JP2001039926A - Alicyclic di(meth)acrylate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful in the field of an ultraviolet curable resin, an electron beam-curable resin, etc., showing high heat resistance, weatherability and transparency, further having proper mechanical strength, containing a norbornane skeleton in the molecule. SOLUTION: This 3,4-bis((meth)acryloyloxy)tricyclo[5.2.1.02.6]decane compound is shown by formula I (R1 is H or a 1-4C alkyl; and R2 and R3 are each H or a 1-10C alkyl) such as 3,4-bis(acryloxyloxy)tricyclo[5.2.1.02/6]decane. The compound of formula I is obtained, for example, by reacting 3,4- dihydroxytricylo[5.2.1.02.6]decane of formula II with an acrylic acid compound of formula III (R4 is H or a 1-10C alkyl) in the presence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a compound represented by the formula [1]:

[0002]

Embedded image

(Wherein R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
4 represents an alkyl group, and R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The present invention relates to 3,4-bis ((meth) acryloyloxy) tricyclo [5.2.1.0 ^2,6 ] decane compound represented by the formula: The compound of the present invention is an alicyclic di (meth) acrylate having two or more (meth) acryl groups, and is used as a UV-curable resin, an electron beam effect resin, a crosslinking agent, and other ethylenically unsaturated compounds. It is useful for use as a comonomer for a copolymer with a.

[0004]

2. Description of the Related Art When a diester of a diol and a (meth) acrylate is obtained, if the diol contains a benzene ring such as xylene diol, a curable resin using the diol has poor weather resistance. There were drawbacks. In addition, when the diol is an aliphatic such as ethylene glycol or propylene glycol, the curable resin has a disadvantage that it becomes very brittle, and when the diol is a hydroxyl-terminated polyether such as polyethylene glycol or polypropylene glycol. Has a drawback of low heat resistance.

Further, there has been reported an example in which 3-cyclohexene-1,1-dimethanol was used as a diol and reacted with acrylic acid under a sulfuric acid catalyst to obtain a corresponding diacrylate ester [AEBotog et al., Zh. .Org.Khim., 18
(1), 90 (1982)], but there is a disadvantage that transparency and the like are inferior. Until now, there has been no di (meth) acrylate that satisfies physical properties such as weather resistance, heat resistance, and hardness.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ultraviolet curable resin, an electron beam curable resin, a curable resin by a crosslinking agent, and a comonomer for a copolymer with another ethylenically unsaturated compound. High heat resistance, weather resistance,
An object of the present invention is to provide a novel di (meth) acrylate which has a norbornane skeleton in a molecule, which exhibits transparency and has appropriate mechanical strength.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.

That is, the present invention relates to the following formula [1]

[0009]

Embedded image

(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
4 represents an alkyl group, and R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The present invention relates to a 3,4-bis ((meth) acryloyloxy) tricyclo [5.2.1.0 ^2,6 ] decane compound represented by the formula: Equation [2]

[0011]

Embedded image

3,4-dihydroxytricyclo [5.2.1.0 ^2,6 ] decane represented by the following formula:

[0013]

Embedded image

Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, and reacting with an acrylic acid compound represented by the following formula under an acid catalyst. [1]
And a process for producing a 3,4-bis ((meth) acryloyloxy) tricyclo [5,2,1,0 ^2,6 ] decane compound represented by the formula:

[0015] Furthermore, 3,4 represented by the above formula [2]
-Dihydroxytricyclo [5.2.1.0 ^2,6 ] decane and formula [4]

[0016]

Embedded image

(Wherein, R ¹ , R ² and R ³ have the same meanings as described above, and X represents a halogen atom). The reaction is carried out in the presence of a base. 3,4-bis ((meth) acryloyloxy) tricyclo [5.2.
1.0 ^2,6 ] decane compound. Less than,
The present invention will be described in detail.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing a 3,4-bis ((meth) acryloyloxy) tricyclo [5.2.1.0 ^2,6 ] decane compound represented by the above formula [1] of the present invention is as follows. ,
It is represented by the following three reaction schemes.

[0019]

Embedded image

(Wherein R ¹ , R ² , R ³ and X have the same meaning as described above, and R ⁴ represents an alkyl group having 1 to 10 carbon atoms.) (1) and (2) The reaction proceeds with an acid catalyst. First, (1) and (2) will be described together.

3,4-dihydrido represented by the formula [2]
Roxytricyclo [5.2.1.0 ^2,6] Decane (below)
Abbreviated as lower TCDOL. ) In the following reaction scheme
Manufactured.

[0022]

Embedded image

That is, tricyclo [5,2,1,
0 ^2,6 ] dec-3-ene (hereinafter abbreviated as TCD)
Is oxidized with oxygen or an organic or inorganic peracid to give 3,4-
Epoxytricyclo [5,2,1,0 ^2,6 ] decane (hereinafter abbreviated as ETCD) is obtained. Further ETCD
Is hydrated with an acid catalyst to obtain TCDOL.

An acrylic acid compound represented by the general formula [3]
R¹Represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
And preferably a hydrogen atom or a carbon number of 1 to 2. Ma
R ², R³And R⁴Has 1 to 10 carbon atoms, and is preferably
Or a hydrogen atom or a carbon number of 1-5.

Specifically, acrylic acid, methacrylic acid, thiglycic acid, 3,3-dimethylacrylic acid, 2-methyl-2-pentenoic acid, 2-ethyl-2-hexenoic acid, 2-octenoic acid, etc. And their acrylate compounds having 1 to 10 carbon atoms, specifically, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl tiglylate, ethyl tiglylate, 3,3-dimethyl Methyl acrylate, 3,3-dimethylethyl acrylate, methyl 2-methyl-2-pentenoate, ethyl 2-methyl-2-pentenoate, methyl 2-ethyl-2-hexenoate, 2-ethyl-2-hexene And ethyl 2-octenoate and ethyl 2-octenoate.

This reaction requires a catalyst. As the catalyst, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid can be used.
Sulfuric acid is preferred. Organic acids such as benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and trifluoroacetic acid can also be used.
-Toluenesulfonic acid and benzenesulfonic acid are preferred.

Further, as a catalyst, tungstic acid, molybdenum,
Denic acid or a heteropoly acid thereof is mentioned. Hete
Specific examples of ropoly acids include H₃PW₁₂O₄₀, H₄
SiW₁₂O₄₀, H₄TiW₁₂O₄₀, H₅CoW
₁₂O₄₀, H₅FeW₁₂O₄₀, H₆P₂W₁₈O
₆₂, H₇PW₁₁O₃₃, H₄TiMo₁₂O₄₀,
H₃PMo₁₂O₄₀, H₇PMo₁₁O₃₉, H₆P
₂Mo₁₈O₆₂, H ₄PMoW₁₁O₄₀, H₄PV
Mo₁₁O₄₀, H₄SiMo₁₂O₄₀, H ₅PV₂
Mo₁₀O₄₀, H₃PMo₆W₆O₄₀, H_0.5C
s_2.5PW_{1 2}O₄₀And their hydrates are typical
It is mentioned as a thing. In addition, these can be converted to carbon or silica.
And the like. These heteropoly
Among the acids, H₃PW₁₂O₄₀, H₃PMo₁₂O
₄₀And their hydrates are particularly preferred.

Further, cation exchange resins such as Amberlyst IR120, H-type zeolites such as H-ZSM-5, and the like can also be used.

Particularly, as a catalyst in the case of the transesterification method, in addition to the aforementioned mineral acids, heteropoly acids, organic acids, cation exchange resins and H-type zeolites, 3ZnO-2B ₂
Fatty acid salts of Group II compounds of the periodic table represented by O ₃ , cadmium acetate, zinc acetate and calcium acetate can be used.

These catalysts can be used in an amount of 0.1 to 100% by weight based on TCDOL.
20% by weight is preferred.

In this reaction, an acrylic acid compound or an acrylic ester compound can be used in a large excess, but the reaction can also be carried out using a solvent by reducing the amount of the allyl alcohol derivative to near the theoretical amount, and usually using a solvent. It is preferred to use. Examples of the type of the solvent include halogenated hydrocarbons such as 1,2-dichloroethane (EDC) and 1,1,1-trichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, 1,2-dimethoxyethane and the like. Ethers such as diethylene glycol dimethyl ether;

The amount of the solvent used is 1 to 2 with respect to TCDOL.
It is 0 times by weight, more preferably 1 to 6 times by weight. Reaction temperature is 50 to 200 ° C, more preferably 70 to 150 ° C.
It is. The reaction can be carried out under normal pressure or under pressure. The reaction time can be 1 to 50 hours, usually 2 to 1 hour.
It is practical to do it in 2 hours. Next, a production method of the reaction scheme (3) will be described.

The acrylic acid halide compound represented by the general formula [4] is obtained by converting the above acrylic acid compound into an acid halide with thionyl halide or the like. Halogen includes F, Cl, Br and I, but the cheapest Cl is used. Specifically, acryloyl chloride, methacryloyl chloride, tiglyloyl chloride, 3,3-dimethylacryloyl chloride, 2-
Methyl-2-pentenoyl chloride, 2-ethyl-2
-Hexenoyl chloride and 2-octeroyl chloride. The amount used is preferably 2.0 to 2.5 equivalents to TCDOL.

In the method represented by the reaction formula (3), a base is indispensable, and the kinds thereof include chain alkylamine compounds represented by trimethylamine, triethylamine and tripropylamine, pyridine, aniline and N-methyl. Aromatic amine compounds such as aniline, 1,
5-diazabicyclo [4,3,0] no-5-ene (DB
N), 1,4-diazabicyclo [2,2,2] octane (DBO) and 1,8-diazabicyclo [5,4,0]
Examples thereof include cyclic alkylamine compounds represented by undec-7-ene (DBU) and the like, and metal carbonates such as sodium carbonate, sodium hydrogencarbonate, potassium carbonate and potassium hydrogencarbonate. Preferred among these bases are:
Triethylamine and tripropylamine. The amount used is preferably 2.0 to 2.5 equivalents to TCDOL (equivalent to acid chloride).

The process preferably employs a solvent. Examples of the solvent include ether compounds such as tetrahydrofuran (THF), 1,2-dimethoxyethane, dioxane, and 2-methoxyethyl ether, N, N-dimethylformamide (DMF), and N, N-dimethylacetamide (DM
Ac), N-methylpyrrolidone and 1,3-dimethyl-
2-imidazolidinone (DMI) and the like are preferred. Of these, inexpensive 1,2-dimethoxyethane and DMF are preferred. The use amount thereof is preferably 1 to 10 times by weight, and particularly preferably 2 to 5 times by weight, relative to TCDOL.

The reaction temperature is from 0 to 100 ° C., particularly from 0 to 5
0 ° C. is preferred. After the reaction, water is added to hydrolyze the residual acid chloride, the solvent is distilled off, and the residue is extracted with a poorly water-soluble solvent (ether or ester), and then purified by distillation or column chromatography. The desired product can be obtained. The above-described reaction and purification of the present invention can be performed in a batch system or a continuous system.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Reference Example 1 3,4-epoxytricyclo [5,2,1,0 ^2,6 ]
Synthesis of decane (ETCD) Tricyclo [5,
2,1,0 ^2,6 ] dec-3-ene (TCD) 13.4
g (100 mmol) and 67 g of 1,4-dioxane were charged, and 22.6 g (110 mmol) of 37% peracetic acid was added to 3
It was added dropwise at 5 to 40 ° C over 1 hour. Then at 45 ° C 5
Stir for hours and determine the raw material TC
It was confirmed that D had disappeared, and a new peak appeared.
The residue was dissolved by adding 100 ml of toluene to the residue by concentration under reduced pressure, and the residue was washed twice with 35 ml of water.
The organic layer was concentrated and dried at 40 ° C. under reduced pressure to obtain 13.9 g of jelly-like crystals (93% yield). The analysis results of the crystals were as follows.

MASS (FAB +, e / m (%)): 1
51 (M + 1, 27), 133 (100), 91 (7
0), 78 (51), 66 (92). ¹ H-NMR (CDCl ₃ , TMS, δ ppm): 1.
35 to 1.53 (m, 6H), 1.72 (t, J = 2.
8 Hz, 1H), 1.75 (t, J = 2.8 Hz, 1
H), 1.83 (dd, J ₁ = 8.8 Hz, J ₂ = 1
4.9 Hz, 1H), 2.11 (s, 1H), 2.35
~ 2.42 (m, 3H), 3.34 (d, J = 2.3H)
z, 1H), 3.53 (t, J = 2.35 Hz, 1
H). ¹³ C-NMR (CDCl ₃ , TMS, δ ppm): 2
2.46, 23.21, 28.19, 38.78, 4
1.32, 42.52, 44.85, 47.9, 60.
73, 61.26. From the above, it was confirmed that this crystal was 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane (ETCD).

Reference Example 2 3,4-dihydroxytricyclo [5.2.1.0
Synthesis of ^2,6 ] decane (hereinafter TCDOL) 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane (ETCD) in a 100 ml four-necked flask
4.50 g (30 mmol) and 1,4-dioxane 22
g, water 22 g and 98% sulfuric acid 0.30 g (3 mmol)
Was heated to 85 ° C. and stirred for 2 hours. It was confirmed by gas chromatography analysis that the raw material ETCD had disappeared. After 1,4-dioxane was distilled off by concentration under reduced pressure, water and ethyl acetate were added to the residue and extracted.

After washing the organic layer with 5% aqueous sodium bicarbonate and water,
It was dehydrated with anhydrous magnesium sulfate. Subsequently, this was filtered and concentrated to obtain 4.24 g (yield: 83.1%) of pale yellow crude crystals. Further, the crystals were recrystallized with heptane / ethyl acetate = 4/1 to obtain white crystals.
85 g (76.3% yield) were obtained. The analysis results of the crystals were as follows.

MASS (FD ⁺ , e / m (%)): 16
8 (M ⁺ , 100), 151 (1), 133 (7), 7
4 (13). ¹ H-NMR (CDCl ₃ , TMS, δ ppm): 1.
36 to 1.59 (m, 7H), 1.74 to 1.79
(M, 1H), 2.04 to 2.10 (m, 2H), 2.
25 to 2.92 (m, 2H), 3.68 (t, J = 8.
17Hz, 1H), 4.00 (s, 2H), 4.83
(S, 2H). ¹³ C-NMR (CDCl ₃ , TMS, δ ppm): 2
1.93, 23.56, 30.00, 37.99, 3
8.82, 39.46, 42.91, 47.95, 7
7.52, 80.61. Melting point: 103-104 ° C. From the above, the crystals were confirmed to be 3,4-dihydroxy-tricyclo [5.2.1.0 ^{2, 6]} decane (TCDOL).

Example 1 In a 50 ml four-necked flask, 3,4-dihydroxytricyclo [5.2.1.0 ^2,6 ] decane (TCDO)
L) 1.68 g (10 mmol), 20 ml of tetrahydrofuran and 2.22 g (2
2 mmol) and 2.17 g (24 mmol) of acryloyl chloride was added dropwise at 5 ° C. with stirring in a stream of N ₂ . After stirring at 5 ° C for 1 hour, the mixture was further stirred at 25 ° C for 1 hour.
Stirred for hours. When the reaction mixture was analyzed by gas chromatography, the starting TCDOL disappeared and a new peak appeared. The reaction solution was concentrated under reduced pressure, and the residue was extracted with 40 ml of 1,2-dichloroethane and 10 ml of 0.5N HCl.

The organic layer was washed with 3% aqueous sodium bicarbonate and water, and concentrated to obtain 2.69 g of pale yellow oil. Subsequently, the oily substance was purified by silica gel chromatography (heptane / ethyl acetate = 6/1) to obtain 2.41 g (yield: 87.3%) of a colorless oily substance. The analysis results of this oil were as follows.

MASS (FD ⁺ , e / m (%)): 276
(M ⁺ , 43), 204 (100). ¹ H-NMR
(CDCl ₃ , TMS, δ ppm): 1.41 to 1.6
0 (m, 6H), 1.80 to 1.84 (m, 1H),
2.05 to 2.21 (m, 3H), 2.35 (s, 1
H), 2.42 to 2.45 (m, 1H), 5.10
5.14 (m, 1H), 5.30 to 5.37 (m, 1
H), 5.80-5.85 (m, 2H), 6.06-
6.14 (m, 2H), 6.36 to 6.41 (m, 2
H). ¹³ C-NMR (CDCl ₃ , TMS, δ ppm): 2
2.08, 23.27, 27.74, 39.00, 3
9.58, 42.77, 46.86, 76.68, 7
9.18, 128.31, 128.36, 128.3
9,128.85,130.89,131.06,13
1.09. From the above, this oily substance was found to be 3,4-bis (acryloyloxy) tricyclo [5.2.1.0 ^2,6 ] decane (T
CDA).

Example 2 3,4-dihydroxytricyclo [5.2.1.0 ^2,6 ] decane (TCDO) was placed in a 50 ml four-necked flask.
L) 1.68 g (10 mmol), acrylic acid 2.16
g (30 mmol), 0.17 g of p-toluenesulfonic acid monohydrate, 0.05 g of hydroquinone and 20 ml of benzene were mixed, heated to 80 to 90 ° C., and stirred while removing water. Five hours later, after cooling, toluene and water were added for extraction, and the toluene layer was washed with water and concentrated to obtain 2.45 g of an oily substance. This oil was chromatographed on silica gel (heptane / ethyl acetate = 6 /
1.86 g of TCDA (yield 6)
7.4%).

Example 3 3,4-Dihydroxytricyclo [5.2.1.0 ^2,6 ] decane (TCDO) was placed in a 50 ml four-necked flask.
L) 1.68 g (10 mmol), 20 ml of tetrahydrofuran and 2.22 g (2
2.51 g (24 mmol) of methacryloyl chloride was added dropwise at 5 ° C. while stirring in a stream of N ₂ . After stirring at 5 ° C. for 1 hour as it was, stirring was further performed at 25 ° C. for 1 hour. When the reaction solution was analyzed by gas chromatography, the raw materials remained, a new peak appeared, and the ratio was constant at the third and fifth hours. The reaction solution was concentrated under reduced pressure, and the residue was extracted by adding 40 ml of toluene and 20 ml of water.

The organic layer is further washed with water and concentrated.
3.13 g of a pale yellow oil was obtained. Subsequently, the oily substance was subjected to silica gel chromatography (heptane / ethyl acetate =
678) to give 1.78 g of a colorless oil.
(58.6% yield) was obtained. The analysis results of this oil were as follows.

MASS (FAB +, e / m (%)): 3
05 (M + 1,94), 219 (100), 133 (7
7). ¹ H-NMR (CDCl ₃ , TMS, δ ppm): 1.
16-1.18 (m, 1H), 1.30-1.60
(M, 7H), 1.83 (s, 6H), 2.08 (s,
2H), 2.27 (s, 1H), 2.35 to 2.37.
(M, 1H), 5.01 (t, J = 8.2 Hz, 1
H), 5.22-5.28 (m, 1H), 5.46-
5.48 (m, 2H), 5.99 to 6.02 (m, 2
H). ¹³ C-NMR (CDCl ₃ , TMS, δ ppm): 1
8.28,22.12,23.32,27,77,3
9.08, 39.55, 39.63, 39.75, 4
2.79, 46.89, 77.00, 79.38, 12
5.63, 125.74, 136.17 (2), 16
6.86, 167.25. From the above, it was confirmed that this oil was 3,4-bis (methacryloyloxy) tricyclo [5.2.1.0 ^2,6 ] decane (TCDM).

Example 4 In Example 2, acrylic acid was replaced with methacrylic acid 2.5.
The reaction and after-treatment were carried out in the same manner except that the amount was changed to 8 g (30 mmol). 1.59 g of a colorless TCDM obtained after purification by silica gel chromatography (yield 52.4).
%)Met.

[0050]

The polyester obtained from the alicyclic monomer is known to have excellent physical and chemical properties such as transparency, heat resistance, chemical resistance and dimensional stability. The polyester using the alicyclic di (meth) acrylate of the present invention is an excellent one in which these properties are further improved, and is useful as various optical materials such as an optical disk, a substrate of an optical card and a substrate for a liquid crystal display. Material. Further, it is a useful material as a monomer of a polymerizable composition having polymer properties excellent in light transmittance, heat resistance, birefringence, adhesiveness, moisture resistance, hardness and the like.

Continued on front page F-term (reference) 4H006 AA01 AA02 AB46 AB49 AC48 AD11 AD17 BA02 BA14 BA28 BA30 BA32 BA34 BA51 BA52 BA75 BB15 BB20 BB24 BB25 BC10 BC34 BC35 BJ30 BT14 FC24 KA03 KA06 KA14 4H039 CA66 CE10 CG10 CG20

Claims (5)

[Claims] [Claim 1] Formula [1] (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom or 1 to 4 carbon atoms.
Represents 10 alkyl groups. 3,4-bis ((meth) acryloyloxy) tricyclo [5.2.
1.0 ^2,6 ] decane compound. 2. Formula [2] 3,4-dihydroxytricyclo [5.2.
1.0 ^2,6 ] decane and formula [3] (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). Reacting an acrylic acid compound with an acrylic acid compound in the presence of an acid catalyst; (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom or 1 to 4 carbon atoms.
Represents 10 alkyl groups. 3,4-bis ((meth) acryloyloxy) tricyclo [5.2.
1.0 ^2,6 ] method for producing a decane compound. 3. The method according to claim 2, wherein the acid catalyst is p-toluenesulfonic acid, benzenesulfonic acid and sulfuric acid.
A method for producing a bis ((meth) acryloyloxy) tricyclo [5.2.1.0 ^2,6 ] decane compound. 4. Formula 2 3,4-dihydroxytricyclo [5.2.
1.0 ^2,6 ] decane and formula [4] (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom or 1 to 4 carbon atoms.
Represents 10 alkyl groups. Wherein the acrylic halide derivative of the formula (1) is reacted in the presence of a base. (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom or 1 to 4 carbon atoms.
Represents 10 alkyl groups. 3,4-bis ((meth) acryloyloxy) tricyclo [5.2.
1.0 ^2,6 ] method for producing a decane compound. 5. The 3,4-bis ((meth) acryloyloxy) tricyclo [5.2.1.] According to claim 4, wherein the base is an alkylamine, an aromatic amine or a metal carbonate. 0 ^2,6 ] decane compound production method.