JPH10330316A - (meth)acrylate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound which is a monomer for resins expressing moderate mechanical strength, high heat resistance, weatherability and curing properties. SOLUTION: This (meth)acrylate is a compound expressed by formula I (R<1> is a 1-4C alkyl or phenyl; R<2> is H or methyl; R<3> is H or methyl), e.g. a compound of formula II. The compound of formula I is obtained, e.g. by reacting (A) (meth)acrylic acid or its derivative (e.g. acryloyl chloride) of the formula; CH2 =C(R<5> )COR<6> [R<5> is H or methyl; R<6> is OH, an alkoxy, Cl, CH2 =C(R<7> )COO (R<7> is H or methyl)] with (B) an alicyclic alcohol (e.g. 2-methyl-1- cyclohexanemethanol) of formula III in the presence of an acid catalyst at 60-180 deg.C in a solvent which boils being azeotropic with water and separates in two phases in a liquid state with removing produced water to the outside of the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION (Meth) acrylates are highly reactive and readily copolymerize alone or with other ethylenically unsaturated compounds in the presence of heat, ultraviolet, radiation, electron beams and radical polymerization agents. In particular, polyfunctional (meth) acrylates having two or more (meth) acrylic groups are used in combination with UV (ultraviolet) curable resins, EB (electron beam) curable resins, crosslinking agents, and other ethylenically unsaturated compounds. Useful as a comonomer for polymers. The present invention relates to a novel (meth) acrylate that gives high heat resistance and weather resistance when used in such applications, and a method for producing the same.

[0002]

2. Description of the Related Art It is common practice to react alcohol with (meth) acrylic acid or a derivative thereof to obtain (meth) acrylate. However, in this case, when the base alcohol contains a benzene ring such as benzyl alcohol, there is a drawback that a resin using such a benzene ring has poor weather resistance. Also, methyl methacrylate in which the base alcohol is methanol has a high mold shrinkage,
In the case of alcohol having a long alkyl group, sufficient heat resistance cannot be obtained. In the case of aliphatics such as ethylene glycol and propylene glycol, the resins obtained therefrom are very brittle. Further, in the case of a polyether having hydroxyl groups at both terminals such as polyethylene glycol and polypropylene glycol, there is a disadvantage that heat resistance is low.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a novel (meth) acrylate which is a resin monomer having a suitable mechanical strength and exhibiting high heat resistance, weather resistance and curability.

[0004]

The present invention provides a compound represented by the general formula (1):

Embedded image (Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² represents hydrogen or a methyl group. R ³
Represents a hydrogen atom or a methyl group. ) Is a novel (meth) acrylate represented by Furthermore, the present invention relates to (meth) acrylic acid represented by the general formula (2) or a derivative thereof, and CH ₂ ＣC (R ⁵ ) COR ⁶ (2) (wherein, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a hydroxyl group, an alkoxy group, a chlorine atom or CH ₂ ＣC (R ⁷ )
Represents a COO- group, and R ⁷ represents a hydrogen atom or a methyl group. ) General formula (3)

Embedded image Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ³ represents a hydrogen atom or a methyl group. Novel (meta) represented by the general formula (1)
This is a method for producing acrylate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. The above-mentioned general formula (1) is specifically composed of an alicyclic alcohol (derivative), (meth) acrylic acid, (meth) acrylic acid chloride, (Meth) acrylic anhydride, (meth) acrylic acid, lower alcohol ester of (meth) such as
The following general formula (1) obtained by reacting with a carboxylic acid derivative containing an acrylic group

Embedded image In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² and R ³ may be the same or different and are a hydrogen atom or a methyl group.

More specifically, it is an alicyclic (meth) acrylate represented by the general formulas (4) and (5).

Embedded image

Embedded image In the formulas (4) and (5), R ² and R ³ may be the same or different and are a hydrogen atom or a methyl group.

The alcohol represented by the general formula (3) of the present invention is, for example, 2-methyl-1-cyclohexanemethanol, 2,3-dimethyl-1-cyclohexanemethanol, 2,4-dimethyl-1-cyclohexanemethanol 2,6-dimethyl-1-cyclohexanemethanol, 2-phenyl-1-cyclohexanemethanol,
-Phenyl-3-methyl-1-cyclohexanemethanol, 2-phenyl-4-methyl-1-cyclohexanemethanol, 2-phenyl-5-methyl-1-cyclohexanemethanol, 2-phenyl-6-methyl-1-cyclohexanemethanol And the like.

The (meth) acrylic acid or (meth) acrylic acid derivative in the present invention includes, for example, acrylic acid, methacrylic acid, methacrylic acid chloride, acrylic acid chloride, methacrylic anhydride, acrylic anhydride, methyl methacrylate. , Methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate and the like. The charged amount of the alicyclic alcohol and the (meth) acrylic acid or the (meth) acrylic acid derivative depends on the kind of the precursor, but the molar ratio of alcohol / (meth) acrylic acid or the (meth) acrylic acid derivative = 0. 0.8 to 8, and particularly preferably 1.0 to 2. As an embodiment of the reaction, when reacting the alcohol and the acid itself, sulfuric acid, p-toluenesulfonic acid, in the presence of an acid catalyst such as methanesulfonic acid,
It is desirable to use a solvent that azeotropes with water, such as benzene and toluene, and that separates into two layers in a liquid state, while removing the generated water from the system and reacting. The reaction can be carried out under reduced pressure to pressurized conditions, but it is generally preferable to carry out the reaction at normal pressure since the reaction apparatus does not become complicated. The reaction temperature is 60 to 180 ° C, preferably 80 to 120 ° C.
It is desirable to select from the range.

When the reaction partner with the alcohol is an acid halide or an acid anhydride, the reaction can be carried out without a solvent or in a suitable inert solvent. When the reaction is performed without using a solvent, the reaction heat is large, so it is necessary to use an appropriate heat removing device or to prevent the reaction from running away, for example, by dropping one of the substrates. Solvents that can be used for the reaction include halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane and trichloroethane, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, benzene, toluene and xylene. And the like; ester compounds such as ethyl acetate and butyl acetate; ketone compounds such as acetone and methyl ethyl ketone; and nitrile compounds such as acetonitrile. When an acid halide is used, hydrogen halide is generated. Therefore, it is desirable that a tertiary amine or the like is present in an equimolar amount or more with the acid halide. In the case of an acid anhydride, the reaction can be carried out without a catalyst or in the presence of a catalyst. Suitable catalysts include sodium acetate and organic amines. The reaction temperature is in the range of 20 to 60 ° C, preferably 20 to 45 ° C for acid halides, and 40 to 120 ° C, preferably 60 to 100 ° C for acid anhydrides.

Also, as the (meth) acrylic acid derivative,
When an ester with a lower alcohol is used, the ester can be synthesized by performing a transesterification reaction in the presence of a suitable base catalyst and distilling off the generated alcohol. The reaction can be carried out under reduced pressure or under increased pressure, but it is preferable to carry out the reaction at normal pressure, because the equipment is not expensive in terms of equipment. The reaction temperature is desirably higher than the boiling point of the alcohol to be produced, and varies depending on the ester used, but is generally in the range of 70 to 180C, preferably 80 to 150C. As a catalyst to be used, potassium carbonate, potassium methoxide, dibutyltin oxide, tetraethoxytitanium and the like can be used.

In order to avoid thermal polymerization, a polymerization inhibitor may be used in combination. Examples of the polymerization inhibitor include 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylhydroquinone, and 2-tert-butyl.
Phenol polymerization inhibitors such as butylhydroquinone monomethyl ether, phenothiazine, copper naphthoate, cobalt naphthoate, and the like can be used. Oxygen in the air also acts as an effective polymerization inhibitor. The polymerization inhibitor is 0.001 to (meth) acrylic acid (derivative).
To 2% by weight, preferably 0.002 to 1% by weight. When the reaction mixture thus obtained contains a solvent, it can be used as a thermosetting resin by removing the solvent under normal pressure or reduced pressure. Can be used.

[0012]

The present invention will be described in more detail with reference to the following examples. Using ^{(1 H-NMR, 13 C} -NMR measurement conditions) JEOL Co., Ltd. JNM-EX400 type (400 MHz), CDCl ₃ as a solvent, it was measured using tetramethylsilane as a standard substance. ¹³ C-NMR is ¹ H
Measured under decoupled conditions. (IR measurement) It was measured by a liquid film method using a KBr plate using an FT / IR7300 infrared spectrometer manufactured by JASCO Corporation.

(GC-MASS measurement) Shimadzu Corporation
The measurement was performed using QP-5000 manufactured by KK. The measurement conditions are shown below. Ionization method: CI Reactive gas: isobutane MS: 60-500 INJECTION temperature: 220 ° C DETECTION temperature: 220 ° C Carrier gas: He

(Example 1) In a 500 ml four-necked flask equipped with a stirrer, a cooling device, a thermometer and a dropping funnel, 2-methyl-1-cyclohexanemethanol (tr) was added.
ans-, cis-mixture) 20 g, triethylamine 16.6
g of the solvent, 200 ml of dichloromethane was added thereto, and a solution of 14.8 g of acrylic acid chloride in dichloromethane was added at room temperature.
After 0 ml was added dropwise over 90 minutes, the reaction was further performed for 1 hour. The reaction mixture was diluted with a saturated aqueous solution of sodium hydrogen carbonate 10
After washing once with 0 ml, it was washed four times with 100 ml of pure water.
The acrylate solution thus obtained was dried over magnesium sulfate. After removing the desiccant by filtration, p
0.03 g of -methoxyphenol was added, and the solvent was distilled off by evaporation to obtain a corresponding ester of methacrylic acid (general formula (6)).

[0015] The ¹ H-NMR of the obtained compound 1,
FIG. 2 shows ¹³ C-NMR, and FIG. 3 shows IR. The spectrum data and assignments are as follows. ^{1 H-NMR (δ, ppm} , CDCl 3): 0.90,0.94 (3H, -CH (C H 3) -) 0.90-2.00 (m, 10H, C (cyclohexane) -H) 4.03d, 4.05d, 4.20 d, 4.24d (2H, -C H 2 O-) 5.81dd, 6.11-6.16m, 6.37d, 6.41d (3H, -CO-C H = C H 2) 13 C-NMR (δ, ppm, CDCl _{3): 14.2,20.2 (-CH (CH} 3) -) 22.0,24.6,24.8,26.1,26.3,30.0,30.3,32.3,34.2,35.6,
39.1,43.6 (C (cyclohexane)) 66.5,67.7 (-CH 2 O-) 128.7,130.3 (-CO- C H = CH 2) 166.4 (-OC (O) -) IR (cm -1, KBr liquid film ) (Cm ^-1 , KBr liquid film): 1727 (v _{c = 0} ) 1296, 1274, 1192 (v _c-0 ) GC / Ms (m / z) 183 [M + H] Compound obtained from the above results Was confirmed to be a compound represented by the general formula (6).

Embedded image

Example 2 14.8 g of the acrylic acid chloride of Example 1 was replaced with 17.9 g of methacrylic acid chloride.
Except that 16.6 g of triethylamine was changed to 17.4 g, the corresponding treatment was carried out in the same manner as in Example 1 to obtain a corresponding methacrylate (general formula (7)). FIG. 4 shows ¹ H-NMR and FIG. 5 shows ¹³ C-NMR of the obtained compound.
FIG. 6 shows the IR. The spectrum data and assignments are as follows.

[0017] ^{1 H-NMR (δ, ppm} , CDCl 3): 0.90d, 0.94d (3H, -CH (C H 3) -) 0.9-2.1 (m, 10H, C (cyclohexane) -H) 1.91 ( s, 3H, -CO-C ( C H 3) = CH 2) 4.01-4.05m, 4.18-4.21dd (2H, -CH 2 O-) 5.54s, 6.09s (2H, -CO-C (CH 3 ) = C H ₂ ) ¹³ C-NMR (δ, ppm, CDCl ₃ ): 14.3,18.3,20.2,22.1 ( -C H ₃ ) 24.7,24.9,26.1,26.4,30.1,30.4,32.4,34.4,35.7, 39.1,
43.7 (C (cyclohexane)) 66.6,67.8 (-CH ₂ O-) 125.1,136.6 (-CO- C (CH ₃ ) = CH ₂ ) 167.5 (-OC (O)-) IR (cm ^-1 , KBr solution) Film): 1721 (vc _{= 0} ) 1322,1297,1170 (vc _-0 ) GC / Ms (m / z) 197 [m / z] From the above results, the compound obtained is represented by the general formula (7) Was confirmed.

Embedded image

Example 3 2-Methyl-1- of Example 1
Cyclohexanemethanol (trans-, cis-mixture) 20
Example 1 except that g was changed to 22.2 g of 2,4-dimethyl-1-cyclohexanemethanol (mixture of isomers).
By the same treatment as described above, a corresponding acrylate ester (general formula (8)) could be obtained. ¹ H of the obtained compound
FIG. 7 shows NMR, FIG. 8 shows ¹³ C-NMR, and FIG.
Shown in

[0019] ^{1 H-NMR (δ, ppm} , CDCl 3): 0.69-0.97m (6H, -CH (C H 3) -) 1.15-1.82m (9H, C (cyclohexane) -H) 4.01-4.26 ( _{2H, -C H 2 O-) 5.80dd} , 6.08-6.16m, 6.36-6.42m (3H, -CO-C H = C H 2) 13 C-NMR (δ, ppm, CDCl 3): 19.5,20.1 _{, 22.5,23.5 (-CH (CH 3)} -) 27.1,28.3,30.1,30.9,32.5,34.1,34.7,39.7,42.1,43.3,
44.6 (C (cyclohexane)) 67.3,67.6 (-CH 2 O-) 128.7,130.3 (-CO- C H = CH 2) 166.3 (-OC (O) -) IR (cm -1, KBr liquid film) ( cm ^-1 , KBr liquid film): 1727 (ν _{c = 0} ) 1296,1273,1193 (ν _c-0 ) GC / Ms (m / z) 197 [M + H]

Embedded image

Example 4 2-Methyl-1- of Example 1
Cyclohexanemethanol (trans-, cis-mixture) 20
Example 1 except that g was changed to 22.2 g of 2,4-dimethyl-1-cyclohexanemethanol (mixture of isomers).
By treating in the same manner as described above, a corresponding acrylate ester (general formula (9)) could be obtained. ¹ H of the obtained compound
-NMR is shown in FIG. 10, ¹³ C-NMR is shown in FIG. 11, and IR is shown in FIG.

[0021] ^{1 H-NMR (δ, ppm} , CDCl 3): 0.69-0.97m (6H, -CH (C H 3) -) 1.15-1.82m (9H, C (cyclohexane) -H) 4.01-4.26 ( _{2H, -C H 2 O-) 5.80dd} , 6.08-6.16m, 6.36-6.42m (3H, -CO-C H = C H 2) 13 C-NMR (δ, ppm, CDCl 3): 19.5,20.1 _{, 22.5,23.5 (-CH (CH 3)} -) 27.1,28.3,30.1,30.9,32.5,34.1,34.7,39.7,42.1,43.3,
44.6 (C (cyclohexane)) 67.3,67.6 (-CH 2 O-) 128.7,130.3 (-CO- C H = CH 2) 166.3 (-OC (O) -) IR (cm -1, KBr liquid film) ( cm ⁻¹ , KBr liquid film): 1727 (ν _{c = 0} ) 1296,1273,1193 (ν _c−0 ) GC / Ms (m / z) 211 [M + H]

Embedded image

Example 5 2-Methyl-1- of Example 1
Cyclohexanemethanol (trans-, cis-mixture) 20
Example 1 except that g was changed to 22.2 g of 2,4-dimethyl-1-cyclohexanemethanol (mixture of isomers).
By the same treatment as described above, a corresponding acrylate (general formula (10)) could be obtained. ¹ of the resulting compound
FIG. 13 shows H-NMR, FIG. 14 shows ¹³ C-NMR, and FIG.
Is shown in FIG.

[0023] ^{1 H-NMR (δ, ppm} , CDCl 3): 0.69-0.97m (6H, -CH (C H 3) -) 1.15-1.82m (9H, C (cyclohexane) -H) 4.01-4.26 ( _{2H, -C H 2 O-) 5.80dd} , 6.08-6.16m, 6.36-6.42m (3H, -CO-C H = C H 2) 13 C-NMR (δ, ppm, CDCl 3): 19.5,20.1 _{, 22.5,23.5 (-CH (CH 3)} -) 27.1,28.3,30.1,30.9,32.5,34.1,34.7,39.7,42.1,43.3,
44.6 (C (cyclohexane)) 67.3,67.6 (-CH 2 O-) 128.7,130.3 (-CO- C H = CH 2) 166.3 (-OC (O) -) IR (cm -1, KBr liquid film) ( cm ⁻¹ , KBr liquid film): 1727 (ν _{c = 0} ) 1296,1273,1193 (ν _c-0 ) GC / Ms (m / z) 245 [M + H] Formula (10)

Embedded image

[0024]

The present invention relates to a novel (meth) acrylate, and the resin comprising the (meth) acrylate of the present invention has a moderate mechanical strength as compared with the conventional (meth) acrylate resin. It shows high heat resistance and weather resistance, and has great industrial utility value.

[Brief description of the drawings]

[1] of the present invention (meth) ¹ H-NMR acrylate
It is a spectrum.

FIG. 2: ¹³ C-NMR of the (meth) acrylate of the present invention
It is a spectrum.

FIG. 3 is an IR spectrum of the (meth) acrylate of the present invention.

FIG. 4 shows ¹ H—N of another (meth) acrylate of the present invention.
It is an MR spectrum.

FIG. 5 shows ¹³ C—N of another (meth) acrylate of the present invention.
It is an MR spectrum.

FIG. 6 is an IR spectrum of another (meth) acrylate of the present invention.

FIG. 7 shows ¹ H—N of another (meth) acrylate of the present invention.
It is an MR spectrum.

FIG. 8 shows ¹³ C—N of another (meth) acrylate of the present invention.
It is an MR spectrum.

FIG. 9 is an IR spectrum of another (meth) acrylate of the present invention.

FIG. 10 shows ¹ H- of another (meth) acrylate of the present invention.
It is an NMR spectrum.

FIG. 11 shows ¹³ C- of another (meth) acrylate of the present invention.
It is an NMR spectrum.

FIG. 12 is an IR spectrum of another (meth) acrylate of the present invention.

FIG. 13 shows ¹ H- of another (meth) acrylate of the present invention.
It is an NMR spectrum.

FIG. 14 shows ¹³ C- of another (meth) acrylate of the present invention.
It is an NMR spectrum.

FIG. 15 is an IR spectrum of another (meth) acrylate of the present invention.

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² represents hydrogen or a methyl group. R ³
Represents a hydrogen atom or a methyl group. (Meth) acrylate represented by). 2. The (meth) acrylate according to claim 1, wherein R ¹ is a methyl group and R ³ is a hydrogen atom. 3. A (meth) acrylic acid represented by the general formula (2) or a derivative thereof, and CH ₂ ＣC (R ⁵ ) COR ⁶ (2) (wherein, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a hydroxyl group, an alkoxy group, a chlorine atom or CH ₂ ＣC (R ⁷ )
Represents a COO- group, and R ⁷ represents a hydrogen atom or a methyl group. ) General formula (3) Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ³ represents a hydrogen atom or a methyl group. The method for producing a (meth) acrylate according to claim 1.