JP2003286226A - Method for transesterification and catalyst for transesterification - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for transesterification, with which a catalyst after reaction completion is isolated and the isolated catalyst is recycled. <P>SOLUTION: The method for transesterification comprises carrying out transesterification in the presence of a gel-like styrene-based polymer or a gel-like polysiloxane-based polymer [A] represented by [PS(polystyrene)-P<SP>+</SP>(Ph)<SB>2</SB>CH<SB>2</SB>CH<SB>2</SB>CO<SB>2</SB><SP>-</SP>][Zn(OAc)<SB>2</SB>] having phosphonium structure (b) containing structure in which an anionic functional group is coordinated with a metal compound (a) containing a transition metal or the metal of an atom belonging to the group IIB, the group IIIA or the group IVA of the periodic table and then separating the catalyst by filtration. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transesterification reaction method and a catalyst used therefor.

[0002]

BACKGROUND OF THE INVENTION Ester compounds are widely used industrially as unsaturated carboxylic acid esters useful as reactive monomers, ester compounds useful as raw materials for medicines and agricultural chemicals, and other polyesters. Among them, unsaturated carboxylic acid esters are resin polymers of various fields,
For example, it is extremely useful as a reactive monomer for resin polymers in various applications such as paint resins, printing inks, UV curable resins, molding resins, films and adhesives.

These ester compounds are usually produced by a direct esterification method in which a carboxylic acid is reacted with an alcohol having a mono- or polyhydroxyl group, and a transesterification method in which a carboxylic acid ester is reacted with an alcohol having a mono- or polyhydroxyl group. Has been done.

Although the direct esterification method is known to produce sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, etc. as a reaction catalyst, it produces coloring of the product and a large amount of by-products, and further increases the purity. It has the disadvantage of low yield. In particular, when producing unsaturated carboxylic acid esters having two or more ester groups, which are useful as a reactive monomer, it is difficult to obtain them in high yield and purity, and further oligomerization by polymerization of unsaturated bonds Therefore, the viscosity of the obtained ester tends to increase.

On the other hand, the transesterification method is an industrial production method of unsaturated carboxylic acid esters,
It is widely used and has the advantage that it can prevent oligomerization during production.

[0006] As an industrial production method of such a transesterification reaction, for example, JP-A-54-41814 discloses:
(Meth) acrylic acid ester by transesterification using at least one tin compound selected from alkyl tin compounds, tin oxides, dialkyl tin oxides, tin alkoxides, tin halides and dialkyl tin dichlorides as a reaction catalyst. A method of making a class is disclosed.

Zinc salts are also known as useful catalysts for the transesterification reaction between alcohols and carboxylic acid esters, and for example, JP-A-57-60331 discloses that
A method for producing an acrylate using at least one zinc compound selected from various zinc compounds as a catalyst is disclosed.

Further, US Pat. No. 4,753,912 discloses a technique of using an organophosphorus compound in which phosphorus is trivalent as a catalyst, and the organophosphorus compound comprises an acrylic ester and a catalyst precursor. It is disclosed that when formed, it exhibits a catalytic action in the transesterification reaction of acrylic acid ester.

[0009]

However, in each of the above-mentioned conventional techniques, for example, the technique using a metal catalyst represented by a tin compound, the reaction yield and the purity of the product are good, but In the purification step after completion of the reaction, a neutralization step with an acid or an alkali is indispensable. Such a neutralization step is extremely complicated in the industry, which lowers productivity and causes a disadvantage of increasing production cost. Further, even if it is possible to remove the catalyst by acid or alkali treatment, it is difficult to recover and reuse the catalyst, which also causes an increase in cost, and there is a problem in terms of environmental protection. Also, US Pat.
The organophosphorus compound described in Japanese Patent No. 753912 has insufficient catalytic activity, and in order to improve the yield,
In addition to being industrially disadvantageous because a large amount of catalyst is required, there is also a problem that a neutralization step is required in the refining step and the production method must be complicated.
Therefore, the problem to be solved by the present invention, in the transesterification reaction method, with excellent reaction yield and purity,
After completion of the reaction, the catalyst is isolated by a simple method, and the separated catalyst is reused to carry out the transesterification reaction.

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in the transesterification reaction between an alcohol and a carboxylic acid ester, the anionic functional group is a transition metal or a cyclic metal. IIB group, IIIA of the table
A gel styrene polymer or gel polysiloxane polymer [A] having a phosphonium structure (b) having a structure coordinated to a metal compound (a) containing a metal atom belonging to Group IVA or Group IVA is used as a catalyst As a result, it has been found that the catalyst can be separated by a simple method such as filtration while achieving an extremely excellent yield and purity, and the separated catalyst can be reused, and thus the present invention is completed. I arrived. That is, the present invention provides a phosphonium structure (b) having a structure in which an anionic functional group is coordinated with a transition metal or a metal compound (a) containing a metal atom belonging to Group IIB, IIIA or IVA of the periodic table. The present invention relates to a transesterification reaction method characterized by carrying out a transesterification reaction between an alcohol and a carboxylic acid ester in the presence of a gel styrene polymer or gel polysiloxane polymer [A] having Further, the present invention provides that the anion portion of the phosphonim group having an anionic functional group is a transition metal or II of the periodic table.
Gel-like styrene-based polymer or gel-like polysiloxane-based polymer having a phosphonium group (b) containing an anionic functional group coordinated to a metal compound (a) containing a metal atom belonging to Group B, Group IIIA or Group IVA The present invention relates to a transesterification reaction catalyst, which is composed of a combined product [A].

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an ester of the present invention comprises:
The gel-type styrene polymer or gel-type polysiloxane polymer [A] is used as a catalyst to perform an ester exchange reaction between an alcohol and a carboxylic acid ester.

Here, as the alcohol that can be used,
Examples include aliphatic alcohols, alicyclic alcohols, aromatic alcohols or polyols. These alcohols include alkyl groups, alkylene groups, alkenyl groups, cycloaliphatic groups, phenyl groups, heterocyclic groups, secondary or tertiary hydroxyl groups, carbonyl groups, ether groups, cyano groups, amino groups,
It may be substituted with at least one functional group selected from an amide group, a nitro group, a halogen atom and an organic phosphorus group. Moreover, the number of carbon atoms constituting the alcohol is preferably in the range of 2 to 30, and particularly preferably in the range of 2 to 20.

Such alcohol is specifically 1
The polyhydric alcohol is, for example, the following structural formula HO- (R ₂ O) _n -R ₃ (wherein R ₂ is an alkylene group having 2 to 8 carbon atoms, R ₃ is an alkyl group or aryl group having 1 to 18 carbon atoms, n is an integer of 1 or more.), alkylene glycol monoalkyl ethers, other furfuryl alcohol,
Tetrahydrofuryl alcohol, benzyl alcohol,
2-phenoxyethanol, cyclohexanol, allyl alcohol, xylose, and nitrogen-containing alcohols include hydroxylamines and hydroxyalkylpyridines such as hydroxyalkylpyridine, N- (hydroxyalkyl) piperidine, and N- (hydroxyalkyl) piperazine. Examples thereof include nitrogen heterocycles.

The present invention has an advantage that a high yield and a high purity can be obtained when esterifying a divalent or higher alcohol in the case of using (meth) acrylate as a raw material, which has been difficult in the prior art. In particular, as the alcohol used in combination with the unsaturated carboxylic acid ester, a divalent to
When a tetravalent one is used, there is a practical advantage that a polyfunctional monomer effective for polymer crosslinking can be easily produced.

2 out of such dihydric or higher alcohols
Examples of the polyhydric alcohol include ethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butanediol, pentanediol,
Hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, hexadecanediol, octadecanediol, cyclohexanediol, cyclodecanediol, tricyclodecanediol, butynediol, butenediol, hexenediol, octenediol, decenediol, polyalkylene Examples include glycol.

Examples of trihydric alcohols include hexanetriol, octanetriol, decanetriol,
Examples include trimethylolethane, trimethylolpropane, ethyloxyl trimethylolpropane, trimethylolbutane, and glycerin.

Examples of tetrahydric alcohols include pentaerythritol, dimethylolpropane, hexitol, sorbitol, mannitol and the like.

In the present invention, in particular, since the product has a high purity, that is, the effect of suppressing the polymerization of the unsaturated group at the time of the reaction is exerted, a polyhydric alcohol,
Particularly, it is extremely effective when a dihydric or trihydric alcohol is used.

Next, as the carboxylic acid ester to be reacted with alcohol, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
Examples include α, β-unsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, and other fatty acid alkyl esters such as butyl butyrate. Examples of the polyester raw material include dimethyl terephthalate, diethyl terephthalate, diethyl phthalate, dimethyl maleate, diethyl maleate, maleic anhydride, diethyl fumarate and the like.

The alkyl ester group in these carboxylic acid esters, that is, the group capable of leaving as an alcohol component by a transesterification reaction is a methyl ester group, an ethyl ester group, a propyl ester group or a butyl ester group. During the exchange reaction, a low-boiling monohydroxy group-containing alcohol (for example, methanol,
(Ethanol, butanol), which is preferable because it can be easily removed continuously outside the reaction system. When an unsaturated carboxylic acid ester is used, it is preferable to add a polymerization inhibitor during the transesterification reaction.

The combination of the above alcohol and carboxylic acid ester can be appropriately selected according to the use of the reaction product. For example, in the use of a reactive monomer, a combination of a polyhydric alcohol and an unsaturated carboxylic acid ester, In addition, for polyester use, a combination of a diol and a dicarboxylic acid diester may, for example, be mentioned.
In addition, in the synthesis of various ester compounds containing an ester group, various monohydric or polyhydric alcohols and saturated or unsaturated carboxylic acid esters can be combined. Among these, since the use of the reactive monomer is extremely useful industrially, it is preferably applied to the transesterification reaction between the alcohol and the unsaturated carboxylic acid ester. Further, in the transesterification reaction of the alcohol and the unsaturated carboxylic acid ester, oligomerization can be favorably prevented, and the ester compound yield,
It is characterized in that it can be produced with high purity and that the catalyst can be easily separated after completion of the reaction.

Next, when the anionic functional group used in the transesterification reaction method of the present invention is a transition metal or a periodic table,
Gel-like styrene-based polymer or gel-like polysiloxane-based polymer [A] having a phosphonium structure (b) having a structure coordinated to a metal compound (a) containing a metal atom belonging to IIB group, IIIA group or IVA group Is used as a solid catalyst. The gel-like styrene polymer or gel-like polysiloxane polymer [A] has the phosphonium structure (b) as a substituent in the gel-like styrene polymer or gel-like polysiloxane polymer. Further, the phosphonium structure (b) has a structure in which an anionic functional group as a group bonded to a phosphorus atom is coordinated with the metal compound (a).

[0022] Examples herein, anionic functional group contained in the gel-like styrene polymer or gel polysiloxane polymer [A] is, -COO ^- group, -SO
Examples thereof include a ₃ ^- group and a carbanion group. In view of stability of the coordination bond to the metal compound (a), -CO
It is preferably an O ^- group.

Next, in the phosphonium structure (b), the metal compound (a) to which an anionic functional group is coordinated is a transition metal or a group IIB or IIIA of the periodic table.
It contains a metal atom belonging to Group IVA or Group IVA.
Among these, particularly from the viewpoint of excellent electron accepting ability from anionic functional groups, good catalyst stability, and good durability upon repeated use, they belong to Group IIB, Group IIIA or Group IVA. A compound containing a metal atom and further a metal atom belonging to Group IIB or Group IVA is preferable. Particularly, zinc is preferable as the IIB group, and tin is preferable as the IVA group. Compounds containing these metal atoms include, for example, metallic tin, metallic lead,
As a simple substance of metal such as metallic zinc, or an organic or inorganic compound of metal, its form may be any form such as powder. Further, the organic or inorganic compound of the metal is preferably an organic salt or an inorganic salt, and when the metal atom is a IIB group, it is generally MX ₂ (wherein, M is a metal atom of IIB group, X is —OCOR or halogen). An atom, R
Is an alkyl group containing 1 to 20 carbon atoms. ) Is represented by the formula.

When the metal atom is a group IVA, the following structural formula

[Chemical 3] (In the formula, M is a metal atom of Group IVA, preferably tin, R ₁
Represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, or _{-CH 2 CH 2 CO 2 R 2} (R 2 Represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 15 carbon atoms, and X ₁ , X ₂ , X ₃ are each independently a halogen atom, -OR _9, -OCOR _9, or -O
COCH = CHCOOR ₂ (R ₂ is as defined above), Y ₁ and Y ₂ are each independently R ₁ , a halogen atom,
_{OR 2, -OCOR 2, -SCH 2} COOR 2, -SCH 2
CH ₂ COOR _2, or -OCOCH = CHCOOR
₂ (R ₂ is as defined above), and Z is —O— or —
Represents OCOCH = CHCOO-, and E is -COCH = C
_{HCO -, - COCH 2 SCH 2} CO-, or -COCH
₂ CH ₂ SCH ₂ CH ₂ CO-. Those represented by) are preferably used.

Among these, metal salts such as acetic acid, oxalic acid, propionic acid, butyric acid, octylic acid, maleic acid, boric acid, citric acid, caproic acid and stearic acid are preferable as the organic salt, and particularly, metal salts. When zinc is used as an atom, zinc compounds such as zinc acetate dihydrate, zinc acrylate, zinc benzoate, zinc chloride and zinc acetylacetonate monohydrate are preferable, and zinc acetate is particularly preferable. When tin is used as the metal atom, dialkyltin oxide, dialkyltin dihalide, dialkyltin dicarboxylate, tin acetylacetonate and the like are preferable, and more specifically, dialkyltin oxide and dialkyltin dihalogen. Compounds, dialkyltin dicarboxylates, 1,5-dihalogenated hexamethyltristannoxane and the like are preferable. Among them, dimethyltin dichloride, diethyltin dichloride, dibutyltin dichloride, 1,3-dihalogenated tetramethyldistannoxane, 1,3-dihalogenated tetrabutyldistannoxane, 1-halo-3-hydroxytetrabutyldistanox Particularly preferred are xanthane, 1,5-dihalogenated hexamethyltristannoxane and the like.

Therefore, the phosphonium structure (b) is
Specifically, the following structural formula

[Chemical 4] (In the formula, R ₁ and R ₂ each independently have 1 to 20 carbon atoms.
Alkyl group, C2-C10 alkenyl group, C5-C10 cycloalkyl group, C5-C5
10 represents a cycloalkenyl group, an aralkyl group having 7 to 15 carbon atoms, an aryl group, X represents a halogen atom, an acyloxy group having 1 to 20 carbon atoms, and R ₃ is alkylene having 1 to 20 carbon atoms. Represents a group, and n is 1 to 20
Represents the integer. ) Structure, or

The following structural formula

[Chemical 5] (In the formula, each of R ₁ , R ₂ and R ₄ independently has 1 carbon atom.
˜20 alkyl group, C 2-10 alkenyl group, C 5-10 cycloalkyl group, C 5-10 cycloalkenyl group, C 7-15
Represents an aralkyl group or an aryl group, X represents a halogen atom, an acyloxy group having 1 to 20 carbon atoms, or a phenyl group, R ₃ represents an alkylene group having 1 to 20 carbon atoms, and n is 1 to 20. , And m represents an integer of 0 or 1. It is preferable that the compound has a so-called phosphine betaine structure represented by the structure represented by (4).

The gel-like styrene-based polymer portion constituting the gel-like styrene-based polymer or gel-like polysiloxane-based polymer [A] is polystyrene, a copolymer of styrene and (meth) acrylic acid, Examples thereof include gelled products of styrene-based polymers such as copolymers of styrene and methyl (meth) acrylate. Of these, a gelled product of polystyrene is particularly preferable because it is easily available. next,
Examples of the gel-like polysiloxane-based polymer portion constituting the gel-like styrene-based polymer or gel-like polysiloxane-based polymer [A] include gelled products of polysiloxane-based polymers such as polysiloxane and polyorganosiloxane. To be Of these, a gelled product of polysiloxane is particularly preferable because it is easily available.

Accordingly, the gel-like styrene polymer or gel-like polysiloxane polymer [A] is specifically one having the following structure: [gel polystyrene-P ⁺ (Ph) _{2
^{CH 2 CH 2 CO 2 -]}} [Zn (OAc) 2], [ gel-state polystyrene _{^{-P + (Ph) 2 CH 2}} CH 2 CO 2 -] [Me 2 SnC
l ₂ ], [gel polystyrene-P ⁺ (Ph) ₂ (CH ₂ ) _{10
^{CO 2 -] [Me 2 SnCl}} 2], [ gel-state polystyrene -P ⁺
_{(Ph) 2 CH 2 CH 2} CO 2 -] [ClMe 2 SnOSnMe
₂ Cl], [gel polystyrene-CH ₂ CH ₂ P ⁺ (Ph)
^{_{2 CH 2 CH 2 CO 2 -}} ] [ClMe 2 SnOSnMe 2 Cl],
[Gelled polystyrene _{^{-P + (Ph) 2 CH 2}} CH 2 CO 2 -]
_{[ClBt 2 SnOSnBt 2 Cl],} [ gel-state polystyrene _{^{-P + (Ph) 2 CH 2}} CH 2 CO 2 -] [ClMe 2 SnO
SnMe ₂ OH], [gel polystyrene-P ⁺ (Ph) _{2
^{CH 2 CH 2 CO 2 -]}} [ClMe 2 SnOSnMe 2 OSnM
e ₂ Cl] [gel polysiloxane-P ⁺ (Ph) ₂ CH ₂ C
^{_{H 2 CO 2 -] [Zn}} (OAc) 2], [ gelled polysiloxane _{^{-P + (Ph) 2 CH 2}} CH 2 CO 2 -] [Me 2 SnCl 2],
[Gel Polysiloxane-P ⁺ (Ph) ₂ (CH ₂ ) ₁₀ CO
_{^{2 -] [Me 2 SnCl 2}} ], [ gelled polysiloxane -P
_{^{+ (Ph) 2 CH 2 CH}} 2 CO 2 -] [ClMe 2 SnOSnM
e ₂ Cl], [gel polysiloxane-CH ₂ CH ₂ P ⁺ (P
_{h) 2 CH 2 CH 2 CO} 2 -] [ClMe 2 SnOSnMe 2 C
l], [gel polysiloxane-P ⁺ (Ph) ₂ CH ₂ CH _{2
^{CO 2 -] [ClBt 2 SnOSnBt}} 2 Cl], [ gelled polysiloxane _{^{-P + (Ph) 2 CH 2}} CH 2 CO 2 -] [ClMe
₂ SnOSnMe ₂ OH], [gel polysiloxane-P ⁺
_{(Ph) 2 CH 2 CH 2} CO 2 -] [ClMe 2 SnOSnMe
₂ OSnMe ₂ Cl] and the like can be preferably used.

The gel-like styrene polymer portion and the gel-like polysiloxane polymer portion are solid at room temperature, and therefore the gel-like styrene polymer or gel-like polysiloxane polymer [A] is used as a solid catalyst. To be done. The gel-like styrene-based polymer or gel-like polysiloxane-based polymer [A] is characterized by excellent catalytic activity and easy isolation. Is preferably powdery or granular, and particularly preferably powdery.

In order to produce the above gel-like styrene polymer or gel-like polysiloxane polymer [A], Journal of Organometallic Chemistry, 1989
, 369, pp. 17-28, gel polysiloxane-CH ₂ CH ₂ PPh ₂ , solid phosphine compounds (b ′) such as polystyridyldiphenylphosphine, and anionic groups. The target gel-like styrene-based compound is prepared by a method of reacting a halogenated organic compound with an equimolar base of the resulting product to form an onium salt, and then reacting with the metal compound (a). A polymer or gel polysiloxane polymer [A] is obtained. The solid phosphine compound (b ′) used here preferably has a phosphorus atom content of 1 mmol / g to 10 mmol / g from the viewpoint of good catalytic activity.

Further, in particular anionic groups -COO ^- method if a group by the addition reaction between the solid phosphine compound and an unsaturated carboxylic acid, to give the phosphonium betaine compound, and then reacted with the metal compound (a) Is preferred. Further, in the latter case, when an unsaturated carboxylic acid ester is used as the carboxylic acid ester that is a raw material for the transesterification reaction, when the alcohol and the unsaturated carboxylic acid ester are charged into the reaction vessel, the solid phosphine compound (b ′ ) And the metal compound (a), and forming the gel styrene polymer or gel polysiloxane polymer [A] in the reaction system during the transesterification reaction is particularly preferable.

Next, the transesterification method of the present invention is carried out using the raw materials and catalysts described in detail above. As a concrete method, 1. A method of preparing the gel-like styrene polymer or gel-like polysiloxane polymer [A] in advance, and charging the same with an alcohol and a carboxylic acid ester in a reaction vessel to carry out a transesterification reaction (hereinafter, referred to as “method 1”). Abbreviated), 2. When an unsaturated carboxylic acid ester is used as the carboxylic acid ester, the metal compound (a) and the solid phosphine compound (b ′) are charged in a reactor together with the unsaturated carboxylic acid ester and alcohol to perform a transesterification reaction. Method (hereinafter, “Method 2”)
Abbreviated).

In the method 1, any of the alcohols mentioned above can be used, and therefore, it can be widely applied not only to the use of the reactive monomer but also to the synthesis of polyester and other various raw material systems. Therefore, fibers, molding materials,
It can be applied to the production of ester compounds, polyesters, unsaturated polyesters, etc. used for applications such as paints and pharmaceuticals.

The amount of the catalyst used in Method 1 is not particularly limited, but the phosphonium structure (b) is contained in the gel-like styrene polymer or gel-like polysiloxane polymer [A] with respect to the hydroxyl group of the alcohol. As a rate
It is 0.01 to 5.0 mol%, and more preferably 0.
It is preferably in the range of 05 to 3.0 mol%.

Next, in the method 2, the solid phosphine compound (b ') and the metal compound (a) may be added to the reaction system at the same time or may be separately added to the reaction system. When these two components are added simultaneously, they may be added in a single dose at the start of the reaction, or may be divided into two or more doses and administered to the reaction system.

The solid phosphine compound (b ')
When the metal compound (a) is added to the reaction system after, for example, about 2 hours have elapsed, the reaction rate is higher than that when two components are simultaneously added at the start of the reaction. Therefore, the reaction time can be shortened.

The amount of the catalyst used is not particularly limited, but the amount of the metal compound (a1) is preferably 0.01 to 5.0 mol% with respect to the hydroxyl group of the alcohol. Preferably, it is in the range of 0.05 to 3.0 mol%. On the other hand, the amount of the solid phosphine compound (b ′) used is not particularly limited, but (a) :( b ′) is 1: 1 in a molar ratio with respect to the metal compound (a).
The range of 0 to 10: 1 is preferable, and the range of 1: 5 to 5: 1 is particularly preferable.

The transesterification reaction of each of the above-mentioned Method 1 and Method 2 is reversible, and in order to complete the reaction, a low-boiling monohydroxyl-containing alcohol (eg, methanol, ethanol, butanol) produced in the transesterification step is used. It is preferable to carry out the reaction by continuously removing the above) outside the reaction system.

Further, in the transesterification reaction of the present invention, the alcohol produced during the transesterification reaction can be efficiently removed to the outside of the system. It is preferable to use an alicyclic hydrocarbon solvent as an auxiliary solvent.

The amount of the auxiliary solvent used is not particularly limited, but is in a range that does not affect the reaction product of the transesterification reaction, specifically, about 5 to 50% by weight, preferably 10% by weight of the starting material. It can be used within a range of up to 30% by mass.

Specific examples of such an auxiliary solvent include n
-Pentane, n-hexane, n-heptane, n-octane, cyclohexane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, ethylbenzene, cumene and the like. Among these, n-hexane, n-heptane, cyclohexane, toluene and the like are preferable. These hydrocarbon solvents are azeotropically recovered, and can be recovered by further extracting alcohol with water.

In addition to using the above-mentioned auxiliary solvent, dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide,
It is preferable to use an aprotic polar solvent such as sulfolane. Such an aprotic polar solvent can be recovered by distillation after the reaction is completed.

In the transesterification method of the present invention, when an unsaturated carboxylic acid ester or an unsaturated alcohol is used as a raw material, the polymerization of an unsaturated bond occurring during the reaction should be suppressed by a polymerization inhibitor. Is preferred. Examples of the polymerization inhibitor that can be used here include benzoquinone, hydroquinone, catechol, diphenylbenzoquinone, hydroquinone monomethyl ether, naphthoquinone, t-butylcatechol, t-butylphenol, dimethyl-t-butylphenol, t-butylcresol, and phenothiazine. Can be mentioned.

The amount of the polymerization inhibitor used depends on the amount of the product, the unsaturated ester and the amount of the unsaturated alcohol, but is usually 5 to 10000 mass ppm, especially 2
It is preferably in the range of 0 to 7,000 mass ppm.

The transesterification method of the present invention is not particularly limited in reaction conditions and can be carried out at atmospheric pressure. The reaction temperature may be appropriately selected depending on the reaction product, particularly the carboxylic acid ester used and the reaction solvent, but is preferably 20 to 160 ° C., for example. That is, 160 ° C
In the following temperature range, the polymerization reaction can be suppressed,
Further, the reaction rate is increased in the temperature range of 20 ° C. or higher. Generally, the higher the reaction temperature, the faster the reaction rate. From the point of balance of these effects, 30-150 ℃
The range of 60 to 130 ° C. is preferable. Further, when the reaction is carried out under reduced pressure to remove the produced alcohol and the reaction temperature is defined by the boiling point of the removed alcohol, the reaction temperature is 60 to 120.
C. is preferred.

In the transesterification reaction method of the present invention, the proportion of alcohol and carboxylic acid ester used is
Although not particularly limited, the molar ratio of carboxylic acid ester to alcohol is usually 1 or more,
Among them, the molar ratio of the carboxylic acid ester to the hydroxyl group of the alcohol, that is, the hydroxyl group of the carboxylic acid ester: alcohol is preferably in the range of 1.1: 1 to 10: 1.

In the transesterification reaction method of the present invention, during the reaction, the reaction mixture is heated with stirring within the appropriate temperature range described above, usually to the reflux temperature of the reaction system. While stirring the reaction mixture, in order to complete the reaction, the alcohol produced by the transesterification reaction during the reaction is often removed as an azeotrope with an excess of carboxylic acid ester or the reaction solvent by a fractionating tube, at the same time. If necessary, the same amount of carboxylic acid ester or reaction solvent is added to the reaction mixture,
It is preferred to keep the amount of reactor contents constant.

During the reaction, the content of the target product in the reaction mixture is traced by gas chromatography analysis or the like,
The reaction is continued until the content of the desired product is 90% or more. The reaction time is not particularly limited, but is usually 6 to 40 hours.

Since the transesterification reaction is reversible, it is preferred that the alcohol residue portion of the carboxylic acid ester is continuously removed outside the system.

After the completion of the reaction, the obtained reaction crude product can be recovered very easily as a gel styrene polymer or gel polysiloxane polymer [A] by filtration. The gel-like styrene-based polymer or gel-like polysiloxane-based polymer [A] thus isolated is
Again, it can be used as a transesterification reaction catalyst.

Then, if desired, volatile components such as unreacted monomer components and organic solvents can be distilled off to isolate the desired ester compound very easily.

When (meth) acrylate is used as the raw material monomer when distilling off the volatile components, it is preferable to introduce air or oxygen gas at the time of heating and mixing to prevent polymerization of the monomer.

The ester compound thus obtained is
Reactive monomers useful for various applications such as paint resins, printing inks, UV curable resins, molding resins, films, adhesives, etc., ester compounds used as raw materials for medicines and agricultural chemicals,
In addition, it is extremely useful industrially as polyester. In particular, when an unsaturated carboxylic acid ester is used as a raw material, it is extremely useful as a so-called reactive monomer that is polymerized by active energy rays, heat, a radical polymerization initiator and the like.

It should be noted that, in the production of such a reactive monomer by a transesterification reaction, generally,
The unsaturated bond is easily polymerized, and particularly with respect to esters containing a (meth) acrylate group, the higher the number of contained (meth) acrylate groups, the higher the purity and the yield of the target ester can be obtained. It is difficult, but according to the transesterification method of the present invention, the object product can be obtained in high purity and high yield with almost no such polymerization. Therefore,
For example, trimethylolpropane triacrylate (T
MPTA), ethoxy modified trimethylolpropane triacrylate (EOTMPTA), neopentyl glycol diacrylate (NPGDA), pentaerythritol triacrylate (PETA), propoxy modified neopentyl glycol diacrylate (PONPGD
A), tripropylene glycol diacrylate, 1,
4-butanediol diacrylate, polyethylene glycol diacrylate (PEGDA), diethylene glycol diacrylate (DEGDA), ethylene glycol diacrylate (EGDA), tetrahydrofurfuryl acrylate (THFA), dipentaerythritol penta and hexaacrylate, and the like. Very useful for the production of the corresponding methacrylates. According to the transesterification method of the present invention, these products have a purity of 90% or more in gas chromatography analysis,
Furthermore, it reaches 95% or more.

[0056]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples of representative aspects of the present invention, and the present invention is not limited thereto. The reagents used are reagent products except those described as industrial products.

(Purity Analysis Method by Gas Chromatography) The purity analysis method by gas chromatography is as follows. Gas chromatography apparatus used: Shimadzu GC-14A type gas chromatography apparatus. GC
Column: 60 mDB-1 (methyl silicon capillary column), injection part temperature: 300 ° C., column temperature: 150-
300 ° C (temperature rising rate: 10 ° C / min), detector: hydrogen flame ionization detector, detection part temperature: 300 ° C, carrier gas:
Ar gas 1.8 mL / min.

(Purity Analysis Method by Gel Permeation Chromatography (GPC)) The purity analysis method by gel permeation chromatography is as follows. GPC device used: SC8010 type fully automatic GPC system manufactured by Tosoh Corporation. Column used: TSK _gel G1000H
Two _XL (30 cm) and TSK _gel G2000H _XL (30 cm) 1
Used by connecting books. Column oven temperature: 40 ° C., detector: differential refractometer, eluent (flow rate): tetrahydrofuran (0.8 mL / min).

Example 1 PS-P ⁺ (Ph) ₂ CH ₂ CH ₂
CO ₂ ^- in the eggplant flask 300mL with synthetic stirrer, polystyrylmethyl Jill diphenylphosphine (Argonaut Technolog
Made by ies Inc., phosphorus content: 1.37 mmol / g) 1
3.1 g (18 mmol), 96 mL of ethyl acetate, 24 mL of acetone, and 1.3 g of acrylic acid (18 mmo
1) was charged, and the mixture was stirred at room temperature under an argon atmosphere. The reaction was completed in 60 hours, and PS- was obtained by filtration.
It was obtained _{^{14.3g - P + (Ph) 2}} CH 2 CH 2 CO 2.

Example 2 PSil-CH ₂ CH ₂ P ⁺ (P
h) Synthesis of ₂ CH ₂ CH ₂ CO ₂ ^{— In} Example 1, polystyridyl diphenylphosphine (manufactured by Argonaut Technologies Inc., phosphorus content:
1.37 mmol / g) Instead of 13.1 g (18 mmol), Journal of Organometallic Chemistr
y), 1989 years, 369 vol, was synthesized by the method described on pages 17-28, polysiloxane - phosphine compound S-CH ₂ CH ₂
PPh ₂ (phosphorus content: 2.16 mmol / g) 8.
The procedure of Example 1 was repeated except that 3 g (18 mmol) was used. After completion of the reaction, PSil-CH _{2 is} obtained by filtration.
^{_{CH 2 P + (Ph) 2}} CH 2 CH 2 CO 2 - was obtained 9.5 g.

Example 3 [PS-P ⁺ (Ph) ₂ CH ₂ CH
^{_{2 CO 2 -] [Zn (}} OAc) 2] Synthesis stirrer, a thermometer, a four-necked flask 100mL having a glass tube to flow fractionator and dry air, methyl acrylate 43 g (0.5 mol ), Zinc acetate dihydrate 5.
3 g (24 mmol) and 0.05 g of p-methoxyphenol were charged. While stirring, polystyridyldiphenylphosphine (manufactured by Argonaut Technologies Inc., phosphorus content: 1.37 mmol / g) 14.6 g (20 m)
mol) was added, the reaction mixture was heated under reflux at 80 ° C. for 12 hours, and the azeotropic mixture of methanol and methyl acrylate was removed from the reaction system from the top of the fractionating tube. At the same time, the same amount of methyl acrylate was added to the reaction system so as to keep the amount in the reactor. The reaction mixture was cooled and then filtered to obtain 19.6 g of the phosphonium zinc compound.

Example 4) [PS-P⁺(Ph)₂CH₂CH₂CO₂ ^-] [ClMe₂S
nOSnMe₂OSnMe ₂Cl] Synthesis Dichlorinated in a reaction vessel equipped with stirrer, thermometer, and dropping funnel.
Dimethyltin 11g (50mmol), water 80ml, eta
Charge 30 ml of knoll and stir to add dimethyl tin dichloride.
Dissolved. Then, with stirring, triethylamine
6.79 g (66.7 mmol) was added dropwise from the dropping funnel.
It was At this time, the reaction temperature was adjusted to 25 to 30 ° C using an ice bath.
I kept it. After dripping, stir for another 2 hours to complete the reaction
Let After the reaction was completed, the precipitate was filtered off and 100 ml of
After washing with water and then 200 ml of ethanol, 10
After drying under reduced pressure at 5 ℃, 1,5-dichlorohexamethyl
Tristanoxane (ClMe₂SnOSnMe₂OSnM
e₂Cl) was obtained. Next, stirrer, temperature
Volume 1 equipped with meter, fractionator and glass tube for flowing dry air
In a 00 mL four-necked flask, add 50 ethyl acrylate.
mL, p-methoxyphenol 0.05 g, and obtained
1,5-dichlorohexamethyltristanoxane (C
lMe₂SnOSnMe₂OSnMe₂Cl) 3.3 g
(6 mmol) was charged and stirred at room temperature for 30 minutes. This
The solution at that time was a heterogeneous solution. There, in Example 1
Synthesized PS-P⁺(Ph)₂CH₂CH₂CO₂ ^-  4.
Charge 8 g (6 mmol) and bring the reaction mixture to 100 ° C.
And refluxed for 2 hours. After cooling the reaction mixture, it is filtered.
Thus, 8.0 g of the phosphonium tin was obtained.

[0063] Example _{5 [PSil-CH 2 CH 2} P + (Ph) 2 CH 2 CH 2 CO 2 -
] [ClMe ₂ SnOSnMe ₂ Cl] Synthesis In a four-necked flask with a capacity of 100 mL equipped with a stirrer, a thermometer, a fractionator, and a glass tube through which dry air flows, 50 g (0.5 mol) of ethyl acrylate, p - methoxyphenol 0.05 g, and 1,3-dichloro-tetramethyl register Roh hexane _{(ClMe 2 SnOSnMe 2 Cl) 2} .
3 g (6 mmol) was charged, and the mixture was stirred at room temperature for 30 minutes. There, synthesized in Example _2, PSil-CH 2 C
^{_{H 2 P + (Ph) 2}} CH 2 CH 2 CO 2 - 1.6g (6mmo
1) was charged and the reaction mixture was heated under reflux at 100 ° C. for 2 hours. After cooling the reaction mixture, 3.8 g of the phosphonium tin was obtained by filtration.

Example 6 Synthesis of 1,4-butanedioldihexanoate 1,4-butane was placed in a 200-mL four-necked flask equipped with a stirrer, a thermometer, a fractionator, and a glass tube for flowing dry air. 22.5 g (0.25 mol) of diol, 78.1 g (0.6 mol) of methyl hexanoate, 40 g of cyclohexane, and [PS-P ⁺ (Ph) synthesized in Example 3]
^{_{2 CH 2 CH 2 CO 2 -}} ] [Zn (OAc) 2] 9.8g (10
mmol) and the reaction mixture is stirred at 80 ° C.
The mixture was heated to reflux with and the azeotropic mixture of methanol and cyclohexane was removed from the reaction system from the top of the fractionating tube. At the same time, the same amount of cyclohexane was added to the reaction system so as to keep the amount of the contents of the reactor. The reaction continued for 14 hours. After the reaction was completed, the reaction mixture was filtered to separate the catalyst. Excess cyclohexane and methyl hexanoate in the filtrate were removed by distillation under reduced pressure to obtain 68 g of a product. As a result of analyzing the product by gas chromatography, 1,4-butanediol monohexanoate: 3.2% and 1,4-butanediol dihexanoate: 96.8% were contained. (Yield 96
%)

Example 7 Synthesis of 1,4-butanediol dihexanoate using recovered catalyst In Example 6, [PS-P ⁺ (Ph) ₂ CH ₂ CH ₂ C
O ₂ ^-] [instead of _{Zn (OAc) 2] 9.8g (} 10mmol), except for using the solid 9.6g recovered in Example 6 was performed according to in Example 6. The reaction was continued for 16 hours and 69 g of product was obtained. As a result of analyzing the product by gas chromatography, 1,4-butanediol monohexanoate: 4.1% and 1,4-butanediol dihexanoate: 95.9% were contained. (Yield 97%).

Example 8 Synthesis of trimethylolpropane triacrylate In a four-necked flask having a capacity of 200 mL equipped with a stirrer, a thermometer, a fractionator, and a glass tube through which dry air flows, 120 g (1.2 mol) of ethyl acrylate was added. , Trimethylolpropane 26.8 g (0.2 mol), dimethyltin dichloride 1.32 g (6 mmol), polystyridyldiphenylphosphine (manufactured by Argonaut Technologies Inc., phosphorus content: 1.61 mmol / g) 3.75 g (6mmo
1) and 0.13 g of p-methoxyphenol were charged. The reaction mixture was heated to reflux with stirring at 100 ° C., and the azeotropic mixture of ethanol and ethyl acrylate was removed from the reaction system from the top of the fractionating tube. At the same time, the same amount of ethyl acrylate was added to the reaction system so as to maintain the amount of the contents of the reactor. The reaction was terminated in 24 hours, the reaction mixture was cooled, and the catalyst was removed by filtration. Elemental analysis of the removed catalyst revealed that the molar ratio of phosphorus atom to tin atom was 1: 0.8. Excess ethyl acrylate contained in the filtrate was removed under reduced pressure to obtain trimethylolpropane triacrylate (TMPTA). The results are shown in Table 1.

Example 9 Synthesis of trimethylolpropane triacrylate In a four-necked flask having a capacity of 300 mL equipped with a stirrer, a thermometer, a fractionator, and a glass tube through which dry air flows, 155 g (1.8 mol) of methyl acrylate was added. , Trimethylolpropane 40.2 g (0.3 mol), and p-methoxyphenol 0.2 g were charged. Next, 4.7 g (21.6 mmol) of zinc acetate dihydrate and polystyridyldiphenylphosphine (manufactured by Argonaut Technologies Inc., phosphorus content: 1.37 mmol / g) 13.1 g (18
mmol) was added to the reaction mixture under stirring.

The reaction mixture was heated to reflux with stirring, and the azeotropic mixture of methanol and methyl acrylate was removed from the reaction system from the upper portion of the fractionating tube. At the same time, the same amount of methyl acrylate was added to the reaction system so as to maintain the amount of the contents of the reactor. The reaction was continued until the trimethylolpropane triacrylate (TMPTA) in the reaction product exceeded 90%. After cooling the reaction mixture, the catalyst was separated by filtration.
Excess methyl acrylate in the filtrate was removed under reduced pressure to obtain the product. The results are shown in Table 1.

Example 10 Synthesis of trimethylolpropane triacrylate using recovered catalyst In Example 9, 4.7 g of zinc acetate dihydrate (21.
6 mmol) and polystyridyldiphenylphosphine (manufactured by Argonaut Technologies Inc., phosphorus content: 1.
The procedure of Example 9 was repeated except that 17.5 g of the solid recovered in Example 9 was used instead of 13.1 g (18 mmol) of 37 mmol / g). The reaction was continued for 30 hours to obtain the product. The results are shown in Table 1.

Example 11 Synthesis of trimethylolpropane triacrylate In a four-necked flask having a capacity of 200 mL equipped with a stirrer, a thermometer, a fractionator, and a glass tube through which dry air flows, 120 g (1.2 mol) of ethyl acrylate was added. , Trimethylolpropane 26.8 g (0.2 mol), p-methoxyphenol 0.13 g, and [PS-P ⁺ synthesized in Example 4].
_{(Ph) 2 CH 2 CH 2} CO 2 -] [ClMe 2 SnOSnM
e ₂ OSnMe ₂ Cl] (8.0 g, 6 mmol) was charged. The reaction mixture was heated to reflux with stirring at 100 ° C., and the azeotropic mixture of ethanol and ethyl acrylate was removed from the reaction system from the top of the fractionating tube. At the same time, the same amount of ethyl acrylate was added to the reaction system so as to maintain the amount of the contents of the reactor. The reaction was continued until the trimethylolpropane triacrylate (TMPTA) in the reaction product exceeded 90%. After completion of the reaction, the reaction mixture was cooled and the catalyst was removed by filtration. Excess ethyl acrylate contained in the filtrate was removed under reduced pressure to obtain the product. The results are shown in Table 1.

Example 12 Synthesis of trimethylolpropane triacrylate using recovered catalyst In Example 11, [PS-P ⁺ (Ph) ₂ CH ₂ CH _{2
^{CO 2 -] [ClMe 2 SnOSnMe}} 2 OSnMe 2 Cl]
The procedure of Example 11 was repeated except that 7.2 g of the solid recovered in Example 11 was used instead of 8.0 g (6 mmol). The reaction was continued until the trimethylolpropane triacrylate (TMPTA) in the reaction product exceeded 90%. The results are shown in Table 1.

Example 13 Synthesis of trimethylolpropane triacrylate In a four-necked flask having a capacity of 200 mL equipped with a stirrer, a thermometer, a fractionator, and a glass tube through which dry air flows, 120 g (1.2 mol) of ethyl acrylate was added. , Trimethylolpropane 26.8 g (0.2 mol), p-methoxyphenol 0.13 g, and [PSil synthesized in Example 5].
^{_{-CH 2 CH 2 P + (Ph}} ) 2 CH 2 CH 2 CO 2 -] [ClM
3.8 g (6 mmol) of e ₂ SnOSnMe ₂ Cl] was charged. The reaction mixture was heated to reflux with stirring at 100 ° C., and the azeotropic mixture of ethanol and ethyl acrylate was removed from the reaction system from the top of the fractionating tube. At the same time, the same amount of methyl acrylate was added to the reaction system so as to maintain the amount of the contents of the reactor. The reaction was continued until the trimethylolpropane triacrylate (TMPTA) in the reaction product exceeded 90%. After completion of the reaction, the reaction mixture was cooled and the catalyst was removed by filtration. Excess ethyl acrylate contained in the filtrate was removed under reduced pressure to obtain the product. The results are shown in Table 2.
Shown in.

Example 14 Synthesis of trimethylolpropane triacrylate using recovered catalyst In Example 13, [PSil-CH ₂ CH ₂ P ⁺ (P
_{h) 2 CH 2 CH 2 CO} 2 -] [ClMe 2 SnOSnMe 2 C
Example 1 was repeated except that 3.4 g of the solid recovered in Example 13 was used instead of 3.8 g. The reaction was continued until the trimethylolpropane triacrylate (TMPTA) in the reaction product exceeded 90%.
The results are shown in Table 2.

Example 15 Synthesis of hexanol acrylate 150 g (1.5 mol) of ethyl acrylate, 51 g (0.5 mol) of hexanol, 0.05 g of p-methoxyphenol, 1.1 g of dimethyltin dichloride (5 mm)
ol), and polystyridyldiphenylphosphine (Ar
Made by gonaut Technologies Inc., phosphorus content: 1.37
mmol / g) 3.7 g (6 mmol) and 4 with a capacity of 300 mL equipped with a stirrer, thermometer, flow divider and dropping funnel.
The reaction was carried out using a one-necked flask. The reaction was continued until a conversion of 90% or higher was obtained. After cooling the reaction mixture, the catalyst was separated by filtration, and excess ethyl acrylate in the filtrate was removed under reduced pressure to obtain hexanol acrylate. The results are shown in Table 2.

Example 16 Synthesis of ethylene glycol diacrylate Volume 30 equipped with stirrer, thermometer, fractionator and dropping funnel
In a 0 mL four-necked flask, 150 g of ethyl acrylate
(1.5 mol), 3.8 g (10 mmol) of 1,3-dichlorotetramethyldistannoxane, 0.1 g of p-methoxyphenol, and PS-P synthesized in Example 1.
^{_{+ (Ph) 2 CH 2 CH}} 2 CO 2 - of 7.9 g (10 mmol
1) was charged and the mixture was heated under reflux at 100 ° C. for 2 hours.
After cooling to 60 ° C, 32 g of ethylene glycol (0.5 m
ol) was charged and reacted in the same manner as in Example 11 until ethylene glycol was converted to 90% or more. After cooling the reaction mixture, the catalyst was separated by filtration, and excess ethyl acrylate in the filtrate was removed under reduced pressure to obtain ethylene glycol diacrylate. The results are shown in Table 2.

Example 17 Synthesis of neopentyl glycol diacrylate In Example 16, 32 g of ethylene glycol (0.
5 mol) instead of neopentyl glycol 52 g
The procedure of Example 15 was repeated except that (0.5 mol) was used. The reaction was continued until the content of neopentyl glycol diacrylate (NPGDA) in the reaction product exceeded 90%. The results are shown in Table 2.

Example 18 Synthesis of trimethylolpropane trimethacrylate In Example 11, 120 g of ethyl acrylate (1.
2 mol), 120 g of methyl methacrylate
The procedure of Example 11 was repeated except that (1.2 mol) was used. The results are shown in Table 2.

Comparative Example 1 Using the same reactor as in Example 11, 20.1 g (0.15 mol) of trimethylolpropane, 100 g (1.0 mol) of ethyl acrylate, 0.4 g of p-methoxyphenol and polystyryl were used. Zirphosphine (Argonaut Tec
Manufactured by hnologies Inc., phosphorus atom content: 1.37 mmo
1 / g) 3.3 g (4.5 mmol) was charged, and the reaction mixture was heated to reflux with stirring at 100 ° C. to remove the azeotrope of ethanol and ethyl acrylate from the reaction system. The reaction was carried out while adding the same amount of ethyl acrylate so as to be constant. Gelation proceeded with the passage of time.

Comparative Example 2 Using the same reactor as in Example 11, 20.1 g (0.15 mol) of trimethylolpropane, 100 g (1.0 mol) of ethyl acrylate, 0.4 g of p-methoxyphenol and polysiloxane were used. -Phosphine compound PSi
_{l-CH 2 CH 2 PPh 2} ( content of phosphorus atoms: 2.16
mmol / g) 2.1 g (4.5 mmol), the azeotrope of ethanol and ethyl acrylate was removed as in Comparative Example 1, and the same amount of ethyl acrylate was added so that the amount of the reaction product was constant. While reacting. Gelation proceeded with the passage of time.

Comparative Example 3 Using the same reactor as in Example 11, 20.1 g (0.15 mol) of trimethylolpropane, 86 g (1.0 mol) of methyl acrylate, 0.4 g of p-methoxyphenol and 1. As in Comparative Example 1, 0 g (4.56 mmol) of zinc acetate dihydrate was removed from the azeotrope of methanol and methyl acrylate, and the same amount of methyl acrylate was added so that the amount of the reaction product was constant. While reacting. No triacrylate was obtained even after 30 hours of reaction. The results are shown in Table 3.

Comparative Example 4 Using the same reactor as in Example 11, 20.1 g (0.15 mol) of trimethylolpropane, 100 g (1.0 mol) of ethyl acrylate, 0.4 g of p-methoxyphenol and 1. Similarly to Comparative Example 1, 0 g (4.55 mmol) of dimethyltin dichloride was removed by removing the azeotrope of ethanol and ethyl acrylate, and the reaction was performed while adding the same amount of ethyl acrylate so that the amount of the reaction product was constant. Let The results are shown in Table 3.

The ratios in the table represent comparative examples, and the symbols have the following meanings. TMP: trimethylol propane (manufactured by Mitsubishi Gas Chemical Co., Ltd.), EGMPE: ethylene glycol monophenyl ether (manufactured by Nippon Emulsion), HEXA: 1-hexanol (manufactured by Wako Pure Chemical Industries), EG: ethylene glycol (manufactured by Wako Pure Chemical Industries), NPG: Neopentyl glycol (manufactured by Wako Pure Chemical Industries), MA: methyl acrylate (manufactured by Mitsubishi Chemical), EA:
Ethyl acrylate (manufactured by Mitsubishi Chemical), MMA: methyl methacrylate (manufactured by Mitsubishi Chemical), PS-PPh _2: polystyryl Gilles diphenylphosphine (Argonaut Technologies an In
c.)

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

According to the transesterification method of the present invention,
In addition to the very good reaction yield and purity of the target ester compound, after the completion of the reaction, a complicated neutralization step is not required, and the catalyst can be isolated very easily by filtration. The catalyst obtained can be reused.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C07B 61/00 300 C07B 61/00 300 F term (reference) 4G069 AA06 BA27A BA27B BC20A BC22A BC22B BC38A BC49A BE28A BE28B BE32A BE32B BE45A BE46A BE46B CB25 CB75 4H006 AA02 AC48 BA07 BA11 BA48 BB11 BB20 BB22 BC10 BC19 BC31 BC34 KA03 KC14 4H039 CA66 CL60

Claims (6)

[Claims] 1. A phosphonium structure (b) having a structure in which an anionic functional group is coordinated to a transition metal or a metal compound (a) containing a metal atom belonging to Group IIB, IIIA or IVA of the periodic table. A transesterification reaction method characterized by carrying out a transesterification reaction between an alcohol and a carboxylic acid ester in the presence of the gel styrene polymer or gel polysiloxane polymer [A]. 2. The method according to claim 1, wherein the carboxylic acid ester is an unsaturated carboxylic acid ester. 3. A phosphonium structure (b) having a structure in which an anionic functional group is coordinated to a transition metal or a metal compound (a) containing a metal atom belonging to Group IIB, IIIA or IVA of the periodic table. , The following structural formula: (In the formula, R ₁ and R ₂ each independently have 1 to 20 carbon atoms.
Alkyl group, C2-C10 alkenyl group, C5-C10 cycloalkyl group, C5-C5
Represents a cycloalkenyl group having 10 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group, X represents a halogen atom, an acyloxy group having 1 to 20 carbon atoms, and R ₃ represents alkylene having 1 to 20 carbon atoms. Represents a group, and n is 1 to 20
Represents the integer. The manufacturing method of Claim 1 represented by these. 4. A phosphonium structure (b) having a structure in which an anionic functional group is coordinated to a transition metal or a metal compound (a) containing a metal atom belonging to Group IIB, IIIA or IVA of the periodic table. , The following, the following structural formula: (In the formula, each of R ₁ , R ₂ and R ₄ independently has 1 carbon atom.
˜20 alkyl group, C 2-10 alkenyl group, C 5-10 cycloalkyl group, C 5-10 cycloalkenyl group, C 7-15
Represents an aralkyl group or an aryl group, X represents a halogen atom, an acyloxy group having 1 to 20 carbon atoms, or a phenyl group, R ₃ represents an alkylene group having 1 to 20 carbon atoms, and n is 1 to 20. , And m represents an integer of 0 or 1. The manufacturing method of Claim 1 represented by these. 5. After the completion of the reaction, the reaction crude product obtained is filtered so that the anion moiety of the phosphonim group having an anionic functional group is a transition metal or a group IIB group of the periodic table,
A gel-like styrene-based polymer or gel-like polysiloxane-based polymer having a phosphonium group (b) containing an anionic functional group coordinated to a metal compound (a) containing a metal atom belonging to Group IIIA or Group IVA [A ] Is isolated and collect | recovered, The reaction method of Claim 1. 6. A transition metal or a group IIB or II of the periodic table, wherein the anion site of the phosphonim group having an anionic functional group is a transition metal.
Gel-like styrene polymer or gel-like polysiloxane polymer having a phosphonium group (b) containing an anionic functional group coordinated to a metal compound (a) containing a metal atom belonging to Group IA or Group IVA [A ] The transesterification reaction catalyst characterized by consisting of these.