JPH10306057A - New (meth)acrylate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new (meth)acrylate useful as a monomer for UV light- curable resins, electron beam-curable resins, etc., and as a comonomer for copolymers with other ethylenically unsaturated compounds, etc., and giving the resins or (co)polymers excellent in transparency, heat resistance, weatherability curability, etc. SOLUTION: A (meth)acrylate of formula I (A is a single bond, a double bond; R<1> is H, a 1-4C alkyl, phenyl; R<2> , R<3> are each H, methyl), e.g. a dimethacrylate of formula II. The compound of formula I is obtained by reacting a (meth)acrylic acid of formula III [R<5> is H, methyl; R<6> is OH, an alkoxy, Cl, CH2 =C(R<5> )COO] or its derivative with an alicyclic diol of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel (meth) acrylate and a method for producing the same. Useful as a comonomer for copolymers with other ethylenically unsaturated compounds, and useful for applications such as novel polyfunctional (meth) acrylates having excellent heat resistance, weather resistance, curability, etc., and a method for producing the same It is about.

[0002]

2. Description of the Related Art (Meth) acrylate is highly reactive,
Easily homopolymerizes or copolymerizes with other ethylenically unsaturated compounds in the presence of heat, ultraviolet, radiation, electron beam, radical polymerization agents. In particular, polyfunctional (meth) acrylates having two or more (meth) acrylic groups are used as ultraviolet-curable resins and electron-beam-curable resins, as well as for crosslinking agents and copolymers with other ethylenically unsaturated compounds. Useful for use as a comonomer.

It is common practice to react a diol with (meth) acrylic acid or a derivative thereof to obtain a diester of (meth) acrylate. However, in this case, when the base diol contains a benzene ring such as xylene dimethanol, there is a disadvantage that a curable resin using such a diol has poor weather resistance. In addition, when the diol is an aliphatic such as ethylene glycol, propylene glycol, or neopentyl glycol, the curable resin obtained therefrom has a disadvantage of being very brittle,
When the diol is a polyether with a hydroxyl group at both ends such as polyethylene glycol or polypropylene glycol, there is a disadvantage that heat resistance is low.

Further, there has been reported an example in which 3-cyclohexene-1,1-dimethanol is used as a diol, and the corresponding diol and acrylic acid are reacted with sulfuric acid as a catalyst to obtain a corresponding diacrylate ester [A]. . E. FIG. Bo
tog et al., Zh. Org. Khim. , 18 (1), 9
0 (1982)], but has a disadvantage of poor transparency.

Heretofore, there has not been obtained any material which sufficiently satisfies physical properties such as weather resistance, heat resistance and hardness.

[0006]

SUMMARY OF THE INVENTION A first object of the present invention is to use a resin as an ultraviolet curable resin or an electron beam curable resin, to cure it with a cross-linking agent, or to use it with other ethylenically unsaturated compounds. It is useful for applications such as use as a comonomer for polymers, and is excellent in transparency, heat resistance, weather resistance, curability, etc., and especially suitable for use as an ultraviolet curable resin or an electron beam curable resin. (Meta) with high strength, high heat resistance, weather resistance, curability and transparency
An object of the present invention is to provide a novel di (meth) acrylate ester which is an acrylate and has a norbornene skeleton or a norbornane skeleton in a molecule. A second object of the present invention is to provide a method for easily producing such a novel (meth) acrylate.

[0007]

The invention of claim 1 of the present invention is a novel (meth) acrylate characterized by being represented by the following general formula (1).

[0008]

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[0009] [In the formula (1), A represents a single bond or a double bond, R ¹ represents any of an alkyl group, phenyl group hydrogen atoms, from 1 carbon atoms to 4, R ² and R ³
Represents the same or different hydrogen or methyl groups]

A second aspect of the present invention is the novel (meth) acrylate according to the ^{first aspect} , wherein R ¹ is a methyl group.

According to a third aspect of the present invention, there is provided a reaction between (meth) acrylic acid represented by the following general formula (2) or a derivative thereof and an alicyclic diol represented by the following general formula (3). 2. A method for producing a novel (meth) acrylate according to claim 1, wherein

[0012]

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[In the general formula (2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a hydroxyl group, an alkoxy group, a chlorine atom or a CH ₂ ＣC (R ⁵ ) COO— group.

[0014]

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[In the general formula (3), A represents a single bond or a double bond, and R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.]

[0016]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. The (meth) acrylate represented by the general formula (1) includes, for example, an alicyclic diol having a norbornene skeleton or a norbornane skeleton in a molecule or a derivative thereof, (meth) acrylic acid, (meth) acrylic chloride, (Meth) acrylic anhydride, (meth) acrylate obtained by reacting with a carboxylic acid derivative containing a (meth) acrylic group such as an ester of a lower alcohol of (meth) acrylic acid, and specifically, For example, alicyclic di (meth) acrylates represented by the following general formulas (4) to (7).

[0017]

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[0018]

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[0019]

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[0020]

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R ² and R in the above general formulas (4) to (7)
³ are of the general formula (1) in the same and R ^2, R ^3, and
Each may be the same or different and is a hydrogen atom or a methyl group.

As the (meth) acrylic acid or the (meth) acrylic acid derivative represented by the general formula (2) used in the present invention, specifically, for example, acrylic acid, methacrylic acid, methacryloyl chloride, acryloyl chloride, Methacrylic anhydride, acrylic anhydride, methyl methacrylate, methyl acrylate, ethyl methacrylate,
Examples include ethyl acrylate and n-butyl acrylate.

As the alicyclic diol represented by the general formula (3) used in the present invention, specifically, for example, 3-methyl-2,2-norbornanedimethanol, 3-methyl-
5-norbornene-2,2-dimethanol, 2,2-norbornane dimethanol, 5-norbornene-2,2-
Dimethanol, 3-ethyl-2,2-norbornane dimethanol, 3-ethyl-5-norbornene-2,2-dimethanol, 3-propyl-2,2-norbornane dimethanol, 3-propyl-5-norbornene- 2,2-
Dimethanol, 3-butyl-2,2-norbornane dimethanol, 3-butyl-5-norbornene-2,2-dimethanol, 3-phenyl-2,2-norbornane dimethanol, 3-phenyl-5-norbornene- 2,2-
Dimethanol and the like.

The amount to be charged when the alicyclic diol is reacted with the (meth) acrylic acid or the (meth) acrylic acid derivative depends on the type of the precursor, but is usually, for example, (hydroxy group in the alicyclic diol). / (Meth) acrylic acid or (meth) acrylic acid derivative) in a molar ratio of 0.8 to 8,
Particularly, 1.0 to 2 is preferable.

As an embodiment of the reaction, when the alicyclic diol is reacted with the acid itself, the reaction is carried out with water such as benzene and toluene in the presence of an acid catalyst such as sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid. It is desirable to use a solvent that azeotropes and separates into two layers in a liquid state while reacting while removing generated water out of the system. 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 because 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 partner to be reacted with the alicyclic diol 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.

Specific examples of the solvent that can be used in the reaction include halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, and trichloroethane; diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane. Examples include ethers, aromatic hydrocarbons such as benzene, toluene and xylene, 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 as a partner to be reacted with the alicyclic diol, 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. When the partner to be reacted with the alicyclic diol is 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 20 to 60 ° C. in the case of an acid halide, preferably 20 to 60 ° C.
45 ° C., and in the case of an acid anhydride, 40 to 12
0 ° C., preferably 60 to 100 ° C.

When the partner to be reacted with the alicyclic diol is an ester with a lower alcohol as the (meth) acrylic acid derivative, the reaction is carried out in the presence of a suitable base catalyst.
It can be synthesized by performing a transesterification reaction and distilling off the generated alcohol. The reaction can be carried out under reduced pressure or under increased pressure. However, 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 70 to 180 ° C, more preferably 80 to 1 ° C.
A range of 50 ° C. is preferred. 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.
Phenolic polymerization inhibitors such as butyl hydroquinone monomethyl ether, phenothiazine, copper naphthoate,
Cobalt naphthoate or the like can be used. Also,
Oxygen in the air also acts as an effective polymerization inhibitor. The polymerization inhibitor is used in an amount of 0.01 to 2% by weight, preferably 0.05 to 1% by weight, based on (meth) acrylic acid or a derivative thereof.

When the reaction mixture thus obtained contains a solvent, the reaction mixture can be used as a thermosetting resin by removing the solvent under normal pressure or reduced pressure. It can be used as it is.

[0032]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the examples unless departing from the gist of the present invention. The compounds obtained in the examples are
¹ H-NMR, ¹³ C-NMR, IR and GC-MAS
S was measured under the following conditions. ^{(1 H-NMR, 13 C} -NMR spectrum measurement condition) manufactured by JEOL Ltd. JNM-EX400 type (400MH
z) was measured using CDCl ₃ as a solvent and tetramethylsilane as a standard substance. ¹³ C-NMR
Was measured under the condition that ¹ H was decoupled.

(IR spectrum measurement conditions) Using a PEBrIN-ELMER1720 manufactured by PerkinElmer or an FT / IR7300 infrared spectrometer manufactured by JASCO Corporation, measurement was performed by a liquid film method using a KBr plate.

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

Example 1 A 500 ml four-necked flask equipped with a stirrer, a cooling device, a thermometer and a dropping funnel was charged with 20 g of 3-methyl-2,2-norbornane dimethanol, 25.1 g of triethylamine and dichloromethane as a solvent. Add 200 ml, and add acrylic acid chloride 2 at room temperature.
After 200 ml of a 2.5 g dichloromethane solution was added dropwise over 90 minutes, the reaction was further performed for 1 hour. The reaction mixture was washed once with 100 ml of a saturated aqueous solution of sodium hydrogen carbonate and then three times with 100 ml of pure water. The acrylate solution thus obtained was dried over magnesium sulfate. After removing the drying agent by filtration, 0.03 g of p-methoxyphenol was added, and the solvent was distilled off by evaporation to obtain a pale yellow liquid.

FIG. 1 shows the ¹ H-NMR spectrum, FIG. 2 shows the ¹³ C-NMR spectrum, and FIG. 3 shows the IR spectrum of the obtained compound. The spectral data and assignments are as follows.

¹ H-NMR (δ, ppm, CDCl
_{3): 0.96 (d, 3H} , -CH (C H 3) -) 1.17-2.16 (m, 9H, C (norborna
ne, sp3) -H) 4.07-4.25 ( m, 4H, -C H 2 O-) 5.82d, 6.11dd, 6.40d (6H, -CO
^{_{-C H = C H 2) 13}} C-NMR (δ, ppm, CDCl 3): 15.5
_{(-CH (C H 3) -} ) 23.7,29.2,35.1,42.2,45.1,
45.1, 45.6 (C (norbornane, sp
_{3)) 64.4,67.3 (-CH 2 O-} ) 128.4,130.7 (-CO- C H = C H 2) 166.1 (-OC (O) -) IR (cm - ¹ , KBr liquid film): 1728 (ν _{C = O} ) 1297, 1267, 1191 (ν _CO ) GC / MS (m / z) 279 [M + H] From the above results, the compound obtained is represented by the following formula (8) ) Was confirmed.

[0038]

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Example 2 22.5 g of the acrylic acid chloride of Example 1 was used for 27.0 g of methacrylic acid chloride.
g, 25.2 g of triethylamine was replaced with 26.2 g to obtain a pale yellow liquid in the same manner as in Example 1.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and IR spectrum of the obtained compound were measured. The spectral data and assignments are as follows.

¹ H-NMR (δ, ppm, CDCl
_{3): 0.98 (d, 3H} , -CH (C H 3) -) 1.17-2.16 (m, 9H, C (norborna
ne, sp3) -H) 1.93 ( s, 6H, -CO-C (C H 3) = CH 2) 4.06-4.21 (m, 4H, -CH 2 O-) 5.55, 6.08 (s, 4H, -CO- C (CH 3)
^{_{= C H 2) 13 C-}} NMR (δ, ppm, CDCl 3): 15.6
_{(-CH (C H 3) -} ) 18.3 (-CO-C (C H 3) = CH 2) 23.7,29.2,35.1,42.3,45.1,
45.2, 46, 8 (C (norbornane, sp
_{3)) 64.5,67.4 (-CH 2 O-} ) 125.5,136.3 (-CO- C (CH 3) = C H
₂ ) 167.2, 167.3 (—OC (O) —) IR (cm ⁻¹ , KBr liquid film): 1718 (ν _{c = o} ) 1297,1231,1163 (ν _CO ) GC / MS (m / z) 307 [M + H] From the above results, it was confirmed that the obtained compound was a dimethacrylate compound represented by the following formula (9).

[0042]

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Example 3 The 3-methyl-2,
A pale yellow liquid was obtained by treating in the same manner as in Example 1 except that 2-methyl-5-norbornene-2,2-dimethanol was replaced with 19.8 g of 2-norbornanedimethanol.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and IR spectrum of the obtained compound were measured. The spectral data and assignments are as follows.

¹ H-NMR (δ, ppm, CDCl
_{3): 1.10 (d, 3H} , -CH (C H 3) -) 1.39-1.45m, 1.75d, 2.46s, 2.
74s (5H, C (norbornene, sp3)-
H) 3.97dd, 4.32dd (4H, -C H 2 O-) 5.80-5.86m, 6.05-6.43m (8H,
-C H = C H -, - CO-C H = C H 2) 13 C-NMR (δ, ppm, CDCl 3): 16.2
_{(-CH (C H 3) -} ) 39.6,44.4,46.5,47.4,50.2
(C (norbornene, sp3)) 65.6,68.4 (-CH 2 O-) 128.4,130.6,130.8,134.1,1
38.5 (- C H = C H -, - CO- C H = C H 2) 165.9,166.0 (-OC (O) -) IR (cm -1, KBr liquid film): 1728 ( ν _{c = O} ) 1296, 1273, 1196 (ν _CO ) GC / MS (m / z) 277 [M + H] From the above results, the obtained compound is a diacrylate compound represented by the following formula (10). It was confirmed that.

[0046]

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Example 4 The 3-methyl-2,
20 g of 2-norbornane dimethanol was added to 3-methyl-5.
To 19.8 g of norbornene-2,2-dimethanol,
22.5 g of acrylic acid chloride was added to 27.0 g of methacrylic acid chloride, and 25.1 g of triethylamine was added to 27.0 g of methacrylic acid chloride.
A pale yellow liquid was obtained in the same manner as in Example 1 except that the amount was changed to 6.2 g.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and IR spectrum of the obtained compound were measured. The spectral data and assignments are as follows.

¹ H-NMR (δ, ppm, CDCl
_{3): 1.07-1.11 (d, 3H} , -CH (C H
₃ )-) 1.24-2.74 (m, 5H, C (norborne
ne, sp3) -H) 1.93,1.95 ( 6H, -CO-C (C H 3) = C
_{H 2) 3.90-4.38 (m, 4H} , -CH 2 O-) 5.52-6.29 (m, 6H, -C H = C H -, - C
_{O-C (CH 3) =} C H 2) 13 C-NMR (δ, ppm, CDCl 3): 16.2
_{(-CH (C H 3) -} ) 18.3 (-CO-C (C H 3) = CH 2) 39.6,44.5,46.7,47.5,50.2
(C (norbornene, sp3)) 66.5,68.6 (-CH 2 O-) 125.5,125.6,134.1,136.2,1
38.5 (- C H = C H -, - CO- C (CH 3) = C
H ₂ ) 167.1, 167.2 (—OC (O) —) IR (cm ⁻¹ , KBr liquid film): 1719 (ν _{c = O} ) 1322, 1295, 1163 (ν _CO ) GC / MS (m / Z) 305 [M + H] From the above results, it was confirmed that the obtained compound was a dimethacrylate compound represented by the following formula (11).

[0050]

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Example 5 20 g of 3-methylnorbornane-2,2-dimethanol of Example 1 was added to 18.1 g of 5-norbornene-2,2-dimethanol, and 22.5 g of acrylic acid chloride was added to methacrylic acid chloride. 27.0
g in the same manner as in Example 1 except that 25.1 g of triethylamine was changed to 26.2 g to obtain a pale yellow liquid.

FIG. 4 shows the ¹ H-NMR spectrum, FIG. 5 shows the ¹³ C-NMR spectrum, and FIG. 6 shows the IR spectrum of the obtained compound. The spectral data and assignments are as follows.

¹ H-NMR (δ, ppm, CDCl
₃ ): 0.95 m, 1.46-1.70 m, 2.78
s, 2.90 s (6H, C (norbornene, s
p3) -H) 1.94 (6H, -CO-C (C H 3) = CH 2) 3.89-4.04dd, 4.29s (4H, -CH 2
O-) 5.56-5.57, 6.06-6.23 m (6H,-
C H = C H -, - CO-C (CH 3) = C H 2) 13 C-NMR (δ, ppm, CDCl 3): 18.3
_{(-CO-C (C H 3} ) = CH 2) 33.2,42.5,46.2,46.3,47.2
(C (norbornene, sp3)) 67.6,68.2 (-CH 2 O-) 125.5,125.7,134.1,136.3,1
37.9 (- C H = C H -, - CO- C (CH 3) = C
H ₂ ) 167.2, 167.3 (—OC (O) —) IR (cm ⁻¹ , KBr liquid film): 1719 (ν _{c = O} ) 1322, 1296, 1163 (ν _CO ) GC / MS (m / Z) 291 [M + H] From the above results, it was confirmed that the obtained compound was a dimethacrylate compound represented by the following formula (12).

[0054]

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[0055]

The (meth) acrylate of the present invention can be used as an ultraviolet curable resin or an electron beam curable resin, cured with a crosslinking agent, or used as a comonomer for copolymers with other ethylenically unsaturated compounds. It is useful for applications such as use as, and is superior in transparency, heat resistance, weather resistance, curability, etc. as compared to conventional (meth) acrylates, and is particularly used as an ultraviolet curable resin and an electron beam curable resin. In some cases, it has moderate mechanical strength, high heat resistance, weather resistance, curability,
Shows transparency and has great industrial utility value. Such a (meth) acrylate can be easily produced by the production method of the present invention.

[Brief description of the drawings]

[1] of the present invention (meth) ¹ H-NM acrylate
2 shows an R spectrum.

FIG. 2: ¹³ C-NM of the (meth) acrylate of the present invention
2 shows an R spectrum.

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

[4] Other (meth) acrylates of the present invention ¹ H-
3 shows an NMR spectrum.

FIG. 5 shows ¹³ C- of another (meth) acrylate of the present invention.
3 shows an NMR spectrum.

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

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C08F 32/02 C08F 32/02

Claims (3)

[Claims] 1. A novel (meth) acrylate represented by the following general formula (1). Embedded image [In the general formula (1), A represents a single bond or a double bond;
R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Represents any of phenyl groups, and R ² and R ³ represent the same or different hydrogen or methyl groups] 2. The novel (meth) acrylate according to claim 1, wherein R ¹ is a methyl group. 3. A (meta) represented by the following general formula (2):
The method for producing a novel (meth) acrylate according to claim 1, wherein acrylic acid or a derivative thereof is reacted with an alicyclic diol represented by the following general formula (3). Embedded image [In the general formula (2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a hydroxyl group, an alkoxy group, a chlorine atom or CH
₂ represents a C (R ⁵ ) COO— group] [In the general formula (3), A represents a single bond or a double bond;
R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Represents any of phenyl groups]