JP2006328012A - Acrylic compound, its production method and acrylic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new acrylic compound which can give acrylic polymers having excellent heat resistance and solvent resistance, to provide a method for producing the same, and to provide an acrylic polymer produced by polymerizing the new acrylic compound. <P>SOLUTION: The 1-acyloxyethyl (meth)acrylate (acyl group is a 1 to 4C alkyl) represented by formula (1). The method for producing the acrylic compound comprises reacting a specific (meth)acrylic acid with a specific vinyl aliphatic carboxylate in the presence of a catalyst. The acrylic polymer produced by polymerizing the acrylic compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an acrylic compound, a method for producing the same, and an acrylic polymer, and more specifically, a novel acrylic compound, a method for producing the same, and the novel acrylic compound as a monomer, heat resistance and solvent resistance. The present invention relates to a novel acrylic polymer having excellent properties.

Polymethyl methacrylate, which is a typical example of an acrylic polymer, is excellent in transparency and weather resistance, and has a good balance of properties such as mechanical properties, thermal properties and moldability. It is used in a wide variety of fields as a molding material for obtaining sheets, pipes and the like.
Polymethyl methacrylate having the above-mentioned characteristics is, for example, OA equipment field such as glazing material, lamp meter cover and printer cover; miscellaneous goods field such as game peripheral parts such as pachinko; display field such as store signboard; Building materials such as ports and bathtubs; Information optical elements such as liquid crystal light guide plates, video discs and audio discs; Light electrical and industrial parts such as vending machine front plates; Molding materials used in lighting fixtures such as lighting covers As widely used.

However, although polymethyl methacrylate known so far has excellent characteristics as described above, there is a problem that the allowable limit temperature that can be used is about 100 ° C. and the heat resistance is poor.
In order to overcome this problem, a method has been proposed in which maleic anhydride or styrene is added to methyl methacrylate and copolymerized to produce a copolymer (see, for example, Patent Document 1).
However, this method has a problem that the copolymerization reaction is slow and the resulting copolymer is inferior in weather resistance.

There has also been proposed a method for improving the heat resistance of the resulting polymer by modifying the monomer itself to be used. As such a method, for example, a method using cyclohexyl acrylate as a monomer (for example, refer to Patent Document 2), a methacrylic acid alicyclic having an alicyclic hydrocarbon having 8 or more carbon atoms such as bonyl methacrylate and adamantyl methacrylate. Examples thereof include a method using a formula hydrocarbon ester (see, for example, Patent Document 3).
However, since these methods are inferior in polymerization reactivity, they are difficult to call economical methods and have problems in practical use.

Furthermore, since the polymethyl methacrylate has poor solvent resistance, there is a problem that the range of use thereof is limited. This deterioration in solvent resistance is attributed to the polymethyl methacrylate having a linear structure. For this reason, a method for producing polymethyl methacrylate having a crosslinked structure by copolymerizing methyl methacrylate and acrylate compounds or methacrylate compounds of various polyhydric alcohols has been proposed (see, for example, Patent Document 4). ).
However, in this production method, although the heat resistance and solvent resistance of the resulting polymethyl methacrylate are improved, the reaction tends to run away suddenly during the copolymerization reaction. There was a problem that was difficult. In addition, it takes a long time to obtain a polymer having a good surface state and low polymerization strain, and has a serious problem in practical use.

JP 58-87104 A Japanese Patent Laid-Open No. 58-13652 JP 2003-221418 A JP-A-63-75022

  In view of the current situation, the present invention is a single amount capable of providing an acrylic polymer having excellent heat resistance and solvent resistance while maintaining the good properties inherent in the acrylic polymer. It is an object of the present invention to provide a novel acrylic compound useful as a body, a method for producing the same, and a novel acrylic polymer having the novel acrylic compound as a monomer.

  In order to solve the above problems, the present inventor has eagerly studied to develop a monomer capable of giving an acrylic polymer having a crosslinked structure by performing a polymerization reaction without using a crosslinking agent. As a result of overlapping, it has been found that the above-mentioned problems can be solved by using an acrylic compound having a specific structure, and the present invention has been completed based on this finding.

That is, the first means for solving the problems of the present invention is:
[1] An acrylic compound represented by the following formula (1).

(式中、Ｒ¹は、水素原子又はメチル基を示し、Ｒ²は、炭素数１〜６のアルキル基を示す。)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 6 carbon atoms.)

The second means for solving the problems of the present invention is as follows:
[2] In the presence of a catalyst, the following formula (2)

(式中、Ｒ¹は、前記と同じである。)
で表される(メタ)アクリル酸と、下記式(３)
ＣＨ₂＝ＣＨ−ＯＣＯＲ² (３)
(式中、Ｒ²は、前記と同じである。)
で表される脂肪族カルボン酸ビニルエステルとを反応させることを特徴とする、下記式(１)

(Wherein R ¹ is the same as described above.)
(Meth) acrylic acid represented by the following formula (3)
^{_{CH 2 = CH-OCOR 2 (}} 3)
(Wherein R ² is the same as described above.)
Wherein the aliphatic carboxylic acid vinyl ester represented by formula (1) is reacted.

(式中、Ｒ¹及びＲ²は、前記と同じである。)
で表されるアクリル系化合物の製造方法である。

(In the formula, R ¹ and R ² are the same as described above.)
It is a manufacturing method of the acryl-type compound represented by these.

The third means for solving the problems of the present invention is as follows:
[3] An acrylic polymer obtained by polymerizing the acrylic compound according to [1] or the acrylic compound and an ethylenically unsaturated compound copolymerizable therewith.

  According to the present invention, a novel useful as a monomer capable of providing an acrylic polymer having excellent heat resistance and solvent resistance while maintaining the good properties inherent in the acrylic polymer. A novel acrylic polymer excellent in heat resistance and solvent resistance using the novel acrylic compound as a monomer is provided without using a crosslinking agent. The

  For this reason, the novel acrylic polymer is, for example, OA equipment field such as glazing material, lamp meter cover and printer cover; miscellaneous goods field such as game peripheral parts such as pachinko; display field such as store signboard; In the field of building materials such as bathtubs; in the field of information optical elements such as light guide plates for liquid crystals, video discs and audio discs; in the field of light electrical and industrial parts such as front plates of vending machines; in the field of lighting fixtures such as lighting covers It can be used as a molding material.

  [1] The acrylic compound of the present invention is represented by the following formula (1).

式中、Ｒ¹は、水素原子又はメチル基を示し、Ｒ²は、炭素数１〜６のアルキル基を示す。

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the acrylic compound represented by the formula (1) include 1-acetyloxyethyl acrylate, 1-propionyloxyethyl acrylate, 1-butyryloxyethyl acrylate, 1-isobutyryl acrylate. Oxyethyl, 1-valeryloxyethyl acrylate, 1-isovaleryloxyethyl acrylate, 1-hexoxyoxyethyl acrylate, 1-heptockoxyethyl acrylate, 1-acetyloxyethyl methacrylate, methacryl 1-propionyloxyethyl acid, 1-propionyloxyethyl methacrylate, 1-butyryloxyethyl methacrylate, 1-isobutyryloxyethyl methacrylate, 1-valeryloxyethyl methacrylate, 1-isovaleryl methacrylate Oxyethyl, 1-hexomethacrylate Kkuokishiechiru, and the like methacrylic acid 1 heptene TOEIC oxyethyl.

  These acrylic compounds are colorless and transparent liquid compounds. For example, in the case of 1-acetyloxyethyl acrylate, the boiling point is 41 to 45 ° C./0.2 kPa, and in the case of 1-acetyloxyethyl methacrylate, the boiling point is 36. ˜40 ° C./0.1 kPa.

  The acrylic compound represented by the formula (1) of the present invention can be used as a raw material for producing various chemical products, and is particularly useful as a monomer for giving an acrylic polymer. The monomer composed of the acrylic compound is a monomer that can give an acrylic polymer having a crosslinked structure by performing a polymerization reaction without using a crosslinking agent.

  [2] The method for producing an acrylic compound according to [1] of the present invention is represented by (meth) acrylic acid represented by the following formula (2) and the following formula (3) in the presence of a catalyst. It is characterized by reacting with an aliphatic carboxylic acid vinyl ester.

式中、Ｒ¹は、前記と同じである。
ＣＨ₂＝ＣＨ−ＯＣＯＲ² (３)
式中、Ｒ²は、前記と同じである。

In the formula, R ¹ is the same as described above.
^{_{CH 2 = CH-OCOR 2 (}} 3)
In the formula, R ² is the same as described above.

  Examples of the (meth) acrylic acid represented by the formula (2) include acrylic acid and methacrylic acid. Examples of the aliphatic carboxylic acid vinyl ester represented by the formula (3) include vinyl acetate and propion. Mention may be made of vinyl acid vinyl, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl isovalerate, vinyl hexanoate and vinyl heptanoate.

There is no particular limitation on the reaction between the (meth) acrylic acid represented by the formula (2) and the aliphatic carboxylic acid vinyl ester represented by the formula (3). (Meth) acrylic acid represented and the aliphatic carboxylic acid vinyl ester represented by the formula (3) are mixed, and an acid catalyst such as Bronsted acid or Lewis acid is used. It can be carried out by stirring at 35 to 45 ° C., usually 0.5 to 20 hours, preferably 3 to 10 hours.
If reaction temperature exists in the range of 20-60 degreeC, it has moderate reaction rate and can prevent or suppress generation | occurrence | production of a polymerization reaction.
The mixing ratio of the (meth) acrylic acid represented by the formula (2) and the aliphatic carboxylic acid vinyl ester represented by the formula (3) is not limited, but in consideration of reactivity and economy. The aliphatic carboxylic acid vinyl ester represented by the formula (3) is usually 0.9 to 1.5 moles, preferably 1 mole of the (meth) acrylic acid represented by the formula (2). It is desirable to set it as 1.0-1.2 mol.

Examples of the Bronsted acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid, and organic acids such as acetic acid, benzoic acid, formic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. .
Examples of the Lewis acid include aluminum chloride, ferric chloride, boron chloride compounds, stannic chloride, antimony fluoride, zinc chloride, titanium compounds, zeolites, and the like.
Of these catalysts, Bronsted acid is preferable, and sulfuric acid and p-toluenesulfonic acid are particularly preferable.
The catalyst is usually 0.5 to 10% by mass based on the total amount of (meth) acrylic acid represented by the formula (2) and the aliphatic carboxylic acid vinyl ester represented by the formula (3). , Preferably 1 to 5% by mass.

  The reaction between the (meth) acrylic acid represented by the formula (2) and the aliphatic carboxylic acid vinyl ester represented by the formula (3) can be carried out without using a solvent. May be used. Examples of the solvent include dichloromethane, heptane, acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, and the like. These solvents may be used in combination of two or more.

When the solvent is used after completion of the reaction, the solvent is removed, and the reaction product is washed, dried and purified according to a conventional method to obtain the target acrylic compound represented by the formula (1). Obtainable.
In such a method for producing an acrylic compound, the (meth) acrylic acid represented by the above formula (2) or the fat represented by the above formula (3) at the time of reaction and washing, drying, purification and storage. It is preferable to add a polymerization inhibitor such as p-methoxyphenol so that the aromatic carboxylic acid vinyl ester does not cause a polymerization reaction.

  [3] The acrylic polymer of the present invention is characterized by polymerizing the acrylic compound according to the above [1] or the acrylic compound and an ethylenically unsaturated compound copolymerizable therewith. To do.

The copolymerizable ethylenically unsaturated compound is not particularly limited, but ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, (meth) methyl acrylate, (meta ) (Meth) acrylic esters such as ethyl acrylate and (meth) butyl acrylate, and acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate and the like.
These ethylenically unsaturated compounds may be used alone or in combination of two or more.
The amount of these ethylenically unsaturated compounds used is usually 0.05 to 0.95 mol, preferably 0.1 to 0.8 mol, with respect to 1 mol of the acrylic compound represented by the formula (1). is there.

Although there is no restriction | limiting in particular in a polymerization method, A polymerization initiator is added to the said acrylic compound or the mixture of this acrylic compound and another ethylenically unsaturated compound, Usually 30-120 degreeC, Preferably 40-100 The polymerization can be carried out by polymerization at a temperature of usually 1 to 20 hours, preferably 2 to 10 hours.
When the polymerization temperature is 30 ° C. or higher, it has an appropriate polymerization rate, and when it is 120 ° C. or lower, coloring and the like can be prevented or suppressed.

Examples of the polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate; 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis-2-methyl-N-1,1-bis (hydroxymethyl) -2-hydroxyethylpropioamide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2 Azo compounds such as' -azobisisobutyronitrile, 1,1'-azobis (1-cyclohexanecarbonitrile); isobutyryl peroxide, 2,4-di-chlorobenzoyl peroxide, 3,5,5'- Diacyl peroxides such as trimethylhexanoyl peroxide; bis (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propiyl Peroxydi-carbonate, di-isopropylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di (2-ethylethylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di ( Peroxydi-carbonates such as 3-methyl-3-methoxybutylperoxy) di-carbonate; (α, α-bis-neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1 ′, 3,3′-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-Hexylperoxypivalate, t-butyl -Oxypivalate, methyl ethyl peroxide, di-t-butyl peroxide, acetyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, di- Examples thereof include isopropyl peroxydicarbonate, di-t-butyl peroxyisophthalate, and t-butyl peroxyisobutyrate.
This polymerization initiator is usually used in a proportion of 0.05 to 5% by mass, preferably 0.2 to 2% by mass, based on the total amount of monomers.

The polymerization of the acrylic compound described in [1] can be performed without using a solvent, but may be performed using a solvent if desired. As this solvent, water and / or an organic solvent can be used. Examples of the organic solvent include methyl alcohol, ethyl alcohol, isopropanol, tertiary butanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, and triethylene glycol. , Ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, dimethylformamide, nitromethane, benzonitrile, chloroform, dichloromethane, hexane, heptane, toluene, xylene, cyclohexane, cyclopentane, etc. it can.
In the polymerization of the acrylic compound, it is not necessary to use a crosslinking agent.

The acrylic polymer of the present invention is excellent in transparency and weather resistance, while maintaining the properties of conventional acrylic polymers such as good mechanical properties, thermal properties and molding processability. It is an acrylic polymer having heat resistance and solvent resistance.
For this reason, the acrylic polymer is, for example, OA equipment field such as glazing material, lamp meter cover, printer cover; miscellaneous goods field such as game peripheral parts such as pachinko; display field such as store signboard; carport, bathtub In the field of building materials such as liquid crystal light guide plates, video discs, audio discs, etc .; in the field of information electronics such as vending machine front plates; in the field of lighting equipment such as lighting covers; Can be used as

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.
In addition, the measuring method of the glass transition temperature and thermal decomposition temperature in a present Example, and the evaluation method of heat resistance, solvent resistance, and transparency are as follows.
[Method of measuring glass transition temperature]
By differential scanning calorimetry (DSC), the temperature was raised from 35 ° C to 20 ° C / min. At 200 ° C, then rapidly cooled with liquid nitrogen, and again from 35 ° C to 20 ° C / min. To 600 ° C. The temperature at which the temperature was increased and showed endotherm was defined as the glass transition temperature.
[Measurement method of thermal decomposition temperature]
By thermogravimetry (TGA), the temperature at which the temperature was increased under a nitrogen stream at 20 ° C./min and the mass decreased by 5% was defined as the thermal decomposition temperature.
[Method for evaluating heat resistance]
The polymer plate was immersed in 180 ° C. silicon oil, taken out after 5 minutes, and visually checked for deformation.
[Solvent Resistance Evaluation Method]
The plate made of the polymer was immersed in acetone at room temperature for 10 minutes, taken out and dried, and the surface state of the plate was observed (solvent resistance 1). Furthermore, the solubility at room temperature in dimethylformamide was examined (solvent resistance 2).
[Method of evaluating transparency]
Using the Suga Test Instruments HZ-2 type, the total light transmittance of the produced polymer plate was measured.

Example 1
[Production Example of Acrylic Compound (A) Represented by Formula (1)]
In a 1 liter flask equipped with a stirrer, a thermometer and a reflux condenser, 144.1 g (2.0 mol) acrylic acid, 172.2 g (2.0 mol) vinyl acetate and 2.0 g (0.0. 02 mol) and stirred at 45 ° C. for 6 hours.
After confirming that all the acrylic acid was consumed by thin layer chromatography (TLC), it was washed once with water containing sodium hydrogen carbonate and then once with pure water.
The organic phase thus obtained was dried over anhydrous magnesium sulfate and then distilled under reduced pressure (0.2 kPa, 41 to 45 ° C.) to obtain a colorless and transparent liquid product.
The yield of this liquid product was 183.4 g (theoretical yield 58.0%).
As a result of analyzing the liquid product by ¹ H-NMR and ¹³ C-NMR, it was identified as an acrylic compound (A) in which R ¹ is hydrogen and R ² is a methyl group in formula (1).
^{A 1} H-NMR chart is shown in FIG. 1, and a ¹³ C-NMR chart is shown in FIG.

Example 2
[Production Example of Acrylic Polymer (A)]
After adding 26 mg (0.5 mol%) of azobisisobutyronitrile to 20 g (0.126 mol) of the acrylic compound (A) produced in Example 1, the mixture was degassed and replaced with nitrogen gas, then 65 ° C. The solution was solidified after 30 minutes. Subsequently, it heated at 65 degreeC in the state left still for 5 hours.
The solidified product thus obtained was pulverized, washed with methanol, and dried to obtain an acrylic polymer (A).
The obtained acrylic polymer (A) was insoluble in any solvent of toluene, methylene chloride, N-methylpyrrolidone and dimethylformamide.
The acrylic polymer (A) was confirmed to have a glass transition temperature of 37 ° C. and a thermal decomposition temperature of 260 ° C.

Example 3
[Production Example of Acrylic Compound (B) Represented by Formula (1)]
In a 1 liter flask equipped with a stirrer, thermometer and reflux condenser, 172.2 g (2.0 mol) of methacrylic acid, 172.2 g (2.0 mol) of vinyl acetate and 2.0 g of concentrated sulfuric acid (0. 02 mol) and stirred at 40 ° C. for 7 hours.
After confirming that all the methacrylic acid was consumed by TLC, it was washed once with water containing sodium hydrogen carbonate and then once with pure water.
The organic phase thus obtained was dried over anhydrous magnesium sulfate and then distilled under reduced pressure (0.1 kPa, 36 to 40 ° C.) to obtain a colorless and transparent liquid product.
The yield of this liquid product was 186.7 g (theoretical yield 54.2%).
As a result of analyzing the liquid product by ¹ H-NMR and ¹³ C-NMR, it was identified as an acrylic compound (B) in which R ¹ and R ^{2 in the} formula (1) are methyl groups.
^{A 1} H-NMR chart is shown in FIG. 3, and a ¹³ C-NMR chart is shown in FIG.

Example 4
[Production Example of Acrylic Polymer (B)]
After 20 mg (0.1 mol%) of azobisisobutyronitrile was placed in a reactor to 20 g (0.116 mol) of the acrylic compound (B) produced in Example 3, and degassed with nitrogen gas, Heated in a 65 ° C. oil bath for 4 hours.
The reactor was then broken and the product removed. This product was a colorless and transparent glassy solid.
The glassy solid was placed in a vacuum dryer at 60 ° C. to remove unreacted monomers, thereby obtaining an acrylic polymer (B).
This acrylic polymer (B) was immersed in dimethylformamide, acetone, ethyl acetate and toluene, but was insoluble in any solvent, the surface was not clouded at all, and a colorless and transparent state was maintained. .
The acrylic polymer (B) had a glass transition temperature of 160 ° C. and a thermal decomposition temperature of 250 ° C.
The obtained acrylic polymer (B) was pulverized, and CPMAS was measured at 100 ° C. by attaching 5 mm CPMAS Probe to a JNM-CMXP302 NMR device manufactured by JEOL Ltd. for this pulverized product. The CPMAS chart is shown in FIG.

Example 5
[Production example of acrylic copolymer (C)]
9.90 g (0.115 mol) of methyl methacrylate, 0.20 g (0.00116 mol) of acrylic compound (B) represented by the formula (1) obtained in Example 3 and 20 mg of azobisisobutylnitrile (0.00012 mol) was placed in the reactor, deaerated and replaced with nitrogen gas, and then heated in an oil bath at 65 ° C. for 4 hours.
The reactor was then broken and the product removed. This product was a colorless and transparent glassy solid.
This glassy solid was placed in a vacuum dryer at 60 ° C. to remove unreacted monomers to obtain an acrylic copolymer (C).
The acrylic copolymer (C) had a glass transition temperature of 105 ° C. and a thermal decomposition temperature of 255 ° C.
The acrylic copolymer (C) was immersed in dimethylformamide, acetone, ethyl acetate and toluene, respectively, but was insoluble in any solvent, and the surface was not clouded at all and kept colorless and transparent. It had been.
Further, when the acrylic copolymer (C) was immersed in an oil bath at 200 ° C., it became a rubber-like elastic body, but the initial shape was maintained.

Example 6
[Other Production Examples of Acrylic Compound (A) Represented by Formula (1)]
In a 1 liter flask equipped with a stirrer, a thermometer and a reflux condenser, 144.1 g (2.0 mol) of acrylic acid, 172.2 g (2.0 mol) of vinyl acetate, 0.1 g of p-methoxyphenol ( put 300 ppm) and concentrated sulfuric acid 2.0 g (0.02 mol) acrylic acid and vinyl acetate based on the total amount of 4 hours at 50 ° C., and stirred.
After confirming that all the acrylic acid was consumed by TLC, it was washed once with water containing sodium hydrogen carbonate and then once with pure water.
After drying the organic phase thus obtained with anhydrous magnesium sulfate, 0.1 g of p-methoxyphenol was added to the organic phase and distilled under reduced pressure (0.2 kPa, 41 to 45 ° C.) to give a colorless transparent liquid. The product was obtained.
The yield of this liquid product was 183.4 g (theoretical yield 53.5%).
For the liquid product, the same NMR chart as in Example 1 was obtained and identified as an acrylic compound (A) in which R ¹ is hydrogen and R ² is a methyl group in the formula (1). It was done.

Example 7
[Other Production Examples of Acrylic Compound (B) Represented by Formula (1)]
In a 1 liter flask equipped with a stirrer, a thermometer and a reflux condenser, 172.2 g (2.0 mol) of methacrylic acid, 172.2 g (2.0 mol) of vinyl acetate, 0.1 g of p-methoxyphenol ( 300 ppm) and 2.0 g (0.02 mol) of concentrated sulfuric acid were added and stirred at 45 ° C. for 5 hours.
After confirming that all of the methacrylic acid was consumed by TLC, it was washed once with water containing sodium hydrogen carbonate and then once with pure water.
After the organic phase thus obtained was dried over anhydrous magnesium sulfate, 0.1 g of p-methoxyphenol was added to the organic phase and distilled under reduced pressure (0.1 kPa, 36 to 40 ° C.) to form a colorless transparent liquid. I got a thing.
The yield of this liquid product was 203.5 g (theoretical yield 59.1%).
For the liquid product, the same NMR chart as in Example 3 was obtained, and in the formula (1), R ¹ and R ² were identified as an acrylic compound (B) having a methyl group.

Examples 8-12
[Evaluation]
To the acrylic compound (B) (monomer 1) represented by the formula (1) produced in Example 3 or a mixture of this monomer 1 and methyl methacrylate (monomer 2), .3 mol% of benzoyl peroxide was added and poured between glass plates having a gap of 2 mm thickness, and cast polymerization was performed at 40 to 80 ° C. to prepare a plate made of a colorless and transparent polymer.
The plate was evaluated for heat resistance, solvent resistance and transparency.
The results are shown in Table 1. Table 1 also shows the ratio of monomer 1 and monomer 2 used to give the polymer.

Comparative Example 1
Using monomer 2, a plate made of a colorless and transparent polymer was prepared in the same manner as in Examples 8 to 12, and the heat resistance, solvent resistance and transparency of this plate were evaluated.
The result is shown in 1.

  The acrylic copolymer of the present invention can be foam-molded. By foam-molding, the acrylic copolymer can be used for a food container for a range, an automobile interior material, a unit bath, or a heat insulating material for piping.

1 is a ¹ H-NMR chart of an acrylic compound (A) produced in Example 1. 2 is a ¹³ C-NMR chart of an acrylic compound (A) produced in Example 1. FIG. 2 is a ¹ H-NMR chart of an acrylic compound (B) produced in Example 3. FIG. 3 is a ¹³ C-NMR chart of an acrylic compound (B) produced in Example 3. FIG. 6 is a CPMAS chart of an acrylic polymer (B) produced in Example 4.

Claims (4)

An acrylic compound represented by the following formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 6 carbon atoms.) In the presence of a catalyst, the following formula (2)

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
(Meth) acrylic acid represented by the following formula (3)
^{_{CH 2 = CH-OCOR 2 (}} 3)
(In the formula, R ² represents an alkyl group having 1 to 6 carbon atoms.)
Wherein the aliphatic carboxylic acid vinyl ester represented by formula (1) is reacted.

(In the formula, R ¹ and R ² are the same as described above.)
The manufacturing method of the acryl-type compound represented by these.   The method for producing an acrylic compound according to claim 2, wherein the catalyst is an acid catalyst. An acrylic polymer obtained by polymerizing the acrylic compound according to claim 1 or the acrylic compound and an ethylenically unsaturated compound copolymerizable therewith.

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