimethylundecylphosphonium bromide, trimethylundecylphosphonium chloride, dodecyltrimethylphosphonium iodide, dodecyltrimethylphosphonium bromide, dodecyltrimethylphosphonium chloride, trimethyltetradecylphosphonium iodide The Methyltetradecylphosphonium bromide, trimethyltetradecylphosphonium chloride, hexadecyltrimethylphosphonium iodide, hexadecyltrimethylphosphonium bromide, hexadecyltrimethylphosphonium chloride, trimethyloctadecylphosphonium iodide, trimethyloctadecylphosphonium bromide, trimethyloctadecylphosphonium chloride, triethylmethylphosphine Boronium iodide, triethylmethylphosphonium bromide, triethylmethylphosphonium chloride, triethylpropylphosphonium iodide, triethylpropylphosphonium bromide, triethylpropylphosphonium chloride, triethylbutylphosphonium iodide, triethylbutylphosphonium bromide, triethyl Ethylbutylphosphonium chloride, triethylpentylphosphonium iodide, triethylpentylphosphonium bromide, triethylpentylphosphonium chloride, triethylhexylphosphonium iodide, triethylhexylphosphonium bromide, triethylhexylphosphonium chloride, triethylphenylphosphonium iodide, triethyl Phenylphosphonium bromide, triethylphenylphosphonium chloride, triethylheptylphosphonium iodide, triethylheptylphosphonium bromide, triethylheptylphosphonium chloride, benzyltriethylphosphonium iodide, benzyltriethylphosphonium bromide, benzyltriethylphosphonium chloride, triethyloctylphosphonium Um iodide, triethyl octyl phosphonium bromide, triethyl octyl phosphonium chloride, triethyl nonyl phosphonium iodide, triethyl nonyl phosphonium bromide, triethyl nonyl phosphonium chloride, triethyl decyl phosphonium iodide, triethyl decyl phosphonium bromide, triethyl decyl phosphonium chloride, triethyl undecyl phosphonium Iodide, triethylundecylphosphonium bromide, triethylundecylphosphonium chloride, triethyldodecylphosphonium iodide, triethyldodecylphosphonium bromide, triethyldodecylphosphonium chloride, triethyltetradecylphosphonium iodide, triethyltetradecylphosphonium bromide, Ethyltetradecylphosphonium chloride, triethylhexadecylphosphonium iodide, triethylhexadecylphosphonium bromide, triethylhexadecylphosphonium chloride, triethyloctadecylphosphonium iodide, triethyloctadecylphosphonium bromide, triethyloctadecylphosphonium chloride, methyltripropylphosphonium iodide, methyltripropyl Propylphosphonium bromide, methyltripropylphosphonium chloride, ethyltripropylphosphonium iodide, ethyltripropylphosphonium bromide, ethyltripropylphosphonium chloride, butyltripropylphosphonium iodide, butyltripropylphosphonium bromide, butyltripropylphosphonium chloride, Nyltripropylphosphonium iodide, Pentyltripropylphosphonium bromide, Pentyltripropylphosphonium chloride, Hexyltripropylphosphonium iodide, Hexyltripropylphosphonium bromide, Hexyltripropylphosphonium chloride, Phenyltripropylphosphonium iodide, Phenyltripropylphosphonium Bromide, phenyltripropylphosphonium chloride, heptyltripropylphosphonium iodide, heptyltripropylphosphonium bromide, heptyltripropylphosphonium chloride, benzyltripropylphosphonium iodide, benzyltripropylphosphonium bromide, benzyltripropylphosphonium chloride, octyltripropylphosphonium Yogi , Octyl tripropyl phosphonium bromide, octyl tripropyl phosphonium chloride,
Nonyltripropylphosphonium iodide, nonyltripropylphosphonium bromide, nonyltripropylphosphonium chloride, decyltripropylphosphonium iodide, decyltripropylphosphonium bromide, decyltripropylphosphonium chloride, tripropylundecylphosphonium iodide, tripropylundecyl Phosphonium bromide, tripropylundecylphosphonium chloride, dodecyltripropylphosphonium iodide, dodecyltripropylphosphonium bromide, dodecyltripropylphosphonium chloride, tetradecyltripropylphosphonium iodide, tetradecyltripropylphosphonium bromide, tetradecyltripropylphosphonium chloride , Hexadecyltripropylphospho Um iodide, hexadecyltripropylphosphonium bromide, hexadecyltripropylphosphonium chloride, octadecyltripropylphosphonium iodide, octadecyltripropylphosphonium bromide, octadecyltripropylphosphonium chloride, tributylmethylphosphonium iodide, tributylmethylphosphonium bromide, tributylmethyl Phosphonium chloride, tributylethylphosphonium iodide, tributylethylphosphonium bromide, tributylethylphosphonium chloride, tributylpropylphosphonium iodide, tributylpropylphosphonium bromide, tributylpropylphosphonium chloride, tributylpentylphosphonium iodide, tributylpentylphosphonium Lomid, tributylpentylphosphonium chloride, tributylhexylphosphonium iodide, tributylhexylphosphonium bromide, tributylhexylphosphonium chloride, tributylphenylphosphonium iodide, tributylphenylphosphonium bromide, tributylphenylphosphonium chloride, tributylheptylphosphonium iodide, tributylheptylphosphonium bromide, Tributylheptylphosphonium chloride, benzyltributylphosphonium iodide, benzyltributylphosphonium bromide, benzyltributylphosphonium chloride, tributyloctylphosphonium iodide, tributyloctylphosphonium bromide, tributyloctylphosphonium chloride, tributylnonyl phosphate Suphonium iodide, tributylnonylphosphonium bromide, tributylnonylphosphonium chloride, tributyldecylphosphonium iodide, tributyldecylphosphonium bromide, tributyldecylphosphonium chloride, tributylundecylphosphonium iodide, tributylundecylphosphonium bromide, tributylundecylphosphonium chloride, Tributyldodecylphosphonium iodide, tributyldodecylphosphonium bromide, tributyldodecylphosphonium chloride, tributyltetradecylphosphonium iodide, tributyltetradecylphosphonium bromide, tributyltetradecylphosphonium chloride, tributylhexadecylphosphonium iodide, tributylhexadecylphosphonium Lomid, Tributylhexadecylphosphonium chloride, Tributyloctadecylphosphonium iodide, Tributyloctadecylphosphonium bromide, Tributyloctadecylphosphonium chloride, Methyltripentylphosphonium iodide, Methyltripentylphosphonium bromide, Methyltripentylphosphonium chloride, Ethyltripentylphosphonium iodide, Ethyltripentylphosphonium bromide, ethyltripentylphosphonium chloride, tripentylpropylphosphonium iodide, tripentylpropylphosphonium bromide, tripentylpropylphosphonium chloride, butyltripentylphosphonium iodide, butyltripentylphosphonium bromide, butyltripentylphosphonium chloride De, hexyl tripentyl phosphonium iodide, hexyl tripentyl bromide, hexyl tripentyl phosphonium chloride,
Tripentylphenylphosphonium iodide, tripentylphenylphosphonium bromide, tripentylphenylphosphonium chloride, heptyllipentylphosphonium iodide, heptyllipentylphosphonium bromide, heptyllipentylphosphonium chloride, benzyltripentylphosphonium iodide, benzyltripentylphosphonium bromide , Benzyltripentylphosphonium chloride, octyltripentylphosphonium iodide, octyltripentylphosphonium bromide, octyltripentylphosphonium chloride, nonyltripentylphosphonium iodide, nonyltripentylphosphonium bromide, nonyltripentylphosphonium chloride, decyltripentylphosphonium iodide De Rutripentylphosphonium bromide, decyltripentylphosphonium chloride, tripentylundecylphosphonium iodide, tripentylundecylphosphonium bromide, tripentylundecylphosphonium chloride, dodecyltripentylphosphonium iodide, dodecyltripentylphosphonium bromide, dodecyltripentylphosphonium Chloride, tetradecyltripentylphosphonium iodide, dodecyltripentylphosphonium bromide, dodecyltripentylphosphonium chloride, tripentyltetradecylphosphonium iodide, tripentyltetradecylphosphonium bromide, tripentyltetradecylphosphonium chloride, hexadecyltripentylphosphonium iodide And hexadecyltri N-tylphosphonium bromide, hexadecyltripentylphosphonium chloride, octadecyltripentylphosphonium iodide, octadecyltripentylphosphonium bromide, octadecyltripentylphosphonium chloride, trihexylmethylphosphonium iodide, trihexylmethylphosphonium bromide, trihexylmethylphosphonium chloride, Ethyltrihexylphosphonium iodide, ethyltrihexylphosphonium bromide, ethyltrihexylphosphonium chloride, trihexylpropylphosphonium iodide, trihexylpropylphosphonium bromide, trihexylpropylphosphonium chloride, butyltrihexylphosphonium iodide, butyltrihexylphosphonium bromide Butylto Rehexylphosphonium chloride, trihexylpentylphosphonium iodide, trihexylpentylphosphonium bromide, trihexylpentylphosphonium chloride, trihexylphenylphosphonium iodide, trihexylphenylphosphonium bromide, trihexylphenylphosphonium chloride, heptyltrihexylphosphonium iodide, Heptyltrihexylphosphonium bromide, heptyltrihexylphosphonium chloride, benzyltrihexylphosphonium iodide, benzyltrihexylphosphonium bromide, benzyltrihexylphosphonium chloride, trihexyloctylphosphonium iodide, trihexyloctylphosphonium bromide, trihexyloctylphosphonium chloride, bird Xylnonylphosphonium iodide, trihexylnonylphosphonium bromide, trihexylnonylphosphonium chloride, decyltrihexylphosphonium iodide, decyltrihexylphosphonium bromide, decyltrihexylphosphonium chloride, trihexylundecylphosphonium iodide, trihexylundecylphosphonium Bromide, trihexylundecylphosphonium chloride, dodecyltrihexylphosphonium iodide, dodecyltrihexylphosphonium bromide, dodecyltrihexylphosphonium chloride, trihexyltetradecylphosphonium iodide, trihexyltetradecylphosphonium bromide, trihexyltetradecylphosphonium chloride,
Hexadecyltrihexylphosphonium iodide, hexadecyltrihexylphosphonium bromide, hexadecyltrihexylphosphonium chloride, trihexyloctadecylphosphonium iodide, trihexyloctadecylphosphonium bromide, trihexyloctadecylphosphonium chloride, methyltriphenylphosphonium iodide, methyltriphenyl Phenylphosphonium bromide, methyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, triphenylpropylphosphonium iodide, triphenylpropylphosphonium bromide, triphenylpropylphosphonium chloride, butyltri Phenylphospho Umiodide, butyltriphenylphosphonium bromide, butyltriphenylphosphonium chloride, hexyltriphenylphosphonium iodide, hexyltriphenylphosphonium bromide, hexyltriphenylphosphonium chloride, pentyltriphenylphosphonium iodide, pentyltriphenylphosphonium bromide, pentyltriphenylphosphonium Chloride, hexyltriphenylphosphonium iodide, hexyltriphenylphosphonium bromide, hexyltriphenylphosphonium chloride, heptyltriphenylphosphonium iodide, heptyltriphenylphosphonium bromide, heptyltriphenylphosphonium chloride, benzyltriphenylphosphonium iodide, benzyltriphenyl Hos Nitrobromide, benzyltriphenylphosphonium chloride, octyltriphenylphosphonium iodide, octyltriphenylphosphonium bromide, octyltriphenylphosphonium chloride, nonyltriphenylphosphonium iodide, nonyltriphenylphosphonium bromide, nonyltriphenylphosphonium chloride, decyltriphenyl Phosphonium iodide, decyltriphenylphosphonium bromide, decyltriphenylphosphonium chloride, triphenylundecylphosphonium iodide, triphenylundecylphosphonium bromide, triphenylundecylphosphonium chloride, dodecyltriphenylphosphonium iodide, dodecyltriphenylphosphonium bromide , Dodecyltriphenylphospho Nium chloride, tetradecyltriphenylphosphonium iodide, tetradecyltriphenylphosphonium bromide, tetradecyltriphenylphosphonium chloride, triphenyltetradecylphosphonium iodide, triphenyltetradecylphosphonium bromide, triphenyltetradecylphosphonium chloride, hexadecyltri Phenylphosphonium iodide, hexadecyltriphenylphosphonium bromide, hexadecyltriphenylphosphonium chloride, octadecyltriphenylphosphonium iodide, octadecyltriphenylphosphonium bromide, octadecyltriphenylphosphonium chloride, triheptylmethylphosphonium iodide, triheptylmethylphosphonium bromide , Triheptylmethyl Suphonium chloride, ethyltriheptylphosphonium iodide, ethyltriheptylphosphonium bromide, ethyltriheptylphosphonium chloride, triheptylpropylphosphonium iodide, triheptylpropylphosphonium bromide, triheptylpropylphosphonium chloride, butyltriheptylphosphonium iodide, butyl Triheptylphosphonium bromide, butyltriheptylphosphonium chloride, triheptylpentylphosphonium iodide, triheptylpentylphosphonium bromide, triheptylpentylphosphonium chloride, triheptylhexylphosphonium iodide, triheptylhexylphosphonium bromide, triheptylhexylphosphonium chloride, triheptyl Heptyloctylphospho Umum iodide, triheptyloctylphosphonium bromide, triheptyloctylphosphonium chloride, triheptylnonylphosphonium iodide, triheptylnonylphosphonium bromide, triheptylnonylphosphonium chloride, decyltriheptylphosphonium iodide, decyltriheptylphosphonium bromide, decyltriheptylphosphonium Chloride, triheptylundecylphosphonium iodide, triheptylundecylphosphonium bromide, triheptylundecylphosphonium chloride, dodecyltriheptylphosphonium iodide, dodecyltriheptylphosphonium bromide, dodecyltriheptylphosphonium chloride, triheptyltetradecylphosphonium iodide , Triheptyltetradecyl Phosphonium bromide, triheptyltetradecylphosphonium chloride, triheptylhexadecylphosphonium iodide, triheptylhexadecylphosphonium bromide, triheptylhexadecylphosphonium chloride, tribenzylmethylphosphonium iodide, tribenzylmethylphosphonium bromide, tribenzylmethylphosphonium chloride , Tribenzylethylphosphonium iodide, tribenzylethylphosphonium bromide, tribenzylethylphosphonium chloride, tribenzylpropylphosphonium iodide, tribenzylpropylphosphonium bromide, tribenzylpropylphosphonium chloride, tribenzylbutylphosphonium iodide, tribenzylbutylphosphonium Bromide, tribenzylbu Ruphosphonium chloride, tribenzylpentylphosphonium iodide, tribenzylpentylphosphonium bromide, tribenzylpentylphosphonium chloride, tribenzylhexylphosphonium iodide, tribenzylhexylphosphonium bromide, tribenzylhexylphosphonium chloride, tribenzylphenylphosphonium iodide, tribenzylpentylphosphonium bromide Benzylphenylphosphonium bromide, tribenzylphenylphosphonium chloride, tribenzylheptylphosphonium iodide, tribenzylheptylphosphonium bromide, tribenzylheptylphosphonium chloride, tribenzyloctylphosphonium iodide, tribenzyloctylphosphonium bromide, tribenzyloctylphosphonium chloride, tribendi Nonylphosphonium iodide, tribenzylnonylphosphonium bromide, tribenzylnonylphosphonium chloride, tribenzyldecylphosphonium iodide, tribenzyldecylphosphonium bromide, tribenzyldecylphosphonium chloride, tribenzylundecylphosphonium iodide, tribenzylundecylphosphonium bromide , Tribenzylundecylphosphonium chloride, tribenzyldodecylphosphonium iodide, tribenzyldodecylphosphonium bromide, tribenzyldodecylphosphonium chloride, tribenzyltetradecylphosphonium iodide, tribenzyltetradecylphosphonium bromide, tribenzyltetradecylphosphonium chloride, tribenzyl Benzylhexadecylphosphonium iodide Tribenzylhexadecylphosphonium bromide, tribenzylhexadecylphosphonium chloride, tribenzyloctadecylphosphonium iodide, tribenzyloctadecylphosphonium bromide, tribenzyloctadecylphosphonium chloride, methyltrioctylphosphonium iodide, methyltrioctylphosphonium bromide, methyltrioctyl Octylphosphonium chloride, ethyltrioctylphosphonium iodide, ethyltrioctylphosphonium bromide, ethyltrioctylphosphonium chloride, trioctylpropylphosphonium iodide, trioctylpropylphosphonium bromide, trioctylpropylphosphonium chloride, butyltrioctylphosphonium iodide, butyl Trioctylphosphoni Muburomido, butyl trioctyl phosphonium chloride, trioctyl pentyl phosphonium iodide, trioctyl pentyl bromide, trioctyl pentyl phosphonium chloride, hexyl trioctyl phosphonium iodide, hexyl trioctyl phosphonium bromide, hexyl trioctyl phosphonium chloride,
Heptyltrioctylphosphonium iodide, heptyltrioctylphosphonium bromide, heptyltrioctylphosphonium chloride, nonyltrioctylphosphonium iodide, nonyltrioctylphosphonium bromide, nonyltrioctylphosphonium chloride, decyltrioctylphosphonium iodide, decyltrioctylphosphonium bromide , Decyltrioctylphosphonium chloride, trioctylundecylphosphonium iodide, trioctylundecylphosphonium bromide, trioctylundecylphosphonium chloride, dodecyltrioctylphosphonium iodide, dodecyltrioctylphosphonium bromide, dodecyltrioctylphosphonium chloride, trioctyl Tetradecylphosphonium iodide , Trioctyltetradecylphosphonium bromide, trioctyltetradecylphosphonium chloride, hexadecyltrioctylphosphonium iodide, hexadecyltrioctylphosphonium bromide, hexadecyltrioctylphosphonium chloride, octadecyltrioctylphosphonium iodide, octadecyltrioctylphosphonium bromide, Octadecyltrioctylphosphonium chloride, diethyldimethylphosphonium iodide, diethyldimethylphosphonium bromide, diethyldimethylphosphonium chloride, dimethyldipropylphosphonium iodide, dimethyldipropylphosphonium bromide, dimethyldipropylphosphonium chloride, dibutyldimethylphosphonium iodide, dibutyldimethylphospho Umbromide, dibutyldimethylphosphonium chloride, dimethyldipentylphosphonium iodide, dimethyldipentylphosphonium bromide, dimethyldipentylphosphonium chloride, dihexyldimethylphosphonium iodide, dihexyldimethylphosphonium bromide, dihexyldimethylphosphonium chloride, dimethyldiphenylphosphonium iodide, dimethyldiphenylphosphonium bromide, Dimethyldiphenylphosphonium chloride, diheptyldimethylphosphonium iodide, diheptyldimethylphosphonium bromide, diheptyldimethylphosphonium chloride, dibenzyldimethylphosphonium iodide, dibenzyldimethylphosphonium bromide, dibenzyldimethylphosphonium chloride, dimethyldioxychloride Tylphosphonium iodide, dimethyldioctylphosphonium bromide, dimethyldioctylphosphonium chloride, dimethyldinonylphosphonium iodide, dimethyldinonylphosphonium bromide, dimethyldinonylphosphonium chloride, didecyldimethylphosphonium iodide, didecyldimethylphosphonium bromide, didecyldimethyl Phosphonium chloride, didodecyldimethylphosphonium iodide, didodecyldimethylphosphonium bromide, didodecyldimethylphosphonium chloride, dimethylditetradecylphosphonium iodide, dimethylditetradecylphosphonium bromide, dimethylditetradecylphosphonium chloride, dihexadecyldimethylphosphonium iodide And dihexadecyldimethylphosphonium Imide, dihexadecyldimethylphosphonium chloride, dimethyldioctadecylphosphonium iodide, dimethyldioctadecylphosphonium bromide, dimethyldioctadecylphosphonium chloride, diethyldipropylphosphonium iodide, diethyldipropylphosphonium bromide, diethyldipropylphosphonium chloride, dibutyldiethylphosphonium Iodide, Dibutyldiethylphosphonium bromide, Dibutyldiethylphosphonium chloride, Diethyldipentylphosphonium iodide, Diethyldipentylphosphonium bromide, Diethyldipentylphosphonium chloride, Diethyldihexylphosphonium iodide, Diethyldihexylphosphonium bromide, Diethyldihexylphosphonium chloride, Diethyl Phenylphosphonium iodide, diethyldiphenylphosphonium bromide, diethyldiphenylphosphonium chloride, diheptyldiethylphosphonium iodide, diheptyldiethylphosphonium bromide, diheptyldiethylphosphonium chloride, dibenzyldiethylphosphonium iodide, dibenzyldiethylphosphonium bromide, dibenzyldiethyl Phosphonium chloride, diethyl dioctyl phosphonium iodide, diethyl dioctyl phosphonium bromide, diethyl dioctyl phosphonium chloride, diethyl dinonyl phosphonium iodide, diethyl dinonyl phosphonium bromide, diethyl dinonyl phosphonium chloride, didecyl diethyl phosphonium iodide, didecyl diethyl phosphonium bromide , Side Didiethylphosphonium chloride, didodecyldiethylphosphonium iodide, didodecyldiethylphosphonium bromide, didodecyldiethylphosphonium chloride, diethylditetradecylphosphonium iodide, diethylditetradecylphosphonium bromide, diethylditetradecylphosphonium chloride, diethyldihexadecyl Phosphonium iodide, diethyldihexadecylphosphonium bromide, diethyldihexadecylphosphonium chloride, diethyldioctadecylphosphonium iodide, diethyldioctadecylphosphonium bromide, diethyldioctadecylphosphonium chloride, dibutyldipropylphosphonium iodide, dibutyldipropylphosphonium bromide, Dibutyldipropylphosphonium chloride Dipentyldipropylphosphonium iodide, dipentyldipropylphosphonium bromide, dipentyldipropylphosphonium chloride, dihexyldipropylphosphonium iodide, dihexyldipropylphosphonium bromide, dihexyldipropylphosphonium chloride, dipropyldiphenylphosphonium iodide, dipropyldiphenylphosphonium bromide , Dipropyldiphenylphosphonium chloride, diheptyldipropylphosphonium iodide, diheptyldipropylphosphonium bromide, diheptyldipropylphosphonium chloride, dibenzyldipropylphosphonium iodide, dibenzyldipropylphosphonium bromide, dibenzyldipropylphosphonium chloride Dipropyl dioctylphosphonium Dido, dipropyl dioctyl phosphonium bromide, dipropyl dioctyl phosphonium chloride, dipropyl dinonyl phosphonium iodide, dipropyl dinonyl phosphonium bromide, dipropyl dinonyl phosphonium chloride, didecyl dipropyl phosphonium iodide, didecyl dipropyl phosphonium bromide , Didecyldipropylphosphonium chloride, didodecyldipropylphosphonium iodide, didodecyldipropylphosphonium bromide, didodecyldipropylphosphonium chloride, dipropylditetradecylphosphonium iodide, dipropylditetradecylphosphonium bromide, dipropyldi Tetradecyl phosphonium chloride, dihexadecyl dipropyl phosphonium iodide, dihexadecyl dipropyl phosphate Suphonium bromide, dihexadecyl dipropyl phosphonium chloride, dipropyl dioctadecyl phosphonium iodide, dipropyl dioctadecyl phosphonium bromide, dipropyl dioctadecyl phosphonium chloride, dibutyl dipentyl phosphonium iodide, dibutyl dipentyl phosphonium bromide, dibutyl dipentyl phosphonium chloride, Dibutyldihexylphosphonium iodide, dibutyldihexylphosphonium bromide, dibutyldihexylphosphonium chloride, dibutyldiphenylphosphonium iodide, dibutyldiphenylphosphonium bromide, dibutyldiphenylphosphonium chloride, diheptyldibutylphosphonium iodide, diheptyldibutylphosphonium bromide, diheptyldibutylphosphine Nium chloride, dibenzyldibutylphosphonium iodide, dibenzyldibutylphosphonium bromide, dibenzyldibutylphosphonium chloride, dibutyldioctylphosphonium iodide, dibutyldioctylphosphonium bromide, dibutyldioctylphosphonium chloride, dibutyldinonylphosphonium iodide, dibutyldinonylphosphonium bromide , Dibutyldinonylphosphonium chloride, dibutyldidecylphosphonium iodide, dibutyldidecylphosphonium bromide, dibutyldidecylphosphonium chloride, dibutyldidodecylphosphonium iodide, dibutyldidecylphosphonium bromide, dibutyldidodecylphosphonium chloride, dibutylditetradecylphosphonium Iodide, dibutylditetra Silphosphonium bromide, dibutylditetradecylphosphonium chloride, dibutyldihexadecylphosphonium iodide, dibutyldihexadecylphosphonium bromide, dibutyldihexadecylphosphonium chloride, dibutyldioctadecylphosphonium iodide, dibutyldioctadecylphosphonium bromide, dibutyldioctadecylphosphonium Chloride, dihexyl dipentylphosphonium iodide, dihexyl dipentyl phosphonium bromide, dihexyl dipentyl phosphonium chloride, dipentyl diphenyl phosphonium iodide, dipentyl diphenyl phosphonium bromide, dipentyl diphenyl phosphonium chloride, diheptyl dipentyl phosphonium iodide, diheptyl dipentyl phosphonium bromide , Diheptyl dipentyl phosphonium chloride, dibenzyl dipentyl phosphonium iodide, dibenzyl dipentyl phosphonium bromide, dibenzyl dipentyl phosphonium chloride, dipentyl dioctyl phosphonium iodide, dipentyl dioctyl phosphonium bromide, dipentyl dioctyl phosphonium chloride, dipentyl dinonyl phosphonium iodide, Dipentyl dinonyl phosphonium bromide, dipentyl dinonyl phosphonium chloride, didecyl dipentyl phosphonium iodide, didecyl dipentyl phosphonium bromide, didecyl dipentyl phosphonium chloride, didodecyl dipentyl phosphonium iodide, didodecyl dipentyl phosphonium bromide, didodecyl dipentyl phosphonium chloride The Nthyl ditetradecyl phosphonium iodide, dipentyl ditetradecyl phosphonium bromide, dipentyl ditetradecyl phosphonium chloride, dihexadecyl dipentyl phosphonium iodide, dihexadecyl dipentyl phosphonium bromide, dihexadecyl dipentyl phosphonium chloride, dipentyl dioctadecyl phosphonium iodide , Dipentyl dioctadecyl phosphonium bromide, dipentyl dioctadecyl phosphonium chloride, dihexyl diphenyl phosphonium iodide, dihexyl diphenyl phosphonium bromide, dihexyl diphenyl phosphonium chloride, diheptyl dihexyl phosphonium iodide, diheptyl dihexyl phosphonium bromide, diheptyl dihexyl phosphonium Dihexyl phosphonium iodide, dibenzyl dihexyl phosphonium bromide, dibenzyl dihexyl phosphonium chloride, dihexyl dioctyl phosphonium iodide, dihexyl dioctyl phosphonium bromide, dihexyl dioctyl phosphonium chloride, dihexyl dinonyl phosphonium iodide, dihexyl dinonyl phosphonium dibromide Nonylphosphonium chloride, didecyl dihexyl phosphonium iodide, didecyl dihexyl phosphonium bromide, didecyl dihexyl phosphonium chloride, didodecyl dihexyl phosphonium iodide, didodecyl dihexyl phosphonium bromide, didodecyl dihexyl phosphonium chloride, dihexyl ditetradecyl phosphonium chloride Jiheki Silditetradecylphosphonium bromide, dihexylditetradecylphosphonium chloride, dihexadecyldihexylphosphonium iodide, dihexadecyldihexylphosphonium bromide, dihexadecyldihexylphosphonium chloride,
Dihexyldioctadecylphosphonium iodide, dihexyldioctadecylphosphonium bromide, dihexyldioctadecylphosphonium chloride, diheptyldiphenylphosphonium iodide, diheptyldiphenylphosphonium bromide, diheptyldiphenylphosphonium chloride, dibenzyldiphenylphosphonium iodide, dibenzyldiphenylphosphonium bromide , Dibenzyldiphenylphosphonium chloride, dioctyldiphenylphosphonium iodide, dioctyldiphenylphosphonium bromide, dioctyldiphenylphosphonium chloride, dinonyldiphenylphosphonium iodide, dinonyldiphenylphosphonium bromide, dinonyldiphenylphosphonium chloride, didecyldiphenylphosphonium -Dide, didecyldiphenylphosphonium bromide, didecyldiphenylphosphonium chloride, didodecyldiphenylphosphonium iodide, didodecyldiphenylphosphonium bromide, didodecyldiphenylphosphonium chloride, diphenylditetradecylphosphonium iodide, diphenylditetradecylphosphonium bromide, diphenyldi Tetradecylphosphonium chloride, dihexadecyldiphenylphosphonium iodide, dihexadecyldiphenylphosphonium bromide, dihexadecyldiphenylphosphonium chloride, diphenyldioctadecylphosphonium iodide, diphenyldioctadecylphosphonium bromide, diphenyldioctadecylphosphonium chloride, dibenzyldiheptyl Phosphonium Yaw Dibenzyl diheptyl phosphonium bromide, dibenzyl diheptyl phosphonium chloride, diheptyl dioctyl phosphonium iodide, diheptyl dioctyl phosphonium bromide, diheptyl dioctyl phosphonium chloride, diheptyl dinonyl phosphonium iodide, diheptyl dinonyl phosphonium bromide, Diheptyl dinonyl phosphonium chloride, didecyl diheptyl phosphonium iodide, didecyl diheptyl phosphonium bromide, didecyl diheptyl phosphonium chloride, didodecyl diheptyl phosphonium iodide, didodecyl diheptyl phosphonium bromide, didodecyl diheptyl phosphonium chloride Diheptylditetradecylphosphonium iodide, diheptylditetradecylphosphonium bromide Imide, diheptylditetradecylphosphonium chloride, diheptyldihexadecylphosphonium iodide, diheptyldihexadecylphosphonium bromide, diheptyldihexadecylphosphonium chloride, diheptyldioctadecylphosphonium iodide, diheptyldioctadecylphosphonium bromide, Diheptyl dioctadecyl phosphonium chloride, dibenzyl dioctyl phosphonium iodide, dibenzyl dioctyl phosphonium bromide, dibenzyl dioctyl phosphonium chloride, dibenzyl dinonyl phosphonium iodide, dibenzyl dinonyl phosphonium bromide, dibenzyl dinonyl phosphonium chloride, dibenzyl Didecylphosphonium iodide, dibenzyldidecylphosphonium bromide, dibenzyldi Silphosphonium chloride, dibenzyldidodecylphosphonium iodide, dibenzyldidodecylphosphonium bromide, dibenzyldidodecylphosphonium chloride, dibenzylditetradecylphosphonium iodide, dibenzylditetradecylphosphonium bromide, dibenzylditetradecylphosphonium chloride , Dibenzyldihexadecylphosphonium iodide, dibenzyldihexadecylphosphonium bromide, dibenzyldihexadecylphosphonium chloride, dibenzyldioctadecylphosphonium iodide, dibenzyldioctadecylphosphonium bromide, dibenzyldioctadecylphosphonium chloride, benzylethyl Dimethylphosphonium iodide, benzylethyldimethylphosphonium bromide, benzyl ester Dimethylphosphonium chloride, benzylpropyldimethylphosphonium iodide, benzylpropyldimethylphosphonium bromide, benzylpropyldimethylphosphonium chloride, benzylbutyldimethylphosphonium iodide, benzylbutyldimethylphosphonium bromide, benzylbutyldimethylphosphonium chloride, benzyldimethylpentylphosphonium iodide, Benzyldimethylpentylphosphonium bromide, benzyldimethylpentylphosphonium chloride, benzylhexyldimethylphosphonium iodide, benzylhexyldimethylphosphonium bromide, benzylhexyldimethylphosphonium chloride, benzylheptyldimethylphosphonium iodide, benzylheptyldimethylphosphonium bromide , Benzyl heptyldimethylphosphonium chloride, benzyldimethyloctylphosphonium iodide, benzyldimethyloctylphosphonium bromide, benzyldimethyloctylphosphonium chloride, benzyldimethylnonylphosphonium iodide, benzyldimethylnonylphosphonium bromide, benzyldimethylnonylphosphonium chloride, benzyldecyldimethylphosphonium Iodide, benzyldecyldimethylphosphonium bromide, benzyldecyldimethylphosphonium chloride, benzyldimethylundecylphosphonium iodide, benzyldimethylundecylphosphonium bromide, benzyldimethylundecylphosphonium chloride, benzyldodecyldimethylphosphonium iodide, benzyldodecyldimethyl Suphonium bromide, benzyldodecyldimethylphosphonium chloride, benzyldimethyltetradecylphosphonium iodide, benzyldimethyltetradecylphosphonium bromide, benzyldimethyltetradecylphosphonium chloride, dibenzylhexadecyldimethylphosphonium iodide, dibenzylhexadecyldimethylphosphonium bromide, di Benzylhexadecyldimethylphosphonium chloride, dibenzyloctadecyldimethylphosphonium iodide, dibenzyloctadecyldimethylphosphonium bromide, dibenzyloctadecyldimethylphosphonium chloride, tetramethylammonium iodide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium iodide, Traethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium iodide, tetrapentylammonium iodide Bromide, tetrapentylammonium chloride, tetrahexylammonium iodide, tetrahexylammonium bromide, tetrahexylammonium chloride, tetraphenylammonium iodide, tetraphenylammonium bromide, tetraphenylammonium chloride, tetraheptylammonium iodide, tetraheptylammonium bromide Imide, tetraheptylammonium chloride, tetrabenzylammonium iodide, tetrabenzylammonium bromide, tetrabenzylammonium chloride, tetraoctylammonium iodide, tetraoctylammonium bromide, tetraoctylammonium chloride, tetranonylammonium iodide, tetranonylammonium bromide, Tetranonylammonium chloride, tetrakisdecylammonium iodide, tetrakisdecylammonium bromide, tetrakisdecylammonium chloride, tetradodecylammonium iodide, tetradodecylammonium bromide, tetradodecylammonium chloride,
Tetrakis tetradecyl ammonium iodide, tetrakis tetradecyl ammonium bromide, tetrakis tetradecyl ammonium chloride, tetrakis hexadecyl ammonium iodide, tetrakis hexadecyl ammonium bromide, tetrakis hexadecyl ammonium iodide, tetrakis octadecyl ammonium iodide, tetrakis octadecyl ammonium bromide, Tetrakisoctadecylammonium chloride, trimethylpropylammonium iodide, trimethylpropylammonium bromide, trimethylpropylammonium chloride, butyltrimethylammonium iodide, butyltrimethylammonium bromide, butyltrimethylammonium chloride, trimethylpentylammonium iodide , Trimethylpentylammonium bromide, trimethylpentylammonium chloride, hexyltrimethylammonium iodide, hexyltrimethylammonium bromide, hexyltrimethylammonium chloride, heptyltrimethylammonium iodide, heptyltrimethylammonium bromide, heptyltrimethylammonium chloride, trimethylphenylammonium iodide, trimethyl Phenylammonium bromide, trimethylphenylammonium chloride, heptyltrimethylammonium iodide, heptyltrimethylammonium bromide, heptyltrimethylammonium chloride, benzyltrimethylammonium iodide, benzyltrimethylammonium bromide, benzyltrimethylan Nium chloride, trimethyloctylammonium iodide, trimethyloctylammonium bromide, trimethyloctylammonium chloride, trimethylnonylammonium iodide, trimethylnonylammonium bromide, trimethylnonylammonium chloride, decyltrimethylammonium iodide, decyltrimethylammonium bromide, decyltrimethylammonium chloride , Trimethylundecylammonium iodide, trimethylundecylammonium bromide, trimethylundecylammonium chloride, dodecyltrimethylammonium iodide, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, trimethyltetradecylammonium iodide, trimethylte Tradecylammonium bromide, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium iodide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, trimethyloctadecylammonium iodide, trimethyloctadecylammonium bromide, trimethyloctadecylammonium chloride, triethylmethylammonium iodide , Triethylmethylammonium bromide, triethylmethylammonium chloride, triethylpropylammonium iodide, triethylpropylammonium bromide, triethylpropylammonium chloride, triethylbutylammonium iodide, triethylbutylammonium bromide, triethylbutyl Ammonium chloride, triethylpentylammonium iodide, triethylpentylammonium bromide, triethylpentylammonium chloride, triethylhexylammonium iodide, triethylhexylammonium bromide, triethylhexylammonium chloride, triethylphenylammonium iodide, triethylphenylammonium bromide, triethylphenylammonium chloride , Triethylheptylammonium iodide, triethylheptylammonium bromide, triethylheptylammonium chloride, benzyltriethylammonium iodide, benzyltriethylammonium bromide, benzyltriethylammonium chloride, triethyloctylammonium iodide, tri Tyloctylammonium bromide, triethyloctylammonium chloride, triethylnonylammonium iodide, triethylnonylammonium bromide, triethylnonylammonium chloride, triethyldecylammonium iodide, triethyldecylammonium bromide, triethyldecylammonium chloride, triethylundecylammonium iodide, triethyl Undecyl ammonium bromide, triethyl undecyl ammonium chloride, triethyl dodecyl ammonium iodide, triethyl dodecyl ammonium bromide, triethyl dodecyl ammonium chloride, triethyl tetradecyl ammonium iodide, triethyl tetradecyl ammonium bromide, triethyl tetradecyl ammonium Um chloride, triethyl hexadecyl ammonium iodide, triethyl hexadecyl ammonium bromide, triethyl hexadecyl ammonium chloride, triethyl octadecyl ammonium iodide, triethyl octadecyl ammonium bromide, triethyl octadecyl ammonium chloride, methyl tripropyl ammonium iodide, methyl tripropyl ammonium bromide, Methyltripropylammonium chloride, ethyltripropylammonium iodide, ethyltripropylammonium bromide, ethyltripropylammonium chloride, butyltripropylammonium iodide, butyltripropylammonium bromide, butyltripropylammonium chloride, pentyltripropylammonium Muzide, pentyltripropylammonium bromide, pentyltripropylammonium chloride, hexyltripropylammonium iodide, hexyltripropylammonium bromide, hexyltripropylammonium chloride, phenyltripropylammonium iodide, phenyltripropylammonium bromide, phenyltripropylammonium Chloride, heptyltripropylammonium iodide, heptyltripropylammonium bromide, heptyltripropylammonium chloride, benzyltripropylammonium iodide, benzyltripropylammonium bromide, benzyltripropylammonium chloride, octyltripropylammonium iodide, octyltripropyl A Moniumuburomido, octyl tripropyl ammonium chloride, nonyl tripropyl ammonium iodide, nonyl tripropyl ammonium bromide, nonyl tripropyl ammonium chloride,
Decyltripropylammonium iodide, decyltripropylammonium bromide, decyltripropylammonium chloride, tripropylundecylammonium iodide, tripropylundecylammonium bromide, tripropylundecylammonium chloride, dodecyltripropylammonium iodide, dodecyltri Propylammonium bromide, dodecyltripropylammonium chloride, tetradecyltripropylammonium iodide, tetradecyltripropylammonium bromide, tetradecyltripropylammonium chloride, hexadecyltripropylammonium iodide, hexadecyltripropylammonium bromide, hexadecyltri Propyl ammonium chloride, octadecyl Ripropylammonium iodide, Octadecyltripropylammonium bromide, Octadecyltripropylammonium chloride, Tributylmethylammonium iodide, Tributylmethylammonium bromide, Tributylmethylammonium chloride, Tributylethylammonium iodide, Tributylethylammonium bromide, Tributylethylammonium chloride, Tributylpropylammonium iodide, tributylpropylammonium bromide, tributylpropylammonium chloride, tributylpentylammonium iodide, tributylpentylammonium bromide, tributylpentylammonium chloride, tributylhexylammonium iodide, tributylhexylammonium iodide , Tributylhexylammonium chloride, tributylphenylammonium iodide, tributylphenylammonium bromide, tributylphenylammonium chloride, tributylheptylammonium iodide, tributylheptylammonium bromide, tributylheptylammonium chloride, benzyltributylammonium iodide, benzyltributylammonium bromide, Benzyltributylammonium chloride, tributyloctylammonium iodide, tributyloctylammonium bromide, tributyloctylammonium chloride, tributylnonylammonium iodide, tributylnonylammonium bromide, tributylnonylammonium chloride, tributyldecylammonium Muiodide, tributyldecylammonium bromide, tributyldecylammonium chloride, tributylundecylammonium iodide, tributylundecylammonium bromide, tributylundecylammonium chloride, tributyldodecylammonium iodide, tributyldodecylammonium bromide, tributyldodecylammonium chloride, tributyltetradecyl Ammonium iodide, tributyltetradecylammonium bromide, tributyltetradecylammonium chloride, tributylhexadecylammonium iodide, tributylhexadecylammonium bromide, tributylhexadecylammonium chloride, tributyloctadecylammonium iodide, tributyloctadecylamine Monium bromide, tributyl octadecyl ammonium chloride, methyl tripentyl ammonium iodide, methyl tripentyl ammonium bromide, methyl tripentyl ammonium chloride, ethyl tripentyl ammonium iodide, ethyl tripentyl ammonium bromide, ethyl tripentyl ammonium chloride, tripentylpropyl ammonium Iodide, tripentylpropylammonium bromide, tripentylpropylammonium chloride, butyltripentylammonium iodide, butyltripentylammonium bromide, butyltripentylammonium chloride, hexyltripentylammonium iodide, hexyltripentylammonium bromide, hexyltripentyl Ammonium Lolide, tripentylphenylammonium iodide, tripentylphenylammonium bromide, tripentylphenylammonium chloride, heptyllipentylammonium iodide, heptyllipentylammonium bromide, heptyllipentylammonium chloride, benzyltripentylammonium iodide, benzyltripentyl Ammonium bromide, benzyltripentylammonium chloride, octyltripentylammonium iodide, octyltripentylammonium bromide, octyllipentylammonium chloride, nonyltripentylammonium iodide, nonyltripentylammonium bromide, nonyltripentylammonium chloride, decyltripentyl Ammonium yo Zido, Decyltripentylammonium bromide, Decyltripentylammonium chloride, Tripentylundecylammonium iodide, Tripentylundecylammonium bromide, Tripentylundecylammonium chloride, Dodecyltripentylammonium iodide, Dodecyltripentylammonium bromide, Dodecyl Tripentylammonium chloride, tetradecyltripentylammonium iodide, dodecyltripentylammonium bromide, dodecyltripentylammonium chloride, tripentyltetradecylammonium iodide, tripentyltetradecylammonium bromide, tripentyltetradecylammonium chloride, hexadecyltri Pentylammonium iodide, hexade Rutripentylammonium bromide, hexadecyltripentylammonium chloride, octadecyltripentylammonium iodide, octadecyltripentylammonium bromide, octadecyltripentylammonium chloride, trihexylmethylammonium iodide, trihexylmethylammonium bromide, trihexylmethylammonium chloride, Ethyltrihexylammonium iodide, ethyltrihexylammonium bromide, ethyltrihexylammonium chloride, trihexylpropylammonium iodide, trihexylpropylammonium bromide, trihexylpropylammonium chloride, butyltrihexylammonium iodide, butyltrihexylammonium bromide Butyltrihexylammonium chloride, trihexylpentylammonium iodide, trihexylpentylammonium bromide, trihexylpentylammonium chloride, trihexylphenylammonium iodide, trihexylphenylammonium bromide, trihexylphenylammonium chloride, heptyltrihexylammonium iodide , Heptyltrihexylammonium bromide, heptyltrihexylammonium chloride, benzyltrihexylammonium iodide, benzyltrihexylammonium bromide, benzyltrihexylammonium chloride, trihexyloctylammonium iodide, trihexyloctylammonium bromide, trihexyloctylammonium chloride Trihexyl nonyl ammonium iodide, trihexyl nonyl ammonium bromide, trihexyl nonyl ammonium chloride, decyl trihexyl ammonium iodide, decyl trihexyl ammonium bromide, decyl trihexyl ammonium chloride, trihexyl undecyl ammonium iodide, trihexyl Undecyl ammonium bromide, trihexyl undecyl ammonium chloride, dodecyl trihexyl ammonium iodide, dodecyl trihexyl ammonium bromide, dodecyl trihexyl ammonium chloride, trihexyl tetradecyl ammonium iodide, trihexyl tetradecyl ammonium bromide, trihexyl tetradecyl Ammonium chloride, hexadecyltrihexyl urea Monium iodide, hexadecyltrihexylammonium bromide, hexadecyltrihexylammonium chloride, trihexyloctadecylammonium iodide, trihexyloctadecylammonium bromide, trihexyloctadecylammonium chloride, methyltriphenylammonium iodide, methyltriphenylammonium bromide, Methyltriphenylammonium chloride, ethyltriphenylammonium iodide, ethyltriphenylammonium bromide, ethyltriphenylammonium chloride, triphenylpropylammonium iodide, triphenylpropylammonium bromide, triphenylpropylammonium chloride, butyltriphenylammonium iodide , Butyl tri Phenylammonium bromide, butyltriphenylammonium chloride, hexyltriphenylammonium iodide, hexyltriphenylammonium bromide, hexyltriphenylammonium chloride, pentyltriphenylammonium iodide, pentyltriphenylammonium bromide, pentyltriphenylammonium chloride, hexyltri Phenylammonium iodide, hexyltriphenylammonium bromide, hexyltriphenylammonium chloride, heptyltriphenylammonium iodide, heptyltriphenylammonium bromide, heptyltriphenylammonium chloride, benzyltriphenylammonium iodide, benzyltriphenylammonium bromide, benzyltol Riphenylammonium chloride, Octyltriphenylammonium iodide, Octyltriphenylammonium bromide, Octyltriphenylammonium chloride, Nonyltriphenylammonium iodide, Nonyltriphenylammonium bromide, Nonyltriphenylammonium chloride, Decyltriphenylammonium iodide, Decyltriphenylammonium bromide, decyltriphenylammonium chloride, triphenylndecylammonium iodide, triphenylndecylammonium bromide, triphenylndecylammonium chloride, dodecyltriphenylammonium iodide, dodecyltriphenylammonium bromide, dodecyltriphenyl Ammonium chloride, tetradecyltri Enylammonium iodide, tetradecyltriphenylammonium bromide, tetradecyltriphenylammonium chloride, triphenyltetradecylammonium iodide, triphenyltetradecylammonium bromide, triphenyltetradecylammonium chloride, hexadecyltriphenylammonium iodide, hexa Decyltriphenylammonium bromide, hexadecyltriphenylammonium chloride, octadecyltriphenylammonium iodide, octadecyltriphenylammonium bromide, octadecyltriphenylammonium chloride, triheptylmethylammonium iodide, triheptylmethylammonium bromide, triheptylmethylammonium chloride , Ethyltri Heptyl ammonium iodide, ethyl tri-heptyl bromide, ethyl tri-heptyl ammonium chloride,
Triheptylpropylammonium iodide, triheptylpropylammonium bromide, triheptylpropylammonium chloride, butyltriheptylammonium iodide, butyltriheptylammonium bromide, butyltriheptylammonium chloride, triheptylpentylammonium iodide, triheptylpentylammonium bromide , Triheptylpentylammonium chloride, triheptylhexylammonium iodide, triheptylhexylammonium bromide, triheptylhexylammonium chloride, triheptyloctylammonium iodide, triheptyloctylammonium bromide, triheptyloctylammonium chloride, triheptylnonylammonium iodide De, G Heptylnonylammonium bromide, triheptylnonylammonium chloride, decyltriheptylammonium iodide, decyltriheptylammonium bromide, decyltriheptylammonium chloride, triheptylundecylammonium iodide, triheptylundecylammonium bromide, triheptylundecylammonium Chloride, dodecyltriheptylammonium iodide, dodecyltriheptylammonium bromide, dodecyltriheptylammonium chloride, triheptyltetradecylammonium iodide, triheptyltetradecylammonium bromide, triheptyltetradecylammonium chloride, triheptylhexadecylammonium iodide , Triheptylhexadecyla Monium bromide, triheptylhexadecyl ammonium chloride, tribenzylmethylammonium iodide, tribenzylmethylammonium bromide, tribenzylmethylammonium chloride, tribenzylethylammonium iodide, tribenzylethylammonium bromide, tribenzylethylammonium chloride, tribenzyl Propylammonium iodide, tribenzylpropylammonium bromide, tribenzylpropylammonium chloride, tribenzylbutylammonium iodide, tribenzylbutylammonium bromide, tribenzylbutylammonium chloride, tribenzylpentylammonium iodide, tribenzylpentylammonium bromide, tri Benzylpentylammonium Chloride, tribenzylhexylammonium iodide, tribenzylhexylammonium bromide, tribenzylhexylammonium chloride, tribenzylphenylammonium iodide, tribenzylphenylammonium bromide, tribenzylphenylammonium chloride, tribenzylheptylammonium iodide, tribenzylheptyl Ammonium bromide, tribenzylheptylammonium chloride, tribenzyloctylammonium iodide, tribenzyloctylammonium bromide, tribenzyloctylammonium chloride, tribenzylnonylammonium iodide, tribenzylnonylammonium bromide, tribenzylnonylammonium chloride, tribenzyldecyl Ammonium Yo Zido, Tribenzyldecylammonium bromide, Tribenzyldecylammonium chloride, Tribenzylundecylammonium iodide, Tribenzylundecylammonium bromide, Tribenzylundecylammonium chloride, Tribenzyldodecylammonium iodide, Tribenzyldodecylammonium bromide, Tribenzyldodecylammonium bromide Benzyldodecylammonium chloride, tribenzyltetradecylammonium iodide, tribenzyltetradecylammonium bromide, tribenzyltetradecylammonium chloride, tribenzylhexadecylammonium iodide, tribenzylhexadecylammonium bromide, tribenzylhexadecylammonium chloride, tribenzyl Benzyl octadecyl ammonium iodide Tribenzyl octadecyl ammonium bromide, tribenzyl octadecyl ammonium chloride, methyl trioctyl ammonium iodide, methyl trioctyl ammonium bromide, methyl trioctyl ammonium chloride, ethyl trioctyl ammonium iodide, ethyl trioctyl ammonium bromide, ethyl trioctyl ammonium chloride, Trioctylpropylammonium iodide, trioctylpropylammonium bromide, trioctylpropylammonium chloride, butyltrioctylammonium iodide, butyltrioctylammonium bromide, butyltrioctylammonium chloride, trioctylpentylammonium iodide, trioctylpentylammonium bromide ,bird Octylpentylammonium chloride, hexyltrioctylammonium iodide, hexyltrioctylammonium bromide, hexyltrioctylammonium chloride, heptyltrioctylammonium iodide, heptyltrioctylammonium bromide, heptyltrioctylammonium chloride, nonyltrioctylammonium iodide, Nonyltrioctylammonium bromide, nonyltrioctylammonium chloride, decyltrioctylammonium iodide, decyltrioctylammonium bromide, decyltrioctylammonium chloride, trioctylundecylammonium iodide, trioctylundecylammonium bromide, trioctylundecyl Ammonium chloride, dode Trioctylammonium iodide, dodecyltrioctylammonium bromide, dodecyltrioctylammonium chloride, trioctyltetradecylammonium iodide, trioctyltetradecylammonium bromide, trioctyltetradecylammonium chloride, hexadecyltrioctylammonium iodide, hexadecyl Trioctylammonium bromide, hexadecyltrioctylammonium chloride, octadecyltrioctylammonium iodide, octadecyltrioctylammonium bromide, octadecyltrioctylammonium chloride, diethyldimethylammonium iodide, diethyldimethylammonium bromide, diethyldimethylammonium chloride, dimethyldipropiol Ammonium iodide, dimethyldipropylammonium bromide, dimethyldipropylammonium chloride, dibutyldimethylammonium iodide, dibutyldimethylammonium bromide, dibutyldimethylammonium chloride, dimethyldipentylammonium iodide, dimethyldipentylammonium bromide, dimethyldipentylammonium chloride, dihexyldimethyl Ammonium iodide, dihexyldimethylammonium bromide, dihexyldimethylammonium chloride, dimethyldiphenylammonium iodide, dimethyldiphenylammonium bromide, dimethyldiphenylammonium chloride, diheptyldimethylammonium iodide, diheptyldimethylammonium bromide, diheptyl Dimethyl ammonium chloride, dibenzyl dimethyl ammonium iodide, dibenzyl dimethyl ammonium bromide, dibenzyl dimethyl ammonium chloride, dimethyl dioctyl ammonium iodide, dimethyl dioctyl ammonium bromide, dimethyl dioctyl ammonium chloride, dimethyl dinonyl ammonium iodide, dimethyl dinonyl ammonium Bromide, dimethyldinonylammonium chloride, didecyldimethylammonium iodide, didecyldimethylammonium bromide, didecyldimethylammonium chloride, didodecyldimethylammonium iodide, didodecyldimethylammonium bromide, didodecyldimethylammonium chloride, dimethylditetradecyl Ammonium iodide, dimethyl Ruditetradecylammonium bromide, dimethylditetradecylammonium chloride, dihexadecyldimethylammonium iodide, dihexadecyldimethylammonium bromide, dihexadecyldimethylammonium chloride, dimethyldioctadecylammonium iodide, dimethyloctadecylammonium bromide, dimethyloctadecylammonium Chloride, diethyldipropylammonium iodide, diethyldipropylammonium bromide, diethyldipropylammonium chloride, dibutyldiethylammonium iodide, dibutyldiethylammonium bromide, dibutyldiethylammonium chloride, diethyldipentylammonium iodide, diethyldipentylammonium bromide, diethyl Pentylammonium chloride, diethyldihexylammonium iodide, diethyldihexylammonium bromide, diethyldihexylammonium chloride, diethyldiphenylammonium iodide, diethyldiphenylammonium bromide, diethyldiphenylammonium chloride, diheptyldiethylammonium iodide, diheptyldiethylammonium bromide, di Heptyl diethylammonium chloride, dibenzyldiethylammonium iodide, dibenzyldiethylammonium bromide, dibenzyldiethylammonium chloride, diethyldioctylammonium iodide, diethyldioctylammonium bromide, diethyldioctylammonium chloride, diethyldinonylammonium iodide , Diethyl dinonyl ammonium bromide, diethyl dinonyl ammonium chloride, didecyl diethyl ammonium iodide, didecyl diethyl ammonium bromide, didecyl diethyl ammonium chloride, didodecyl diethyl ammonium iodide, didodecyl diethyl ammonium bromide, didodecyl diethyl ammonium chloride Diethylditetradecylammonium iodide, diethylditetradecylammonium bromide, diethylditetradecylammonium chloride, diethyldihexadecylammonium iodide, diethyldihexadecylammonium bromide, diethyldihexadecylammonium chloride, diethyldioctadecylammonium iodide Diethyldioctadecylammonium bromide, di Tildioctadecylammonium chloride, dibutyldipropylammonium iodide, dibutyldipropylammonium bromide, dibutyldipropylammonium chloride, dipentyldipropylammonium iodide, dipentyldipropylammonium bromide, dipentyldipropylammonium chloride, dihexyldipropylammonium iodide , Dihexyl dipropyl ammonium bromide, dihexyl dipropyl ammonium chloride, dipropyl diphenyl ammonium iodide, dipropyl diphenyl ammonium bromide, dipropyl diphenyl ammonium chloride, diheptyl dipropyl ammonium iodide, diheptyl dipropyl ammonium bromide, diheptyl di Propylammonium chloride,
Dibenzyldipropylammonium iodide, dibenzyldipropylammonium bromide, dibenzyldipropylammonium chloride, dipropyldioctylammonium iodide, dipropyldioctylammonium bromide, dipropyldioctylammonium chloride, dipropyldinonylammonium iodide, di Propyl dinonyl ammonium bromide, dipropyl dinonyl ammonium chloride, didecyl dipropyl ammonium iodide, didecyl dipropyl ammonium bromide, didecyl dipropyl ammonium chloride, didodecyl dipropyl ammonium iodide, didodecyl dipropyl ammonium bromide, Didodecyl dipropyl ammonium chloride, dipropyl ditetradecyl ammonium iodide, di Ropil ditetradecyl ammonium bromide, dipropyl ditetradecyl ammonium chloride, dihexadecyl dipropyl ammonium iodide, dihexadecyl dipropyl ammonium bromide, dihexadecyl dipropyl ammonium chloride, dipropyl dioctadecyl ammonium iodide, di Propyl dioctadecyl ammonium bromide, dipropyl dioctadecyl ammonium chloride, dibutyl dipentyl ammonium iodide, dibutyl dipentyl ammonium bromide, dibutyl dipentyl ammonium chloride, dibutyl dihexyl ammonium iodide, dibutyl dihexyl ammonium bromide, dibutyl dihexyl ammonium chloride, dibutyl diphenyl ammonium iodide Dibutyl diphenyla Monium bromide, dibutyldiphenylammonium chloride, diheptyldibutylammonium iodide, diheptyldibutylammonium bromide, diheptyldibutylammonium chloride, dibenzyldibutylammonium iodide, dibenzyldibutylammonium bromide, dibenzyldibutylammonium chloride, dibutyldioctylammonium iodide Dibutyl dioctyl ammonium bromide, dibutyl dioctyl ammonium chloride, dibutyl dinonyl ammonium iodide, dibutyl dinonyl ammonium bromide, dibutyl dinonyl ammonium chloride, dibutyl didecyl ammonium iodide, dibutyl didecyl ammonium bromide, dibutyl didecyl ammonium chloride, Dibutyl didodecyl Ammonium iodide, dibutyldidodecylammonium bromide, dibutyldidodecylammonium chloride, dibutylditetradecylammonium iodide, dibutylditetradecylammonium bromide, dibutylditetradecylammonium chloride, dibutyldihexadecylammonium iodide, dibutyldihexadecyl Ammonium bromide, dibutyldihexadecylammonium chloride, dibutyldioctadecylammonium iodide, dibutyldioctadecylammonium bromide, dibutyldioctadecylammonium chloride, dihexyldipentylammonium iodide, dihexyldipentylammonium bromide, dihexyldipentylammonium chloride, dipentyldiphenylammonium iodide The Nethyldiphenylammonium bromide, dipentyldiphenylammonium chloride, diheptyldipentylammonium iodide, diheptyldipentylammonium bromide, diheptyldipentylammonium chloride, dibenzyldipentylammonium iodide, dibenzyldipentylammonium bromide, dibenzyldipentylammonium chloride, dipentyl Dioctyl ammonium iodide, dipentyl dioctyl ammonium bromide, dipentyl dioctyl ammonium chloride, dipentyl dinonyl ammonium iodide, dipentyl dinonyl ammonium bromide, dipentyl dinonyl ammonium chloride,
Didecyl dipentyl ammonium iodide, didecyl dipentyl ammonium bromide, didecyl dipentyl ammonium chloride, didodecyl dipentyl ammonium iodide, didodecyl dipentyl ammonium bromide, didodecyl dipentyl ammonium chloride, dipentyl ditetradecyl ammonium iodide, dipentyl ditetradecyl Ammonium bromide, dipentyl ditetradecyl ammonium chloride, dihexadecyl dipentyl ammonium iodide, dihexadecyl dipentyl ammonium bromide, dihexadecyl dipentyl ammonium chloride, dipentyl dioctadecyl ammonium iodide, dipentyl dioctadecyl ammonium bromide, dipentyl dioctadecyl ammonium chloride , Jihe Didiphenylammonium iodide, dihexyldiphenylammonium bromide, dihexyldiphenylammonium chloride, diheptyldihexylammonium iodide, diheptyldihexylammonium bromide, diheptyldihexylammonium chloride, dibenzyldihexylammonium iodide, dibenzyldihexylammonium bromide, dibenzyl Dihexyl ammonium chloride, dihexyl dioctyl ammonium iodide, dihexyl dioctyl ammonium bromide, dihexyl dioctyl ammonium chloride, dihexyl dinonyl ammonium iodide, dihexyl dinonyl ammonium bromide, dihexyl dinonyl ammonium chloride, didecyl dihexyl ammonium iodide, didecyl Hexyl ammonium bromide, didecyl dihexyl ammonium chloride, didodecyl dihexyl ammonium iodide, didodecyl dihexyl ammonium bromide, didodecyl dihexyl ammonium chloride, dihexyl ditetradecyl ammonium iodide, dihexyl ditetradecyl ammonium bromide, dihexyl ditetradecyl ammonium chloride Dihexadecyl dihexyl ammonium iodide, dihexadecyl dihexyl ammonium bromide, dihexadecyl dihexyl ammonium chloride, dihexyl dioctadecyl ammonium iodide, dihexyl dioctadecyl ammonium bromide, dihexyl dioctadecyl ammonium chloride, diheptyl diphenyl ammonium iodide, diheptyl diph Phenylammonium bromide, diheptyldiphenylammonium chloride, dibenzyldiphenylammonium iodide, dibenzyldiphenylammonium bromide, dibenzyldiphenylammonium chloride, dioctyldiphenylammonium iodide, dioctyldiphenylammonium bromide, dioctyldiphenylammonium chloride, dinonyldiphenylammonium iodide , Dinonyl diphenyl ammonium bromide, dinonyl diphenyl ammonium chloride, didecyl diphenyl ammonium iodide, didecyl diphenyl ammonium bromide, didecyl diphenyl ammonium chloride, didodecyl diphenyl ammonium bromide, didodecyl diphenyl ammonium bromide, didodecyl diphenyl Ammonium chloride, diphenylditetradecylammonium iodide, diphenylditetradecylammonium bromide, diphenylditetradecylammonium chloride, dihexadecyldiphenylammonium iodide, dihexadecyldiphenylammonium bromide, dihexadecyldiphenylammonium chloride, diphenyldioctadecyl Ammonium iodide, diphenyl dioctadecyl ammonium bromide, diphenyl dioctadecyl ammonium chloride, dibenzyl diheptyl ammonium iodide, dibenzyl diheptyl ammonium bromide, dibenzyl diheptyl ammonium chloride, diheptyl dioctyl ammonium iodide, diheptyl dioctyl ammonium bromide Diheptyl dioctyl Ammonium chloride, diheptyl dinonyl ammonium iodide, diheptyl dinonyl ammonium bromide, diheptyl dinonyl ammonium chloride, didecyl diheptyl ammonium iodide, didecyl diheptyl ammonium bromide, didecyl diheptyl ammonium chloride, didodecyl dichloride Heptylammonium iodide, didodecyldiheptylammonium bromide, didodecyldiheptylammonium chloride, diheptylditetradecylammonium iodide, diheptylditetradecylammonium bromide, diheptylditetradecylammonium chloride, diheptyldihexadecylammonium Iodide, diheptyl dihexadecyl ammonium bromide, diheptyl dihexadecyl ammonium chloride, diheptyl Ptyl dioctadecyl ammonium iodide, diheptyl dioctadecyl ammonium bromide, diheptyl dioctadecyl ammonium chloride, dibenzyl dioctyl ammonium iodide, dibenzyl dioctyl ammonium bromide, dibenzyl dioctyl ammonium chloride, dibenzyl dinonyl ammonium iodide, dibenzyl Dinonyl ammonium bromide, dibenzyl dinonyl ammonium chloride, dibenzyl didecyl ammonium iodide, dibenzyl didecyl ammonium bromide, dibenzyl didecyl ammonium chloride, dibenzyl didodecyl ammonium iodide, dibenzyl didodecyl ammonium bromide, di Benzyl didodecyl ammonium chloride, dibenzyl ditetradecyl ammonium iodide Dibenzylditetradecylammonium bromide, dibenzylditetradecylammonium chloride, dibenzyldihexadecylammonium iodide, dibenzyldihexadecylammonium bromide, dibenzyldihexadecylammonium chloride, dibenzyldioctadecylammonium iodide , Dibenzyldioctadecylammonium bromide, dibenzyldioctadecylammonium chloride, benzylethyldimethylammonium iodide, benzylethyldimethylammonium bromide, benzylethyldimethylammonium chloride, benzylpropyldimethylammonium iodide, benzylpropyldimethylammonium bromide, benzylpropyldimethyl Ammonium chloride, benzylbutyldimethyl Ammonium iodide, benzylbutyldimethylammonium bromide, benzylbutyldimethylammonium chloride, benzyldimethylpentylammonium iodide, benzyldimethylpentylammonium bromide, benzyldimethylpentylammonium chloride, benzylhexyldimethylammonium iodide, benzylhexyldimethylammonium bromide, benzylhexyl Dimethylammonium chloride, benzylheptyldimethylammonium iodide, benzylheptyldimethylammonium bromide, benzylheptyldimethylammonium chloride, benzyldimethyloctylammonium iodide, benzyldimethyloctylammonium bromide, benzyldimethyloctylammonium chloride, benzyl Didimethylnonylammonium iodide, benzyldimethylnonylammonium bromide, benzyldimethylnonylammonium chloride, benzyldecyldimethylammonium iodide, benzyldecyldimethylammonium bromide, benzyldecyldimethylammonium chloride, benzyldimethylundecylammonium iodide, benzyldimethylundecyl Ammonium bromide, benzyldimethylundecylammonium chloride, benzyldodecyldimethylammonium iodide, benzyldodecyldimethylammonium bromide, benzyldodecyldimethylammonium chloride, benzyldimethyltetradecylammonium iodide, benzyldimethyltetradecylammonium bromide, benzyldimethyltetradecyl Ammonium chloride, dibenzyl hexadecyl dimethyl ammonium iodide, dibenzyl hexadecyl dimethyl ammonium bromide, dibenzyl hexadecyl dimethyl ammonium chloride, dibenzyl octadecyl dimethyl ammonium iodide, dibenzyl octadecyl dimethyl ammonium bromide, dibenzyl octadecyl dimethyl ammonium chloride,
Methyl pyridinium iodide, methyl pyridinium bromide, methyl pyridinium chloride, ethyl pyridinium iodide, ethyl pyridinium bromide, ethyl pyridinium chloride, propyl pyridinium iodide, propyl pyridinium bromide, propyl pyridinium chloride, butyl pyridinium iodide, butyl pyridinium bromide, butyl pyridinium Chloride, pentylpyridinium iodide, pentylpyridinium bromide, pentylpyridinium chloride, hexylpyridinium iodide, hexylpyridinium bromide, hexylpyridinium chloride, heptylpyridinium iodide, heptylpyridinium bromide, heptylpyridinium chloride, octylpyridiniumpyridinium iodide Octylpyridinium chloride, nonylpyridinium iodide, nonylpyridinium bromide, nonylpyridinium chloride, decylpyridinium iodide, decylpyridinium bromide, decylpyridinium chloride, undecylpyridinium iodide, undecylpyridinium bromide, undecylpyridinium chloride, dodecylpyridinium chloride, dodecylpyridinium chloride Iodide, dodecylpyridinium bromide, dodecylpyridinium chloride, tetradecylpyridinium iodide, tetradecylpyridinium bromide, tetradecylpyridinium chloride, hexadecylpyridinium iodide, hexadecylpyridinium bromide, hexadecylpyridinium chloride, octadecylpyridinium iodide, octadecylpyridinium iodide Bromide, ok Decylpyridinium chloride, 1,3-dimethylimidazolium iodide, 1,3-dimethylimidazolium bromide, 1,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium iodide, 1-ethyl-3- Methyl imidazolium bromide, 1-ethyl-3-methyl imidazolium chloride, 1-propyl-3-methyl imidazolium iodide, 1-propyl-3-methyl imidazolium bromide, 1-propyl-3-methyl imidazolium chloride, 1-butyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-pentyl-3-methylimidazolium iodide, 1-pentyl- 3-methylimidazolium bromide, 1-pentyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium iodide, 1-hex -3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-heptyl-3-methylimidazolium iodide, 1-heptyl-3-methylimidazolium bromide, 1-heptyl-3-methylimidazole Lilium chloride, 1-octyl-3-methylimidazolium iodide, 1-octyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride, 1-nonyl-3-methylimidazolium iodide, 1 -Nonyl-3-methylimidazolium bromide, 1-nonyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium iodide, 1-decyl-3-methylimidazolium bromide, 1-decyl-3- Methylimidazolium chloride, 1-undecyl-3-methylimidazolium iodide, 1-undecyl-3-methylimidazolium bromide, 1-undecyl-3-methyl Dazolium chloride, 1-dodecyl-3-methylimidazolium iodide, 1-dodecyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium iodide, 1-tetradecyl-3-methylimidazolium bromide, 1-tetradecyl-3-methylimidazolium chloride, 1-hexadecyl-3-methylimidazolium iodide, 1-hexadecyl-3-methylimidazolium bromide, 1-hexadecyl-3 -Methylimidazolium chloride, 1-octadecyl-3-methylimidazolium iodide, 1-octadecyl-3-methylimidazolium bromide, 1-octadecyl-3-methylimidazolium chloride, 2,3,5-triphenyltetrazolium iodide 2,3,5-triphenyltetrazolium bromide, 2,3,5-triphenyltetrazolium bromide Lido, 2,3,5-Tolyltetrazolium iodide, 2,3,5-Tolyltetrazolium bromide, 2,3,5-Tolyltetrazolium chloride, Tetramethylarsonium iodide, Tetramethylarsonium bromide, Tetra Methylarsonium chloride, tetraethylarsonium iodide, tetraethylarsonium bromide, tetraethylarsonium chloride, tetrapropylarsonium iodide, tetrapropylarsonium bromide, tetrapropylarsonium chloride, tetrabutylarsonium iodide, tetrabutylarso Nitrobromide, Tetrabutylarsonium chloride, Tetrapentylarsonium iodide, Tetrapentylarsonium bromide, Tetrapentylarsonium chloride, Tetrahexylarsonium Muzide, tetrahexylarsonium bromide, tetrahexylarsonium chloride, tetraphenylarsonium iodide, tetraphenylarsonium bromide, tetraphenylarsonium chloride, tetrapentylarsonium iodide, tetrapentylarsonium bromide, tetrapentylarsonium Chloride, tetratolylarsonium iodide, tetratolylarsonium bromide, tetratolylarsonium chloride, methyltriphenylarsonium iodide, methyltriphenylarsonium bromide, methyltriphenylarsonium chloride, ethyltriphenylarsonium iodide, Ethyltriphenylarsonium bromide, ethyltriphenylarsonium chloride, propyltriphenylarso Um iodide, propyltriphenylarsonium bromide, propyltriphenylarsonium chloride, butyltriphenylarsonium iodide, butyltriphenylarsonium bromide, butyltriphenylarsonium chloride, pentyltriphenylarsonium iodide, pentyltriphenylarso Nitrobromide, pentyltriphenylarsonium chloride, hexyltriphenylarsonium iodide, hexyltriphenylarsonium bromide, hexyltriphenylarsonium chloride, benzyltriphenylarsonium iodide, benzyltriphenylarsonium bromide, benzyltriphenyl Examples include arsonium chloride.
In all the above cases, the alkyl group is not limited to the n-form, and may be iso-, sec-, tert-, cyclo- or other branched forms, and is not necessarily limited to these onium salts. These may have a cyclic structure in which the substituents are bonded to each other, or may contain an unsaturated bond or a hetero element.
These onium salts are not necessarily required to coexist with the substrate from the beginning of the reaction, and any one or more of them may be produced in the reactor. Specifically, substances containing these onium salt hydroxides, carbonates and the like are mixed with acids containing chloride ions, bromide ions, iodide ions, or raw materials such as organic amines, organic phosphines, organic arsines, It can also be produced in the system by reacting organic antimony with an alkyl halide, aryl halide, or vinyl halide.
The onium salt may be used by mixing other onium salts, other salts, metal complexes and the like. In particular, when bromide or iodide salt is added, the same effect as ion exchange can be obtained.

  As the inorganic solid substance in the second embodiment, the same materials as those shown in the first embodiment can be used.

  The quantity ratio of the ionic substance containing the Group 15 element and the inorganic solid substance in the first and second embodiments may be arbitrary, and preferably the ionic substance containing the Group 15 element is 0% of the weight of the inorganic solid substance. It is desirable to include about 0.001 to 1000 times.

  As an advantage of using a mixed system catalyst of an ionic substance containing a Group 15 element and an inorganic solid substance of the second aspect, the catalytic activity is enhanced and the reaction is accelerated, and the recovery of the catalyst after the reaction is also possible. It can be easier. In particular, since silica efficiently adsorbs and precipitates the onium salt in the product cyclic carbonate, most of the catalyst is deposited on the silica only by cooling the product after the reaction to near or below room temperature. It is recovered and product purification is facilitated including distillation.

  The catalyst system of the second aspect works sufficiently just by mixing two kinds of substances in a reaction vessel, but it is necessary to uniformly disperse an ionic substance (onium salt) containing a Group 15 element in advance. Is also possible. For this purpose, any organic solvent in which an onium salt is dissolved, preferably ketones or alcohols having a boiling point of 100 ° C. or lower, esters such as ethylene carbonate or propylene carbonate, dimethylacetamide, dimethylformamide, N-methyloxazolidinone, N, N It is effective to immerse an inorganic solid material in amides such as' -dimethylpyrrolidinone, or to impregnate a column filled with the inorganic solid material with a similar organic solvent in which an onium salt is dissolved from above. An inorganic solid material impregnated with an onium salt can be prepared by washing with a low boiling point solvent such as methanol, acetone, diethyl ether, and drying under normal pressure or reduced pressure conditions or under reduced pressure at low temperature. In preparing a similar impregnation catalyst, it is not always necessary to use an onium salt as a raw material. An inorganic solid substance is immersed in an organic solvent containing a base such as tetraalkylammonium hydroxide and an acid such as hydrogen halide in water. A similar material is formed in the system and the catalyst can be prepared. Alternatively, even if phosphine and alkyl halide, etc. are used as they are or mixed with an appropriate organic solvent, an onium salt is similarly produced in the system, and a catalyst having almost the same properties can be prepared by immersing an inorganic solid substance in the solution. . Preparation of the catalyst by such impregnation is not always necessary for the catalyst to show activity, but such a pretreatment of the catalyst has an effect of increasing the reaction time in the case of a reaction in a short time. The catalyst thus prepared may be mixed with another solid and / or a solid impregnated with another onium salt. Further, the solid thus prepared may be mixed with other solids such as metals and polymers, or may be immobilized on them. It is also possible for another organic solvent to coexist in the reaction system. Examples of such organic solvents include aliphatic and aromatic organic solvents, organic solvents containing heteroatoms, and more specifically, alcohols, ethers, esters, amides, tertiary amines, pyridines, sulfides, phosphines, and the like. Specifically, pentane, hexane, heptane, benzene, toluene, methanol, ethanol, diethyl ether, methyl-tert-butyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, ethyl acetate, ethylene carbonate, propylene carbonate, dimethylformamide, dimethyl Acetamide, N, N′-dimethylpyridazolinone, pyridine, triethylamine, dibutyl sulfide, tributylphosphine, and the like can be used.

  Moreover, in the catalyst system of the second embodiment, any solid may be further mixed or combined by some method. Examples of such solids include, but are not limited to, silica, alumina, zeolite, silicon carbide, clay minerals (such as montmorillonite), silica-alumina, zirconia, and organic polymers.

As a reaction mode in the present invention using the above catalyst, a generally used method such as a stirring type or a fixed bed type can be used, and any of a batch type, a semi-batch type and a continuous flow type can be used. It is.
The batch method is performed as follows, for example. An autoclave equipped with a stirrer is charged with epoxide and catalyst, and then filled with carbon dioxide and sealed. Thereafter, the inside of the autoclave is heated to a predetermined temperature while stirring, and further filled with carbon dioxide to adjust the internal pressure to a predetermined pressure, and after reacting for a predetermined time, the produced cyclic carbonate is separated by a desired means.

  The continuous flow type is, for example, a high-pressure fluid feed pump (A, B), a fluid mixer (C), a reaction tube (D), a pressure control device (E), and a temperature control device (F) shown in FIG. For example, after mixing propylene carbonate and supercritical carbon dioxide using a flow reaction apparatus (FIG. 1) combined with the like, the reaction may be continuously performed by heating in a reaction tube (D) filled with a catalyst. Further, propylene oxide as a raw material and a substance as a solvent other than carbon dioxide may coexist and be distributed. Specific examples of the solvent used at this time include aliphatic and aromatic organic solvents, organic solvents containing heteroatoms, and more specifically, alcohols, ethers, esters, amides, tertiary amines, pyridines, sulfides, phosphines, etc. Specifically, pentane, hexane, heptane, benzene, toluene, methanol, ethanol, diethyl ether, methyl-tert-butyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, ethyl acetate, ethylene carbonate, propylene carbonate, dimethyl phosphine Amides, dimethylacetamide, N-methylpyridazine, N, N′-dimethylpyridazolinone, pyridine, triethylamine, dibutyl sulfide, tributylphosphine, and the like can be used.

  In carrying out the present invention, the reaction temperature is not particularly limited, but is preferably in the range of room temperature to 300 ° C, more preferably 50 to 250 ° C. The reaction pressure is not particularly limited and is determined by the production cost of the pressure device used for the reaction, but is preferably in the range of 0.1 to 100 MPa, more preferably 0.1 to 25 MPa.

  The amount of the ionic substance in the catalyst varies depending on the conditions such as the form of the reactor used, the type of epoxide as the raw material, the reaction temperature, the reaction pressure, and the desired productivity. For example, it is carried out using a batch reactor. In this case, the amount of the catalyst is such that the weight ratio to the raw material epoxide is 1 / 10,000 to 10,000, preferably 1/1000 to 1000, and more preferably 1/100 to 10,000.

  The form of the catalyst used in the present invention is not particularly limited, but is usually fine powder, thin film, or spherical or columnar particles having an average particle size of about 0.1 to 10 mm. Pretreatment of the catalyst is not particularly required, but it is evacuated at room temperature to 120 ° C., preferably 50 to 100 ° C., or in an inert gas stream such as helium, argon, nitrogen, carbon dioxide, or in the air before the reaction. By doing so, the yield of cyclic carbonate can be improved.

EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited at all by these examples.
[Preparation of surface catalyst]
[Catalyst preparation by substitution reaction]

Example 1
The phosphonium salt surface-modified silica was prepared by the following method. SiO ₂ -C ₃ H ₆ Cl (manufactured by Aldrich, 3-chloropropyl functionalized silica gel, functionalization rate per unit weight: 0.71 mmol / g) 7.00 g was suspended in 50 ml of toluene under argon, and 200 ml stirring blades While slowly stirring in a three-necked flask, add 3.00 g of tributylphosphine. The suspension is reacted at 110 ° C. for 1 week under a stream of argon while continuing to stir. Liquid was filtered off from the suspension after the reaction, and the resulting solid was washed with methanol, acetone and ether in this order, air-dried and then dried at room temperature for 6 hours under vacuum of 1 mm or less as it was as a catalyst. Using. The above reaction is schematically represented by chemical formula (7). As a result of elemental analysis, P 0.23 mmol / g and Cl 0.7 mmol / g were contained.

[イオン交換法による触媒調製] Example 2
By reacting in the same manner as in the previous section except that 3-bromopropyl functionalized silica gel SiO ₂ —C ₃ H ₆ Br (weight functionalization rate: 1.43 mmol / g) is used as a raw material, the chemical formula (8) Silica gel SiO ₂ —C ₃ H ₆ PBu ₃ Br surface-modified with tributylphosphonium bromide can be obtained. The elemental analysis values were P 0.48 mmol / g and Br 0.85 mmol / g.

[Catalyst preparation by ion exchange method]

Example 3
Silica gel surface-modified with tributylphosphonium chloride described in Example 1 was replaced with bromide by ion exchange. Specifically, a solution obtained by dissolving sodium bromide in SiO ₂ —C ₃ H ₆ PBu ₃ Cl in 50 ml to 3000 ml of methanol per 5 g to about 100 times the theoretical exchange capacity (0.7 mmol per g). It was adjusted and allowed to flow slowly over catalyst particles packed on a column or filter. After completion, the product was washed with methanol, washed with acetone and ethanol, air-dried, transferred to a Schlenk tube, and vacuum-dried at room temperature to 100 ° C. to obtain SiO ₂ —C ₃ H ₆ PBu ₃ Br. As a result of elemental analysis, Cl was 0.4 mmol / g, Br 0.36 mmol / g, and P 0.32 mmol / g.

Example 4
In the same manner as in Example 3, the silica gel surface-modified with tributylphosphonium chloride shown in Example 2 was replaced with iodide by ion exchange. Specifically, SiO ₂ —C ₃ H ₆ PBu ₃ I was obtained in the same manner as in Example 3 except that potassium iodide was used instead of sodium bromide with respect to SiO ₂ —C ₃ H ₆ PBu ₃ Cl. It was. The results of elemental analysis were P 0.32 mmol / g, Cl 0.47 mmol / g, and P 0.26 mmol / g.

Example 5
SiO ₂ —C ₃ H ₆ PEt ₃ Cl was obtained in the same manner as in Example 1 except that triethylphosphine was used instead of tributylphosphine. Using this material as a raw material, SiO ₂ —C ₃ H ₆ PEt ₃ Cl was obtained in the same manner as in Example 3.

Example 6
SiO ₂ —C ₃ H ₆ PPh ₃ Br was obtained in the same manner as in Example 2 except that triphenylphosphine was used instead of tributylphosphine. As a result of elemental analysis, it contained P 0.31 mmol / g and Br 0.89 mmol / g.

Example 7
SiO ₂ —C ₃ H ₆ NC ₅ H ₅ Br was obtained in the same manner as in Example 2 except that pyridine was used instead of tributylphosphine and the reaction temperature was 50 ° C. The elemental analysis results were C 7.58 mmol / g, H 17.9 mmol / g, N 0.64 mmol / g, Br 1.08 mmol / g.

Example 8
SiO ₂ —C ₃ H ₆ NC ₅ H ₄ ^t C ₄ H ₉ Br was obtained in the same manner as in Example 8 except that 4-tert-butylpyridine was used instead of pyridine and the reaction temperature was 50 ° C. . The elemental analysis results were C 7.66 mmol / g, H16.87 mmol / g, N 0.39 mmol / g, Br 1.08 mmol / g.

Example 9
Commercially available catalyst SiO ₂ -C ₃ H ₆ NMe ₃ (CO ₃ ) _1/2 (made by Aldrich, loading 0.7 mmol / g) surface-modified with trimethylammonium carbonate, containing an equal amount of HBr water SiO ₂ —C ₃ H ₆ —NMe ₃ Br can be obtained by reacting with a methanol solution. Specifically, a methanol solution containing 10% of HBr water was gradually added to SiO ₂ —C ₃ H ₆ NMe ₃ (CO ₃ ) _1/2 suspended in ethanol to carry out a neutralization reaction, and the pH of the solution was adjusted. After checking and neutralizing by adding HBr ethanol solution until pH becomes 4 or less, the catalyst was collected by filtration, washed with acetone and ether, air dried, and vacuum dried at room temperature to 100 ° C. SiO ₂ —C ₃ H ₆ NMe ₃ Br was obtained. The results of elemental analysis were C 4.25 mmol / g, H 14.9 mmol / g, N 0.60 mmol / g, and Br 0.58 mmol / g.

Example 10
A neutralization reaction was carried out in exactly the same manner except that HI was used in place of HBr using the same raw materials as in Example 10 to obtain SiO ₂ —C ₃ H ₆ NMe ₃ I.

Example 11
Silica gel SiO ₂ —C ₆ H ₄ CH ₂ Cl (loading: 1.3 mmol / g) surface-modified with a phenylmethylene chloride group was used as a raw material, and tributylphosphine was prepared in the same manner as in Example 1 except that this was used. Reaction was performed to obtain SiO ₂ —C ₆ H ₄ CH ₂ PBu ₃ Cl. The results of elemental analysis were P 0.46 mmol / g and Cl 1.0 mmol / g.

Example 12
Using SiO ₂ —C ₆ H ₄ CH ₂ PBu ₃ Cl obtained in Example 11 as a raw material and using this, ions were obtained using a sodium bromide methanol solution in exactly the same manner as in Example 3. Exchange was performed to obtain SiO ₂ —C ₆ H ₄ CH ₂ PBu ₃ Br. The results of elemental analysis were P 0.40 mmol / g, Cl 0.41 mmol / g, and Br 0.48 mmol / g.
[Catalyst activity evaluation]

Example 13
The propylene carbonate synthesis reaction was carried out by the following method. After charging propylene oxide (57.2 mmol) and 800 mg of the SiO ₂ —C ₃ H ₆ PBu ₃ Cl catalyst prepared in Example 1 and 50 mg of adamantane as an internal standard in an argon atmosphere into a 20 mL volume autoclave containing a stir bar Filled with carbon dioxide and sealed. Thereafter, the inside of the autoclave was heated to 100 ° C. with stirring, and further charged with carbon dioxide, thereby adjusting the internal pressure to 14 MPa and allowing the reaction to proceed for 8 hours. After cooling, the remaining carbon dioxide was released, and the reaction mixture was analyzed by gas chromatography. The results are shown in Table 1.

Example 14
Propylene carbonate was synthesized in the same manner as in Example 13 except that SiO ₂ —C ₃ H ₆ PBu ₃ Br synthesized in Example 2 was used as a catalyst and the reaction time was changed to 4 hours. The results are shown in Table 1.

Example 15
Propylene carbonate was synthesized in the same manner as in Example 13 except that the reaction was performed at a CO ₂ pressure of 10 MPa and a temperature of 150 ° C. The results are shown in Table 1.

Example 16
Propylene carbonate was synthesized in the same manner as in Example 13 except that the reaction was performed at a CO ₂ pressure of 0.95 MPa and a temperature of 100 ° C. The results are shown in Table 1.

Example 17
Propylene was produced in the same manner as in Example 13 except that SiO ₂ —C ₃ H ₆ PBu ₃ Br prepared by the ion exchange method in Example 3 was used as a catalyst and the reaction time was 1 hour at 100 ° C. and 10 MPa. Carbonate was synthesized. The results are shown in Table 1.

Example 18
Propylene carbonate was synthesized in the same manner as in Example 17 except that SiO ₂ —C ₃ H ₆ PBu ₃ I prepared by the ion exchange method in Example 4 was used as a catalyst. The results are shown in Table 1.

Example 19
Propylene carbonate was synthesized under the same conditions as in Example 17 except that SiO ₂ —C ₃ H ₆ PEt ₃ Br prepared using triethylphosphine in Example 5 was used as a catalyst. The results are shown in Table 1.

Example 20
Propylene carbonate was synthesized under the same conditions as in Example 17 except that SiO ₂ —C ₃ H ₆ PPh ₃ Br prepared using triphenylphosphine in Example 6 was used as a catalyst. The results are shown in Table 1.

Example 21
Propylene carbonate was synthesized under the same conditions as in Example 17 except that SiO ₂ —C ₃ H ₆ NC ₅ H ₅ Br synthesized in Example 7 was used as a catalyst. The results are shown in Table 1.

Example 22
Propylene carbonate was synthesized under the same conditions as in Example 17 except that SiO ₂ —C ₃ H ₆ NC ₅ H ₅ (4-tert-C ₄ H ₉ ) Br synthesized in Example 8 was used as a catalyst. The results are shown in Table 1.

Example 23
Propylene carbonate was synthesized under the same conditions as in Example 17, except that commercially available SiO ₂ —C ₃ H ₆ NMe ₃ (CO ₃ ) _1/2 (Aldrich) was used as the catalyst and the temperature was 180 ° C. did. The results are shown in Table 1.

Example 24
In Example 9, the catalyst SiO ₂ —C ₂ H ₆ NMe ₃ Br prepared from the SiO ₂ —C ₃ H ₆ NMe ₃ (CO ₃ ) _1/2 by the neutralization reaction with hydrobromic acid was used. Propylene carbonate was synthesized in the same manner. The results are shown in Table 1.

Example 25
Example 10 and Example 17 using the catalyst SiO ₂ —C ₂ H ₆ NMe ₃ I prepared by neutralization with hydroiodic acid from SiO ₂ —C ₃ H ₆ NMe ₃ (CO ₃ ) _1/2 in Example 10 Propylene carbonate was synthesized in the same manner. The results are shown in Table 1.

Example 26
Propylene carbonate was synthesized in the same manner as in Example 17 except that SiO ₂ —C ₆ H ₄ CH ₂ PBuCl synthesized in Example 11 was used as a catalyst. The results are shown in Table 1.

Example 27
Propylene carbonate was synthesized in the same manner as in Example 17 except that SiO ₂ —C ₆ H ₄ CH ₂ PBuBr prepared from SiO ₂ —C ₆ H ₄ CH ₂ PBuCl in Example 12 by an ion exchange method was used as a catalyst. The results are shown in Table 1.

Comparative example

Comparative Example 1
A propylene carbonate synthesis reaction was performed in the same manner as in Example 1 using commercially available PBu ₄ Br. The results are shown in Table 1.

Comparative Example 2
Propylene carbonate synthesis reaction was carried out in the same manner as in Example 1G using commercially available surface-modified silica gel, SiO ₂ —C ₃ H ₆ Br. The results are shown in Table 1.

Comparative Example 3
PS-C ₆ H ₄ CH ₂ Cl polystyrene resin, commercially available beaded polystyrene resin (ArgoPore-Cl) and tributylphosphine (PBu ₃ ) in which part of the phenyl group has a chloromethyl group at the 4-position Were reacted in the same manner as in Example 1 to synthesize a partially phosphonium ionized polystyrene resin PS-C ₆ H ₄ CH ₂ PBu ₃ Cl. This was led to PS-C ₆ H ₄ CH ₂ PBu ₃ Br by an ion exchange method using sodium bromide in the same manner as in Example 3 as a raw material. A propylene carbonate synthesis reaction was performed in the same manner as in Example 13 using the resin thus obtained as a catalyst. The results are shown in Table 1.

Comparative Example 4
PS-C ₆ H ₄ PBu ₃ Cl synthesized in Comparative Example 3 was used as a raw material, and it was led to PS-C ₆ H ₄ CH ₂ PBu ₃ I by an ion exchange method using potassium iodide as in Example 4. A propylene carbonate synthesis reaction was performed in the same manner as in Example 13 using the resin thus obtained as a catalyst. The results are shown in Table 1.

Comparative Example 5
Part of the phenyl group in the polyethylene resin represented by PS-C ₆ H ₄ CH (CH ₂ (OC ₂ H ₄ ) _n Cl) ₂ has two chloroethyl groups via a polyethylene glycol chain at the 4-position. A commercially available bead-shaped polystyrene resin (ArgoGel) modified with a methyl group and tributylphosphine are used as raw materials and reacted in the same manner as in Example 1 to partially have phosphonium ions via polyethylene glycol. Polystyrene resin PS-C ₆ H ₄ CH (CH ₂ (OC ₂ H ₄ ) _n PBu ₃ Cl) ₂ was synthesized. Elemental analysis values P 0.8%, Cl 1.4%, C 61.9% Functional group conversion 60% estimated from elemental analysis. A propylene carbonate synthesis reaction was performed in the same manner as in Example 13 using the resin thus obtained as a catalyst. The results are shown in Table 1.
[Continuous flow reaction]

Example 28
After mixing propylene carbonate and supercritical carbon dioxide using the reaction apparatus shown in FIG. 1, in a reaction tube having an internal volume of 20 ml filled with the catalyst SiO ₂ —C ₃ H ₆ PBu ₃ Br described in Example 2. An experiment was conducted in which the product was continuously obtained by heating. The product was trapped for a certain time with DMF in which a standard substance had been dissolved in advance, and its composition was analyzed by gas chromatography. After continuing the reaction for 24 hours, sampling was performed in the same manner and analysis was performed. The reaction temperature was 90 ° C. and the pressure was 10 MPa. The results are shown in Table 2.

Comparative Example 6
An experiment was conducted in which PS-C ₆ H ₄ CH ₂ PBu ₃ Br prepared by the method shown in Example 4 was filled in a reaction tube in the same reactor as in Example 28 to continuously obtain a product. . Analysis of the product was performed as in Example 28. However, since the yield was too low even at a reaction temperature of 120 ° C., the pressure was changed to 140 ° C. after 4 hours and the pressure was 10 MPa. The results are shown in Table 2.

表中SiO₂はシリカゲルを、PSはポリスチレンを表す。Buはn-Butyl基、^tBuはtert-Butyl基、Meはメチル基、Etはエチル基、Phはフェニル基、Bzはベンジル基、C₆H₄はp-フェニレン基、PyはNでリンカーと結合したピリジニウム基、（4-^tBuPy）はNでリンカーと結合した4-位を置換されたピリジニウム基等をそれぞれ表す。
反応条件：触媒量は官能基変換率100％を過程して基質であるプロピレンオキシド（4ml、57.2mmol）に対して1％モルにあたる0.57mmol相当量を用いた。収率はアダマンタンを標準物質としてガスクロマトグラフィーにて決定。

In the table, SiO ₂ represents silica gel and PS represents polystyrene. Bu is n-Butyl group, ^t Bu is tert-Butyl group, Me is methyl group, Et is ethyl group, Ph is phenyl group, Bz is benzyl group, C ₆ H ₄ is p-phenylene group, Py is N and linker And (4- ^t BuPy) represents a pyridinium group substituted at the 4-position and bound to the linker by N, respectively.
Reaction conditions: The amount of catalyst used was 0.57 mmol equivalent to 1% mol of propylene oxide (4 ml, 57.2 mmol) as a substrate through a functional group conversion rate of 100%. The yield was determined by gas chromatography using adamantane as a standard substance.

［オニウム塩とシリカの混合触媒系］

[Mixed catalyst system of onium salt and silica]

Example 29
Commercially available tetrabutylphosphonium bromide 0.57mmol, silica gel (Kanto, silica gel 60N, 100-200Mesh) 500mg and adamantane 50mg as internal standard were charged under argon into a 20ml autoclave equipped with a stirrer, pressure gauge, needle valve, After adding 4 ml of propylene oxide using a syringe, it is sealed and filled with liquid CO ₂ at room temperature via a needle valve. This is sealed and heated for about 5 minutes with stirring in an oil bath set to a predetermined temperature. In addition, pressurize high-pressure CO ₂ from the valve to maintain a constant pressure, and continue the heating to urge the reaction. If the pressure drops significantly during the reaction, CO ₂ is further added from the needle valve, and the reaction is continued for a certain time while keeping the internal pressure almost constant. After the reaction, when the pressure of the container is released, the gas released is trapped through the DMF trap as completely as possible to the raw material propylene oxide and a part of the product propylene carbonate. The combined DMF solution and the reaction solution were thoroughly homogenized and filtered, and the solution obtained by mixing the filtered silica gel together with the washing solution washed again with DMF was analyzed by gas chromatography. The yield was calculated from the amount of propylene carbonate produced, and the selectivity was calculated in consideration of the amount of by-product produced. The results are shown in Table 3.

[Data analysis]
As for the reaction with a selectivity of about 100% (when no by-products other than the main product are detected at all), it turns into a 100% product by a long-time reaction, and it turns out that the reaction proceeds primarily with respect to the raw material. ing. For this reason, the time change of the quantity of a product follows 1-Exp (-t / (tau)) by making the whole quantity into 1. In this equation, t is the reaction time, and here the unit is measured using minutes. τ is a time constant of the reaction, and this reciprocal 1 / τ = k ′ is an apparent first-order reaction rate constant. In the case of a primary reaction with respect to the catalyst, a value k obtained by dividing k ′ by the mole fraction of the catalyst with respect to the substrate shows a constant value. If the molar fraction (yield) of the product at time t is y (t), y (t) = 1−Exp (−t / τ) to τ = −t / ln (1−y (t)) Furthermore, k ′ = − ln (1-y (t)) / t and a rate constant can be obtained. Since k = k ′ / ([number of moles of catalyst] / [number of moles of propylene oxide]) ideally shows a constant value regardless of the amount of catalyst, it is effective as a parameter for objectively indicating the catalytic ability. When the reaction takes place according to an exponential function, one molecule of the catalyst corresponds to the number of molecules of the product produced per unit time at the beginning of the reaction, and is generally called the initial rate of TOF (turnover frequency) Is equal to In Table 1, the reaction rate constant k is determined according to this equation so that the capacity per mole of the catalyst under these conditions can be compared.

Examples 30-70
Instead of tetrabutylphosphonium chloride in Example 29, commercially available tetrabutylphosphonium bromide (Examples 30 and 31), tetrabutylphosphonium iodide (Example 32), tetraphenylphosphonium bromide (Example 33), benzyltributylphosphonium bromide (Example 34), benzyltriphenylphosphonium bromide (Example 35), butyltriphenylphosphonium bromide (Example 36, Example 37), tetramethylammonium bromide (Example 38), ethyltrimethylammonium iodide (Example) 39), triethylmethylammonium bromide (Example 40), tetraethylammonium chloride (Example 41), tetraethylammonium bromide (Examples 42 to 44), tetraethylammonium Umiozide (Example 45), tetrabutylammonium bromide (Example 46), tetraheptylammonium bromide (Example 47), hexadecyltrimethylammonium bromide (Example 48), dimethyldioctadecylammonium bromide (Example 49), trimethyl Phenylammonium iodide (Example 50), benzyltriethylammonium bromide (Example 51), acetylcholine bromide (Example 52), butylmethylimidazolium bromide (Example 53), methyloctylimidazolium chloride (Example 54), Methylpyridinium chloride (Example 55), ethylpyridinium bromide (Example 56), hexadecylpyridinium bromide (Example 57), 2,3,5-triphenyltetrazolium iodide (actual Example 58), tetraphenylarsonium chloride (Example 59), tetramethylammonium nitroxide (Example 60), tetramethylammonium sulfate (Example 61), tetramethylammonium hydrosulfate (Example 62), tetramethyl Ammonium acetate (Example 63), tetraethylammonium tosylate (Example 64), tetraethylammonium trifluoroacetate (Example 65), tetrabutylammonium cyanide (Example 66), tetrabutylammonium dihydrophosphate (Example 68) ), Tetraethylammonium tetrafluoroborate (Example 69), pyridinium trimethylene sulfone hydroxide internal salt (Example 70), partially different temperatures, and EC ( Addition to coexist Ji Ren carbonate) experimented similarly are shown in Table 3 the results of data analysis in the same manner as described above.

Comparative Examples 7 to 48
The reaction was carried out without adding silica gel as in Examples 29-74. Specifically, tetrabutylphosphonium chloride (Comparative Example 7), tetrabutylphosphonium chloride (Comparative Example 8), tetrabutylphosphonium bromide (Comparative Examples 9 and 10), tetrabutylphosphonium iodide (Comparative Example 11), tetraphenylphosphonium Bromide (Comparative Example 12), benzyltributylphosphonium bromide (Comparative Example 13), benzyltriphenylphosphonium bromide (Comparative Example 14), butyltriphenylphosphonium bromide (Comparative Example 15 and Comparative Example 16), tetramethylammonium bromide (Comparative Example) 17), ethyltrimethylammonium iodide (Comparative Example 18), triethylmethylammonium bromide (Comparative Example 19), tetraethylammonium chloride (Comparative Example 20), tetraethylammonium bromide (Comparative Example) 1-23), tetraethylammonium iodide (Comparative Example 24), tetrabutylammonium bromide (Comparative Example 25), tetraheptylammonium bromide (Comparative Example 26), hexadecyltrimethylammonium bromide (Comparative Example 27), dimethyldioctadecylammonium Bromide (Comparative Example 28), trimethylphenylammonium iodide (Comparative Example 29), benzyltriethylammonium bromide (Comparative Example 30), acetylcholine bromide (Comparative Example 31), butylmethylimidazolium bromide (Comparative Example 32), methyloctylimidazo Lilium chloride (Comparative Example 33), Methylpyridinium chloride (Comparative Example 34), Ethylpyridinium bromide (Comparative Example 35), Hexadecylpyridinium bromide (Comparative Example 36), 2,3,5-Triphe Niltetrazolium iodide (Comparative Example 37), tetraphenylarsonium chloride (Comparative Example 38), tetramethylammonium nitroxide (Comparative Example 39), tetramethylammonium sulfate (Comparative Example 40), tetramethylammonium hydrosulfate (Comparative) Example 41), tetramethylammonium acetate (Comparative Example 42), tetraethylammonium tosylate (Comparative Example 43), tetraethylammonium trifluoroacetate (Comparative Example 44), tetrabutylammonium cyanide (Comparative Example 45), tetrabutylammonium Experiments corresponding to Examples were conducted using dihydrophosphate (Comparative Example 46), tetramethylammonium tetrafluoroborate (Comparative Example 47), and pyridine trimethylene sulfoxide (Comparative Example 48). Table 3 shows the results of data analysis in the same manner as described above,
Each was used. The results are shown in Table 3.
[Mixed catalyst system of onium salt and other metal oxides]

Examples 71-74
In place of 500 mg of silica, 500 g of inorganic metal salt was added, and the performance of each catalyst was evaluated by the same method as in Example 29 in the presence of tetraethylammonium bromide. Specifically, except silica, it is active for alumina (Example 71), magnesia (Example 60), zinc oxide (Example 72), zirconia (Example 73), and silica gel for drying with blue indicator (Example 74). The selectivity was examined.

Comparative Examples 49-53
The activity of each metal oxide catalyst alone was evaluated by the same method as in Example 8 in the presence of tetraethylammonium bromide using only 500 mg of inorganic metal salt. Specifically, alumina (Comparative Example 49), magnesia (Comparative Example 50), zinc oxide (Comparative Example 51), zirconia (Comparative Example 52), and silica gel for drying with a blue indicator (Comparative Example 53) other than silica.

Comparative Examples 54 and 55
In the same manner as in Example 13, the reaction was carried out under two conditions using only silica gel without using an onium salt, and the same analysis was performed. The results are shown in Table 3.

  As is apparent from Table 3, the activity was improved by 2 to 150 times or more compared to the case where only the corresponding onium salt was used as a catalyst by adding silica. In particular, when the melting point of the onium salt is high and the solubility is low, it appears that those that apparently have no activity become active. It can also be seen that the difference only in the alkyl group does not have a large difference, and that the acceleration effect due to the addition of silica is remarkable when the anion is I or Br, and this effect is generally small when the anion is Cl. Since silica alone does not show any catalytic activity, a cooperative effect by mixing silica-onium salt was found. In this way, the catalyst that uses silica and onium salt in combination has not only high product selectivity but also greatly improves the reaction rate and at the same time facilitates catalyst recovery and reuse. In addition, it has many industrial advantages such as low cost and long life.

表中、Me,Et,Bu、Ph,Bz、Py等は表1に準じる。Imはここでは1,3位をアルキル置換されたイミダゾリウム基をあらわす。ⁿHpはn-ヘプチル基を、ⁿOctはn-オクチル基をそれぞれ表す。^ｎC₁₂、ⁿC₁₈等はそれぞれn-C₄H₉、n-C₁₂H₂₅、n-C₁₈H₃₇等をあらわす。OAcはアセチル基を、AcOはアセタトイオンをそれぞれあらわす。一方C₂OAcはアセチロキシエチル基を表す。OTsはトシラート基＝p-トルエンスルホニル基を、BF₄はテトラフルオロボレートイオンを表す。PyⁿC₁₆Brはヘキサデシルピリジニウムブロミドを、TetPh₃Iは2,3,5トリフェニルテトラゾリウムヨージドを示し、PyC₃SO₄はピリジニウムトリメチレンスルホンヒドロキシド内部塩を表す。SiO₂blueはやや特殊であり、化合物名ではなく、青色インジケーター入り乾燥用シリカゲルを表す。反応条件（特に注釈のない場合）プロピレンオキシド4ml、触媒／プロピレンオキシド：＝lmol%。SiO₂（もしくはほかの固体添加物）：500mg。
［他の基質への応用］

In the table, Me, Et, Bu, Ph, Bz, Py and the like are in accordance with Table 1. Im here represents an imidazolium group alkyl-substituted at positions 1 and 3. ⁿ Hp represents an n-heptyl group, and ⁿ Oct represents an n-octyl group. ⁿ C ₁₂ , ⁿ C _18, etc. represent nC ₄ H ₉ , nC ₁₂ H ₂₅ , nC ₁₈ H _37, etc., respectively. OAc represents an acetyl group, and AcO represents an acetate ion. On the other hand, C ₂ OAc represents an acetyloxyethyl group. OTs represents a tosylate group = p-toluenesulfonyl group, and BF ₄ represents a tetrafluoroborate ion. Py ⁿ C ₁₆ Br represents hexadecylpyridinium bromide, TetPh ₃ I represents 2,3,5 triphenyltetrazolium iodide, and PyC ₃ SO ₄ represents a pyridinium trimethylene sulfone hydroxide inner salt. SiO ₂ blue is a little special, not a compound name, but a dry silica gel with a blue indicator. Reaction conditions (unless otherwise noted) 4 ml propylene oxide, catalyst / propylene oxide: = lmol%. SiO ₂ (or other solid additive): 500 mg.
[Application to other substrates]

Example 75
A cyclic carbonate synthesis reaction was carried out in the same manner as in Example 13 except that 4 ml of isobutylene oxide was used as a raw material, the catalyst was NEt ₄ Br, and the reaction conditions were 100 ° C. and 6 hours. The product was quantified by gas chromatography. The results are shown in Table 4.

Example 76
A cyclic carbonate synthesis reaction was carried out in the same manner as in Example 13 except that 4 ml of styrene oxide was used as a raw material, the catalyst was NEt ₄ B, and the reaction conditions were 120 ° C. for 4 hours. The product was quantified by gas chromatography. Since the product became a solid, it was dissolved in DMF for quantification. The results are shown in Table 4.

Example 77
A cyclic carbonate synthesis reaction was carried out in the same manner as in Example 13 except that 4 ml of cyclohexene oxide was used as a raw material, 0.57 mmol of NEt ₄ Br and silica were used as catalysts, and the reaction was carried out at 120 ° C. for 4 hours. The product was quantified by gas chromatography. The results are shown in Table 4.

Example 78
A cyclic carbonate synthesis reaction was carried out in substantially the same manner as in Example 13, except that 5 g of trans-stilbene oxide was used as a raw material, 0.57 mmol of NEt ₄ Br and 1 g of silica were used as a catalyst, and the reaction was carried out at 100 ° C. and 25 MPa for 100 hours. went. Like styrene oxide, the product is a solid. Quantified by ¹ H NMR. The results are shown in Table 4.

Example 79
Using 500 mg of tetracyanoepoxide as a raw material, this was dissolved in 4 ml of DMF, and then cyclic carbonate synthesis reaction was carried out in the same manner as in Example 13 using 0.57 mmol of Net ₄ Br as a catalyst under the reaction conditions of 100 ° C., 10 MPa, 4 hours. . The product was quantified by gas chromatography. The results are shown in Table 4.

  As shown so far, the cyclic carbonate synthesis catalyst from the epoxide according to the present invention is very versatile and has a remarkable effect. In particular, it has an effect on a 4-substituted epoxide. Although many metal oxide solids have a reaction accelerating effect, the use of silica is most industrially promising because it does not impair selectivity, has a large acceleration effect, is inexpensive, and has low toxicity.

Claims (2)

(Tributyl phosphonium bromide) - alkylene group having 2 to 8 carbon atoms _{(-C n H 2n PBu 3 Br} , n = 2~8), ( triethyl phosphonium bromide) - alkylene group having 2 to 8 carbon atoms (-C _n H _2n PEt ₃ Br, n = 2 to 8) or (tributylphosphonium iodide) -an alkylene group having 2 to 8 carbon atoms (—C _n H _2n PBu ₃ I, n = 2 to 8) A catalyst used when synthesizing a cyclic carbonate from epoxide and carbon dioxide, comprising silica having a surface modification. The epoxide and carbon dioxide are cyclically reacted with each other using the catalyst according to claim 1 under a high pressure condition of 0.95 MPa or more without using a solvent other than the reaction product. A method of synthesizing carbonate.

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