JPH07101903A - Acrylic ester derivative - Google Patents

Abstract

PURPOSE:To obtain a new acrylic ester derivative useful as a comonomer for acrylic rubber, capable of forming a copolymer to give a vulcanized material having excellent heat resistance and compression set resistance. CONSTITUTION:This acrylic ester derivative is shown by formula I [R<1> is H or lower alkyl; R<2> and R<3> are X or XCH2CO (X is halogen) with the proviso that R<2> and R<3> are not X at the same time; n is 0 or 1]. The compound wherein R<2> and R<3> are XCH2COO among the compound of formula I is obtained by hydrolyzing an epoxy compound of formula A in a hydrous solvent in the presence of an acid to give a diol compound of formula B and reacting the diol compound of formula B with an acid halide of formula D in the presence of a base.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel acrylic ester derivative.

[0002]

2. Description of the Related Art Conventionally, a compound having an unsaturated bond and a halogen atom in its side chain is generally used as a synthetic raw material or a monomer for polymerization because it has high reactivity. For example, vinyl chloroacetate is used as a comonomer of acrylic rubber containing acrylic acid ester as a main component. Acrylic rubber is generally excellent in heat resistance, oil resistance, and ozone resistance, and is mainly used in the automobile field. However, higher performance is required as the performance of automobiles increases in recent years. Therefore, it has been attempted to improve the performance by vulcanizing vinyl chloroacetate as a comonomer as described above, but it is still unsatisfactory in terms of heat resistance and compression set resistance. It was

[0003]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors under such circumstances, the acrylic ester derivative represented by the following formula (2) is a novel compound and is used as a comonomer for acrylic rubber. They have found that they are useful, and that the vulcanized copolymers obtained can improve heat resistance and compression set resistance, and have completed the present invention based on this finding.

[0004]

Thus, according to the present invention, there is provided an acrylic ester derivative characterized by being represented by the formula (2).

[Chemical 2] (In the formula, R ¹ represents a hydrogen atom or a lower alkyl group.
R ² and R ³ represent X— or XCH ₂ COO—, and X represents a halogen atom. However, R ² and R ³ are not X at the same time. n represents 0 or 1. )

The acrylic ester derivative of the present invention is represented by the above formula (2) and is a novel compound not described in any literature. In the formula, R ¹ represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a propyl group or an isopropyl group. Of these, a hydrogen atom or a methyl group is preferred. R ²
And R ³ represents an X- or XCH ₂ COO-, X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine halogen atom such as iodine atom. Of these, chlorine atom is preferable. Such R
² and R ³ cannot be X at the same time.

The acrylic ester derivative of the present invention can be synthesized by a conventional method. For example, R ² and R ³ are X
When it is CH ₂ COO-, it can be obtained by employing the following steps.

[Chemical 3]

(1) First, the epoxy compound (A) is hydrolyzed in a water-containing solvent in the presence of an acid to obtain a diol compound (B). The water-containing solvent is a solvent that can be mixed with water in an arbitrary ratio, for example, ethers such as dioxane and glyme; ketones such as acetone and methyl ethyl ketone; sulfoxides such as dimethyl sulfoxide; and amides such as dimethylformamide. And a mixed solvent of water and water is used. The amount of water is usually 0.1 to 10 relative to the solvent.
It is twice the weight. Further, the amount of the water-containing solvent used is appropriately selected within a range in which the concentration of the epoxy body (A) in the water-containing solvent is 0.1 to 10 mol / liter.

Examples of the acid include concentrated sulfuric acid, perchloric acid, periodic acid, trifluoroacetic acid, trinitrobenzenesulfonic acid and the like. The amount of acid used is the epoxy body (A) 1
It is usually 0.01 to 100 mol per mol. The reaction is usually performed in an inert atmosphere such as nitrogen gas.
The reaction temperature is 0 to 100 ° C., and the reaction time is 1 to 10 hours.

(2) Next, diol (B) and formula (4)
By reacting with an acid halide represented by the formula (2) in the presence of a base, R ² and R ³ of the formula (2) are XCH ₂ COO.
It is possible to obtain the acrylic ester derivative (C) which is −.

[Chemical 4] (In the formula, X and Y represent halogen atoms which may be the same or different.) The amount of the acid halide used is usually 2 to 3 mol per 1 mol of the diol (B).

As the base, tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, dimethylethylamine, dimethyllaurylamine, dimethylstearylamine, methylethylpropylamine and tribenzylamine are used. The amount of the base used is usually 1 to 2 mol with respect to 1 mol of the acid halide.

A solvent may be present in the reaction. The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene; alicyclic hydrocarbons such as cyclohexane; carbon tetrachloride, dichloroethane, chlorobenzene, bromobenzene, etc. And halogenated hydrocarbons; ethers such as anisole, dibutyl ether and dioxane; ketones such as acetone and acetophenone; esters such as ethyl acetate. The amount of solvent used is the diol (B)
Is appropriately selected within the range of 0.1 to 10 mol / liter in the solvent. The reaction is usually performed in an inert atmosphere such as nitrogen gas. Reaction temperature is -20 to +5
The reaction time is 1 to 10 hours at 0 ° C.

In the above reactions (1) and (2), a polymerization inhibitor can be present in the reaction system. As the polymerization inhibitor, p-methoxyphenol, diphenylpicrylhydrazyl, tri-p-nitrophenylmethyl, N- (3-N-oxyanilino-1,3-diphenylbutylidene) aniline oxide, p-benzoquinone,
P-tert-butyl catechol, nitrosobenzene, picric acid, dithiobenzoyl sulfide, etc. are exemplified. The amount of the polymerization inhibitor used is usually 0.00 based on 1 mol of the epoxy compound (A) or the diol compound (B).
It is 1 to 0.1 mol.

After completion of the reaction, the acrylic ester derivative can be isolated from the reaction solution by a conventional method. For example, a highly pure acrylic ester derivative can be obtained by washing the reaction solution, distilling off the solvent, and purifying by column chromatography.

On the other hand, when R ² and R ^{3 in} the above formula (2) are X- or XCH ₂ COO- and different from each other, the acrylate derivative can be obtained by adopting the following steps. it can.

[Chemical 5] The halohydrin compound obtained in this step is a mixture of structural isomers of (D) and (E), and the acrylic ester derivative finally obtained has R ² of X— and R ³ of XCH ₂
When (F) is COO-, R ² is XCH ₂ COO-, R ³
Is a mixture of structural isomers with (G) where -X.

(3) First, an acid is added dropwise to the epoxy compound (A) in an inert solvent to form the halohydrin compound (D).
And (E) are obtained. Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloromethane. Are used. The amount of the solvent used is appropriately selected in such a range that the concentration of the epoxy compound (A) in the solvent is 0.1 to 10 mol / liter. As the acid, hydrochloric acid, hydrobromic acid, hydroiodic acid or the like is used. The amount of the acid used is usually 1 to 1.5 mol per 1 mol of the epoxy body (A). The reaction is usually performed in an inert atmosphere such as nitrogen gas. The reaction temperature is -10 to + 100 ° C, and the reaction time is 1 to 1.
It's 0 hours.

(4) Next, a halohydrin compound (D) and
(E) and the acid halide represented by the above formula (4)
By reacting in the presence of R of the formula (2)²Over
And R³ Is X- or XCH₂COO-, different from each other
Acrylic acid ester derivative (F) and
(G) can be obtained. The amount of acid halide used is
Usually, relative to 1 mol of the rohydrin form (D) and (E),
It is 1 to 2 mol. The base is the same tertiary amine as described above.
Used. The amount of base used is 1 mol of acid halide
In general, it is 1 to 2 mol. In the reaction,
A similar solvent may be present. The amount of solvent used is halo
The concentration of the hydrin forms (D) and (E) in the solvent was 0.
It is appropriately selected within the range of 1 to 10 mol / liter.
The reaction is usually performed in an inert atmosphere such as nitrogen gas.
It Reaction temperature is -20 to + 50 ° C, reaction time is 1 to 10
It's time.

Also in the above reactions (3) and (4), the same polymerization inhibitor as described above can be present in the reaction system. The amount of the polymerization inhibitor used is 1 mol of the epoxy compound (A) or the halohydrin compound (D) and (E),
Usually, it is 0.001 to 0.1 mol. After completion of the reaction, the acrylic ester derivative can be isolated from the reaction solution by a conventional method. For example, a highly pure acrylic ester derivative can be obtained by washing the reaction solution, distilling off the solvent, and purifying by column chromatography.

The acrylic ester derivative thus obtained is a novel substance and has a polymerizable carbon-carbon double bond, and is useful as various synthetic raw materials and monomers for polymerization. For example, it can be copolymerized by a conventional method with a monoethylenically unsaturated monomer represented by acrylic acid ester which is the main component of acrylic rubber. By vulcanizing the obtained copolymer with a sulfur-based vulcanizing agent, a vulcanized product having excellent heat resistance and compression set can be obtained.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Parts and% in the examples and comparative examples are based on weight unless otherwise specified. Example 1 Under a nitrogen atmosphere, the reactor was charged with 18.1 grams of 3,4-epoxy-1-cyclohexylmethyl methacrylate and 100 milliliters of toluene. After cooling with ice, concentrated hydrochloric acid 11
Milliliter was gradually added dropwise, and the mixture was reacted under ice cooling for 1 hour and at room temperature for 2 hours. The toluene layer was separated, saturated aqueous sodium hydrogen carbonate,
The extract was washed with saturated saline and dried over magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography to give a halohydrin compound as a colorless liquid substance in a yield of 90.2%.
Got with.

The spectral data of the halohydrin form is shown below. IR (cm ^-1 ): 3700 to 3050, 1715, ^{1
635 · 1 H-NMR (CDCl} 3) δ: 1.55~2.40
(M, 7H), 1.95 (s, 3H), 2.20 (b
r, 1H), 3.85 (m, 1H), 3.95 (m, 1
H), 4.05 (d, 2H), 5.60 (s, 1H),
6.15 (s, 1H) -GC-mass spectrum: 232.5

From the above spectrum data, in the halohydrin form, in the above formulas (D) and (E), X is Cl and n is 0,
It is presumed to be a mixture of structural isomers in which R ¹ is —CH ₃ .

Then, under a nitrogen atmosphere, 18.0 g of the halohydrin compound and 100 ml of dichloromethane were added and dissolved in the reactor. After cooling with ice, 13 ml of triethylamine was added, and a dichloromethane solution containing 9.6 g of chloroacetic acid chloride was added dropwise over 30 minutes. Then, the mixture was stirred under ice cooling for 5 hours, and then the reaction solution was washed with diluted hydrochloric acid water, saturated sodium hydrogen carbonate solution and saturated saline solution. The organic layer is dried over magnesium sulfate, the solvent is distilled off,
After purification by column chromatography, an acrylate derivative (hereinafter referred to as Compound 1) was obtained as a pale yellow liquid substance.
Is written. ) Was obtained with a yield of 86.9%.

The spectral data of Compound 1 is shown below. ^{· IR (cm -1): 1760,1715,1635} · 1 H-NMR (CDCl 3) δ: 1.40~2.40
(M, 7H), 1.95 (s, 3H), 4.05 (d,
2H), 4.10 (s, 2H), 4.15 to 4.30.
(M, 1H), 5.05 to 5.25 (m, 1H), 5.
60 (s, 1H), 6.15 (s, 1H) -GC-mass spectrum: 309

From the above spectral data, compound 1 is
It is presumed to be a mixture of structural isomers in which X in the formulas (F) and (G) is Cl, n is 0, and R ¹ is —CH ₃ .

Example 2 5,6-Epoxy-2-bicyclo [2,2,1] heptylmethyl acrylate 18.9 was charged to a reactor under a nitrogen atmosphere.
Grams and 100 milliliters of toluene were added. After cooling with ice, 12 ml of concentrated hydrochloric acid was gradually added dropwise, and the mixture was reacted under ice cooling for 1 hour and at room temperature for 2 hours. The toluene layer was separated, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. When the solvent was distilled off and the residue was purified by column chromatography, a halohydrin compound was obtained as a colorless liquid substance in a yield of 59.9%.

The spectral data of the halohydrin form is shown below. IR (cm ^-1 ): 3700 to 3050, 1725, ^{1
635,1620 · 1 H-NMR (CDCl} 3) δ: 0.65~2.60
(M, 8H), 4.00 (m, 2H), 4.05 (m,
1H), 4.10 to 4.25 (m, 1H), 5.85
6.50 (m, 3H) -GC-mass spectrum: 230.5

From the above spectrum data, in the halohydrin form, X in the above formulas (D) and (E) is Cl and n is 1,
It is presumed to be a mixture of structural isomers in which R ¹ is -H.

Then, under a nitrogen atmosphere, 11.0 g of the halohydrin compound and 100 ml of dichloromethane were added and dissolved in the reactor. After cooling with ice, 8 ml of triethylamine was added, and a dichloromethane solution containing 9.6 g of chloroacetic acid chloride was added dropwise over 30 minutes. Then, the mixture was stirred under ice cooling for 5 hours, and then the reaction solution was washed with diluted hydrochloric acid water, saturated sodium hydrogen carbonate solution and saturated saline solution. The organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by column chromatography. As a result, an acrylic ester derivative (hereinafter referred to as compound 2) was obtained as a pale yellow liquid in a yield of 76.9%. Got with.

The spectral data of Compound 2 is shown below. IR (cm ^-1 ): 1760, 1725, 1635, ¹
620. ¹ H-NMR (CDCl ₃ ) δ: 0.70 to 2.85
(M, 7H), 3.95 (m, 1H), 4.05 (d,
2H), 4.10 (s, 2H), 4.80 to 5.00
(M, 1H), 5.80 to 6.55 (m, 3H) -GC-mass spectrum: 307

From the above spectral data, compound 2 is
It is presumed to be a mixture of structural isomers in which X in the above formulas (F) and (G) is Cl, n is 1, and R ¹ is —H.

Example 3 Under a nitrogen atmosphere, 18.0 g of 3,4-epoxy-1-cyclohexylmethyl methacrylate, 100 ml of dioxane and 30 ml of distilled water were added to the reactor. After adding 0.6 g of concentrated sulfuric acid, the mixture was reacted at 50 ° C. for 2 hours. After adding sodium bicarbonate to neutralize, the solvent was distilled off,
Purification by column chromatography gave a diol as a colorless liquid substance in a yield of 89.5%.

The spectrum data of the diol are shown below.・ IR (cm ^-1 ): 3700 to 3000, 1720, ¹
635 · ¹ H-NMR (CDCl ₃ ) δ: 1.40 to 2.30
(M, 7H), 1.95 (s, 3H), 2.75 (b
r, 2H), 3.40 to 3.75 (m, 2H), 4.1
0 (m, 2H), 5.55 (s, 1H), 6.15
(S, 1H) -GC-mass spectrum: 214

From the above spectrum data, it is estimated that the diol has a structure in which n in formula (B) is 0 and R ¹ is —CH ₃ .

Then, under a nitrogen atmosphere, 16.6 g of the diol compound and 100 ml of dichloromethane were added and dissolved in the reactor. After cooling with ice, 26 ml of triethylamine was added, and a dichloromethane solution containing 19.3 g of chloroacetic acid chloride was added dropwise over 1 hour. Then, the mixture was stirred under ice cooling for 5 hours, and then the reaction solution was washed with diluted hydrochloric acid water, saturated sodium hydrogen carbonate solution and saturated saline solution. The organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by column chromatography. As a result, an acrylic ester derivative (hereinafter referred to as compound 3) was obtained as a pale yellow liquid in a yield of 72.1%. Got with.

The spectral data of compound 3 is shown below. ^{· IR (cm -1): 1760,1715,1635} · 1 H-NMR (CDCl 3) δ: 1.40~2.25
(M, 7H), 1.95 (s, 3H), 4.10 (m,
6H), 4.95 to 5.20 (m, 2H), 5.60.
(S, 1H), 6.10 (s, 1H) -GC-mass spectrum: 367

From the above spectral data, compound 3 is
It is presumed that X in the formula (C) is Cl, n is 0, and R ¹ is —CH ₃ .

Reference Example 1 A 2 liter separable flask was equipped with a thermometer, a stirrer, a nitrogen introducing tube and a pressure reducing device. First, after charging each component of the polymerization formulation (A) shown below to a flask, the pH of the mixture in the flask was adjusted to 7, the temperature of the system was set to 5 ° C. with stirring, and degassing and nitrogen substitution were performed. Was repeated to remove oxygen in the system. Then, each component of the polymerization formulation (B) shown below was added to initiate polymerization. The polymerization temperature was 5 ° C and the polymerization time was about 16 hours. Polymerization conversion rate (A) is 9
6% and (B) were 98%. After completion of the polymerization, the polymerization components were salted out, washed thoroughly with water, dried under reduced pressure and dried for 24 hours to obtain a copolymer. The Mooney viscosity (ML1 + 4, 100 ° C.) of this copolymer was 52.

Polymerization Formula (A) (grams) Water 1000 Sodium dodecylbenzene sulfonate 20 Sodium naphthalene sulfonate 10 Sodium sulfate 3 Ethylenediaminetetraacetic acid tetrasodium salt 0.2 Ethylenediaminetetraacetic acid sodium ferric salt 0.005 Compound 1 32 Ethyl acrylate 968

Polymerization Formula (B) (Grams) Na ₂ S ₂ O ₄ 0.2 Sodium Formaldehyde Sulfoxylate 0.2 p-Methane Hydroperoxide 0.1

100 parts of the above copolymer, a diphenylamine-based antioxidant (manufactured by Uniroyal Chemical Co., Naug
ard445) 2 parts, stearic acid 1 part, furnace black (manufactured by Tokai Carbon Co., Seast 116) 50 parts,
A mixture of 3 parts of sodium stearate, 0.5 part of potassium stearate and 0.3 part of sulfur was added at 170 ° C. for 2 hours.
Press vulcanize for 0 minutes, then in a gear oven, 170
A vulcanized product was obtained by heat treatment at 4 ° C for 4 hours.

The characteristics of this vulcanized product at room temperature are shown in JIS K-6.
It measured according to 301. The results are shown below. Tensile Strength: 146 (Kgf / cm ²⁾ Elongation: 400 (%) 100% Modulus: 28 (Kg / cm ²⁾ Hardness (JIS-A): 58 · compression strain ratio (%): 23 .2

Further, this vulcanized product was subjected to an air heating aging test (aging condition: left at 175 ° C. for 168 hours) to examine heat resistance. The results are shown below.・ Tensile strength change rate: -40 (%) ・ Elongation change rate: -8 (%) ・ 100% Tensile stress change rate: -7 (%) Elongation change rate is change from absolute value before air heating aging test Expressed as a rate.

Reference Example 2 Substituting 19 grams of Compound 3 for Compound 1,
Polymerization was performed in the same manner as in Reference Example 1 except that 981 g of ethyl acrylate was used to obtain a copolymer. The Mooney viscosity (ML1 + 4, 100 ° C.) of this copolymer was 53. Then, this copolymer was treated in the same manner as in Reference Example 1 to obtain a vulcanized product. The properties of this vulcanizate at room temperature are JISK-
It measured according to 6301. The results are shown below. Tensile Strength: 144 (Kgf / cm ²⁾ Elongation: 370 (%) 100% Modulus: 28 (Kg / cm ²⁾ Hardness (JIS-A): 57 · compression strain ratio (%): 21 .2

Further, this vulcanized product was subjected to an air heating aging test (aging condition: left at 175 ° C. for 168 hours) to examine heat resistance. The results are shown below.・ Tensile strength change rate: -50 (%) ・ Elongation change rate: 19 (%) ・ 100% Tensile stress change rate: -25 (%)

Comparative Example 1 Polymerization was carried out in the same manner as in Reference Example 1 except that 12 g of monochlorovinyl acetate was used instead of Compound 1 and 988 g of ethyl acrylate was used to obtain a copolymer. The Mooney viscosity of this copolymer (ML1 + 4,100
C.) was 51. Then, this copolymer was treated in the same manner as in Reference Example 1 to obtain a vulcanized product. The properties of this vulcanizate at room temperature were measured according to JIS K-6301. The results are shown below. Tensile Strength: 143 (Kgf / cm ²⁾ Elongation: 260 (%) 100% Modulus: 32 (Kg / cm ²⁾ Hardness (JIS-A): 58 · compression strain ratio (%): 35 .7

Further, this vulcanized product was subjected to an air heating aging test (aging condition: left at 175 ° C. for 168 hours) to examine heat resistance. The results are shown below. -Tensile strength change rate: -90 (%)-Elongation change rate: 200 (%)-100% Tensile stress change rate: -69 (%)

Claims (1)

[Claims] 1. An acrylic acid ester derivative represented by the formula (1). [Chemical 1] (In the formula, R ¹ represents a hydrogen atom or a lower alkyl group.
R ² and R ³ represent X— or XCH ₂ COO—, and X represents a halogen atom. However, R ² and R ³ are not X at the same time. n represents 0 or 1. )