JPH11269160A - (meth)acrylic acid ester, its production and its (co) polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an acrylic monomer having a γ-butyrolactone ring, and useful as a constituent monomer of a coating material, an adhesive, a tacky agent, a resin for an ink, or the like, and further to provide a method for producing the acrylic monomer, and to obtain a (co)polymer containing the acrylic monomer as a constituent unit. SOLUTION: This (meth)acrylic ester of the general formula (R is hydrogen or methyl) is obtained by reducing α-acetyl-γ-butyrolactone, and esterifying the obtained product with a (meth)acrylic acid, a (meth)acrylic ester or a (meth) acrylic chloride. The (co)polymer containing the (meth)acrylic ester as a constituent unit has 1,000-100,000 weight average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an acrylic monomer containing a γ-butyrolactone ring which is a highly polar functional group, a method for producing the acrylic monomer, and a paint containing the acrylic monomer as a constituent unit. adhesive,
The present invention relates to a (co) polymer useful for an adhesive, a resin for ink, and the like.

[0002]

2. Description of the Related Art Acrylic monomers containing a γ-butyrolactone ring, which is a chemically stable and highly polar functional group, are useful as constituent monomers for paints, adhesives, adhesives, and resins for inks. Though possible,
Previously unknown. Also, of course, its production method and its (co) polymer are not known.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an acrylic monomer containing a γ-butyrolactone ring which is useful as a constituent monomer of paints, adhesives, pressure-sensitive adhesives, resins for inks, etc. An object of the present invention is to provide a method for producing a monomer and a (co) polymer containing the acrylic monomer as a constitutional unit.

[0004]

A first aspect of the present invention is a (meth) acrylate ester represented by the general formula (1).

[0005]

Embedded image

A second aspect of the present invention is the above-mentioned general formula (A) wherein α-acetyl-γ-butyrolactone is reduced and then esterified with (meth) acrylic acid, (meth) acrylic acid ester or (meth) acrylic acid chloride. This is a method for producing the (meth) acrylic ester shown in 1).

A third aspect of the present invention is a (co) polymer containing the (meth) acrylate represented by the general formula (1) as a constitutional unit and having a weight average molecular weight of 1,000 to 1,000.
100,000 (co) polymer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION γ-butyrolactone itself is
Since it is a good solvent for various organic low-molecular and high-molecular compounds, it also has water solubility. Therefore, it is expected that a (meth) acrylate ester having γ-butyrolactone as a functional group also has such a unique property. Further, the γ-butyrolactone ring has almost no polymerizability in the ring itself like a β-propiolactone ring, a δ-valerolactone ring or an ε-caprolactone ring, is extremely stable chemically and has good thermal stability. Therefore, it is expected that a (meth) acrylate having γ-butyrolactone as a functional group also has excellent stability.

The present inventors have found that the (meth) acrylate represented by the general formula (1) satisfies such conditions. The (meth) acrylate represented by the general formula (1) of the present invention specifically refers to 1- (γ-) when R in the general formula (1) is a hydrogen atom.
Butyrolactone-2-yl) ethyl acrylate and 1- (γ-butyrolactone-2-yl) ethyl methacrylate when R in the general formula (1) is a methyl group. In order to improve the polymerizability of the (meth) acrylate represented by the general formula (1), R in the general formula (1) is preferably a hydrogen atom.

The (meth) acrylic acid ester represented by the general formula (1) is stable under neutral conditions, but has an (meth) acryloyloxy group at the β-position of the lactone ring, so that an acid or a base can be used. Is expected to be a latent carboxyl monomer since it is easily eliminated by the action of to generate a carboxyl group.

[0011] However, despite the above-mentioned usefulness, the production method has not been known. Therefore, such a (meth) acrylic acid ester containing a γ-butyrolactone ring has been conventionally known. Had not been.

As a result of intensive studies, the present inventors have found a method for producing a (meth) acrylic acid ester having a γ-butyrolactone ring represented by the general formula (1) in an extremely short process. However, the (meth) acrylate represented by the general formula (1) of the present invention is not necessarily limited to this production method.

That is, the second aspect of the present invention is to provide α-acetyl-
general formula (1) wherein γ-butyrolactone is reduced and then esterified with (meth) acrylic acid, (meth) acrylic acid ester, or (meth) acrylic acid chloride
Is a method for producing a (meth) acrylic acid ester represented by the formula:

The method for reducing α-acetyl-γ-butyrolactone is not particularly limited, and examples thereof include a catalytic hydrogenation method and a method of reacting a metal hydride. The compound obtained by this reduction is α- (1-hydroxy)
Ethyl-γ-butyrolactone.

The catalyst used for reducing α-acetyl-γ-butyrolactone by the above-mentioned catalytic hydrogenation method includes, for example, general catalytic reduction catalysts containing nickel, iron, platinum, palladium, copper and the like. . The amount of the catalyst used varies depending on the catalytic activity, reaction conditions, and the like, and cannot be specified unconditionally. Usually, however, it is present in an amount of 1 / 10,000,000 equivalent to 1/10 equivalent of α-acetyl-γ-butyrolactone. The reaction conditions for this reduction method include a reaction pressure of 50 KP
a to 15 MPa and a reaction temperature of 0 to 200 ° C. are industrially preferable.

The metal hydride used for reducing α-acetyl-γ-butyrolactone by the action of the above metal hydride includes, for example, sodium borohydride, lithium borohydride, potassium borohydride, hydride Diisobutylaluminum, lithium aluminum hydride, triethyllithium borohydride, bis (2
-Methoxyethoxy) sodium aluminum and the like. Although the amount of these metal hydrides cannot be specified unconditionally, it is usually 0.2 to 2 equivalents to α-acetyl-γ-butyrolactone. This reduction method is usually carried out at a reaction pressure of 50 KPa to 1 MPa and a reaction temperature of -80 to 150 ° C., and has the advantage that there is little restriction on equipment because high pressure is not required.

Α- (1-hydroxy) ethyl-γ-butyrolactone obtained by reduction of α-acetyl-γ-butyrolactone is subsequently treated with (meth) acrylic acid and (meth) acrylic acid.
The (meth) acrylic ester represented by the general formula (1) is produced by esterification with an acrylic ester or (meth) acrylic chloride. The obtained product may be purified by a conventional method, if necessary.

When α- (1-hydroxy) ethyl-γ-butyrolactone is esterified with (meth) acrylic acid, the reaction temperature of the esterification reaction is usually -30 to 100.
° C. In this reaction, since the starting alcohol is unstable to acid, it is preferable to use a condensing agent instead of an acid catalyst as the esterification catalyst. The condensing agent is not particularly limited as long as it is a general condensing agent for esterification, for example, N,
N'-dicyclohexylcarbodiimide, 2-chloro-
1,3-dimethylimidazolium chloride, propanephosphonic anhydride and the like. At this time, an amine base such as 4-methylaminopyridine or triethylamine may be used in combination.

When α- (1-hydroxy) ethyl-γ-butyrolactone is esterified with (meth) acrylic acid ester, the transesterification reaction temperature is usually 20.
C. to 120C. As the (meth) acrylate used at this time, methyl acrylate or methyl methacrylate having a high transesterification rate is preferable.
As a catalyst for this reaction, a known catalyst for transesterification can be used. Such transesterification catalysts include, for example, tetramethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, triisopropoxyaluminum, tri-n-butoxyaluminum, dimethoxymagnesium, diethoxymagnesium, tetraisotitanium Propoxy zirconium,
Examples thereof include tetra-n-butoxyzirconium, dibutyltin oxide, and dioctyltin oxide.

When α- (1-hydroxy) ethyl-γ-butyrolactone is esterified with (meth) acrylic acid chloride, the reaction temperature of the esterification reaction is usually -80.
１００100 ° C. At this time, it is desirable to add a base catalyst in an equivalent amount or more to the acid chloride in the reaction system. Such a base catalyst is not particularly limited as long as it neutralizes the generated acid, for example, triethylamine,
Pyridine, sodium hydrogen carbonate and the like can be mentioned.

That is, according to the present invention, as shown in the formula (2), an inexpensive α-acetyl-γ-butyrolactone is used as a raw material, which is reduced, and further reduced to (meth) acrylic acid, (meth) acrylate, or The (meth) acrylic acid ester containing γ-butyrolactone represented by the general formula (1) is produced in an extremely short step of esterification with (meth) acrylic acid chloride.

[0022]

Embedded image

A third aspect of the present invention is a (co) polymer containing the (meth) acrylate represented by the general formula (1) as a constitutional unit, and having a weight average molecular weight of 1,000 to 1,000.
100,000 (hereinafter referred to as the (co) polymer of the present invention). Paints, adhesives, adhesives,
For applications such as ink resins, the weight average molecular weight of the (co) polymer of the present invention is preferably from 1,000 to 100,000. Further, the (co) polymer of the present invention has the general formula (1)
It is preferable to contain 30 to 100 mol% of a (meth) acrylate represented by the following formula as a constitutional unit. In order to improve the heat resistance of the (co) polymer of the present invention, R in the general formula (1) is preferably a methyl group.

The (co) polymer of the present invention may be a homopolymer of the (meth) acrylate represented by the general formula (1) or the (meth) acrylate represented by the general formula (1). Copolymers of other monomers may be used. When the (co) polymer of the present invention is a copolymer of the (meth) acrylate represented by the general formula (1) and another monomer, the copolymer composition is not particularly limited. The other monomer is not particularly limited as long as it can be copolymerized with the (meth) acrylate represented by the general formula (1). Such monomers include:
Examples include methacrylic acid, styrene, methyl methacrylate, mevalonolactone methacrylate, 2-methyladamantyl methacrylate, and the like.

When the copolymer of the present invention is a copolymer of a (meth) acrylate represented by the general formula (1) and a monomer having an alicyclic skeleton, the copolymer has the general formula (1) In addition to the property of high polarity derived from the (meth) acrylic acid ester shown in (1), it also has hydrophobicity and heat resistance derived from a monomer having an alicyclic skeleton. Examples of such a monomer having an alicyclic skeleton include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentadienyl (meth) acrylate. And their substituents.

According to the process for producing a (co) polymer of the present invention, the (co) polymer obtained contains a (meth) acrylate represented by the general formula (1) as a structural unit. Having a weight average molecular weight of 1,000 to 100,
The method is not particularly limited as long as it is 000, and a known polymerization method can be used. Such a production method includes, for example, a batch polymerization method in which polymerization is started by mixing all of the monomers and the like.

[0027]

The present invention will be described below in detail with reference to Examples, but it should not be construed that the invention is limited thereto. The analysis in the examples was performed by gas chromatography (hereinafter, referred to as GC) and NMR. Purity was calculated from the peak area of GC by the following formula. Purity (%) = (A / B) × 100 where A represents the peak area of the target product, and B represents the sum of all peak areas. The actual yield was calculated by the following equation. Actual yield (%) = (C / D) × 100 where C is the number of moles of the target product (calculated by multiplying the weight of the target product containing impurities by the purity and dividing by the molecular weight of the target product). ) And D represent the number of moles of the reference raw material.

The physical properties of the copolymer were measured by the following methods.・ Weight average molecular weight Gel permeation chromatography (GP
It was determined by C) in terms of polymethyl methacrylate. Chloroform was used as a solvent. The (co) polymer composition of the structural unit was measured by ¹ H-NMR and determined from the integrated intensity ratio. Heavy chloroform was used as a solvent.

Example 1 (1) Synthesis of α- (1-hydroxy) ethyl-γ-butyrolactone α-acetyl-γ-butyrolactone was placed in a glass flask equipped with a stirrer, a dropping funnel, a thermometer, and a Dimroth condenser. 128 g (1.0 mol), dry methanol 300 m
sodium borohydride while cooling with ice.
9 g (0.5 mol) were added. The reaction exothermed to about 30 ° C. After stirring for 3 hours, 100 g of water was added, and 50 g (0.5 mol) of 36.5% hydrochloric acid was further added for neutralization while cooling with ice. This was concentrated to remove methanol, and extracted twice with 500 ml of ethyl acetate, and the organic layer was dried over 30 g of anhydrous magnesium sulfate. This was filtered and concentrated to obtain crude α- (1-hydroxy) ethyl-γ-butyrolactone 1
10 g were obtained. This was purified by distillation, and 46.2 g of α- (1-hydroxy) ethyl-γ-butyrolactone was obtained.
(0.35 mol) was obtained.

The resulting α- (1-hydroxy) ethyl-
The purity of γ-butyrolactone is 98% and the actual yield is 35%
(Based on α-acetyl-γ-butyrolactone).
The ¹ H-NMR spectrum data of the product was as follows. ¹ H-NMR (CDCl ₃ ), 1.3 (3 H, d, J = 5.9 Hz), 1.98 to 2.05 (1 H, m),
2.23 ~ 2.37 (1H, m), 2.50 ~ 2.57 (1H, m), 3.89 ~ 3.94 (1H, m
m), 4.21-4.25 (1H, m), 4.37-4.44 (1H, m)

(2) Synthesis of 1- (γ-butyrolactone-2-yl) ethyl methacrylate α- (1-hydroxy) ethyl- was added to a glass flask equipped with a stirrer, a dropping funnel, a thermometer, and a Dimroth condenser.
46 g (0.35 mol) of γ-butyrolactone and 300 ml of dry methylene chloride were charged, and 46.5 g (0.46 mol) of triethylamine was charged to one of the dropping funnels, and 44 g (0.42 mol) of methacrylic acid chloride was charged to the other. After replacing the inside with nitrogen, the inside was cooled to −60 to −70 ° C. in a dry ice-acetone bath. While stirring the inside of the glass flask, triethylamine and methacrylic acid chloride were added dropwise while adjusting the amount of triethylamine to methacrylic acid in a small excess. After completion of the dropwise addition, stirring was continued for 2 hours. The reaction solution was washed three times with 300 ml of water in a separating funnel, and then washed with magnesium sulfate 3 times.
0 g was added and dried, and the filtrate was concentrated.
40 g of (γ-butyrolactone-2-yl) ethyl methacrylate was obtained. This was purified by silica gel column chromatography to obtain 34 g (0.17 mol) of 1- (γ-butyrolactone-2-yl) ethyl methacrylate.

The obtained 1- (γ-butyrolactone-2-
The purity of yl) ethyl methacrylate was 97%, and the actual yield was 48.6% (based on α- (1-hydroxy) ethyl-γ-butyrolactone). This 1- (γ-butyrolactone-2-yl) ethyl methacrylate has a syn form, a
The mixture was obtained as a mixture of nti-forms, and the ratio was about 20% for the syn-form and about 80% for the anti-form from the integrated value of the ¹ H-NMR spectrum. The ¹ H-NMR spectrum data of the product was as follows. syn form: ¹ H-NMR (CDCl ₃ ) 1.4 (3H, d, J = 5.9Hz), 1.9 (3H, s), 2.33 ~
2.46 (2H, m), 2.8 (1H, dt, J = 3.8Hz, J = 9.0Hz), 4.21 ~ 4.42 (2
H, m), 5.28~5.39 (1H , m), 5.6 (1H, s), 6.1 (1H, s) anti _{^{body: 1 H-NMR (CDCl 3}} ) 1.4 (3H, d, J = 5.9Hz), 1.9 (3H, s), 2.33-2.4
6 (2H, m), 2.9 (1H, dt, J = 3.8Hz, J = 9.0Hz), 4.21 ~ 4.42 (2H, m
m), 5.28-5.39 (1H, m), 5.6 (1H, s), 6.1 (1H, s)

Example 2 In a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, under a nitrogen atmosphere, 2-methyladamantyl methacrylate 23.4.
g, 1- (γ-butyrolactone-2-yl) ethyl methacrylate 29.8 g, 1,4-dioxane 82.5
g, 3.8 g of azobisisobutyronitrile,
While stirring, raise the temperature of the hot water bath to 80 ° C.
Polymerized for hours. Then, the obtained reaction solution was diluted about 2-fold with tetrahydrofuran and added dropwise to about 10-fold amount of methanol while stirring, to obtain a white precipitate.
The obtained precipitate was separated by filtration and dried under reduced pressure at 60 ° C. for about 40 hours to obtain 37.2 g of a copolymer. The weight average molecular weight of the obtained copolymer was 12,000, and the copolymer composition of 1- (γ-butyrolactone-2-yl) ethyl methacrylate structural unit was 60 mol%.

[0034]

The γ of the present invention represented by the general formula (1)
-(Meth) acrylic acid esters containing a butyrolactone ring can be widely used as constituent monomers for paints, adhesives, pressure-sensitive adhesives, resins for inks and the like.

Further, according to the production method of the present invention, a (meth) acrylic acid ester containing γ-butyrolactone represented by the above general formula (1) can be produced from inexpensive α-acetyl-γ-butyrolactone as a raw material. It can be manufactured in a short process.

Further, the present invention is a (co) polymer containing the (meth) acrylic acid ester represented by the above general formula (1) as a constitutional unit and having a weight average molecular weight of 1,000 to 1,000.
The (co) polymer having a molecular weight of 100,000 contains a highly polar γ-butyrolactone ring in its structure and is useful as a paint, an adhesive, a pressure-sensitive adhesive, a resin for ink, and the like.

Claims (3)

[Claims] 1. A (meth) acrylic acid ester represented by the general formula (1). Embedded image 2. The general formula (1) according to claim 1, wherein α-acetyl-γ-butyrolactone is reduced and then esterified with (meth) acrylic acid, (meth) acrylic acid ester or (meth) acrylic acid chloride. )). 3. A (co) polymer comprising a (meth) acrylate represented by the general formula (1) according to claim 1 as a constitutional unit, and having a weight average molecular weight of 1,000 to 1,000.
100,000 (co) polymer.