JP2000302774A - Production of bisoxetane ethers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject bisoxetane ether that is useful as paint and coating materials having excellent heat resistance, mechanical properties, flatness and adhesion by allowing a sulfonic ester of 3-alkyl-3-hydroxymethyloxetane to react with a diol in the presence of a base. SOLUTION: A compound of formula I (R is a 1-6C alkyl; and X is methyl, phenyl or the like) [for example, 2-(3-oxetane)propyl mesilate)] and a compound of the formula: HO-Y-OH (Y is a 2-16C divalent aliphatic chain group) (for example, ethylene glycol) are allowed to react with each other in the presence of a base in a organic solvent (for example, dimethyl sulfoxide) in an amount of 500-2,000 ml per mole of the compound of formula I to give the objective compound of formula II (Y is -CH2CH=CHCH2-) that bears the cationically polymerizable oxetane ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing bisoxetane ether compounds having an oxetane ring capable of cationic polymerization. In addition, the photocurable or thermosetting resin derived from these bisoxetane ether compounds has excellent heat resistance, mechanical properties, flatness and adhesion, and is used as a coating material and a coating material.

[0002]

2. Description of the Related Art Bisoxetane ether compounds are compounds that have received attention in recent years as monomers capable of photoinitiated cationic polymerization or curing, and methods for producing many monofunctional and polyfunctional bisoxetane ether compounds. And novel bisoxetane ether compounds. As a method for producing bisoxetane ether compounds, for example, Bull.Chem.Soc.Jpn., 61, pp.1653 (1988), P.
ure Appl. Chem., A29 (10), pp915 (1992), Pure Appl. Ch.
em., A30 (2 & 3), pp189 (1993) and JP-A-6-16804, 3-alkyl-3-hydroxymethyloxetane and α, ω
A method for synthesizing a bisoxetane ether compound by contacting a dibromoalkane with an aqueous alkali metal hydroxide solution and a phase transfer catalyst is disclosed. However, this method requires an extremely large amount of α, ω-dibromoalkane since a relatively expensive α, ω-dibromoalkane is easily dehydrobrominated with an alkali metal hydroxide, and also requires various auxiliary processes. There is a problem that the yield of the target bisoxetane ether compound is low because the product is produced. DE 1,021,858 also includes 3-alkyl-3-
A method for synthesizing a bisoxetane ether compound by contacting halomethyloxetane with an alkali metal phenolate of a dihydric phenol is disclosed. However, this method has problems such as difficulty in industrially synthesizing 3-alkyl-3-halomethyloxetane and low yield of the target product.

[0003] Also, JP-A-7-53711, JP-A-7-173
No. 279, JP-A-8-245783, JP-A-9-309950 and JP-A-10-212343, various bis oxetane ether compounds are disclosed, but in any of the references There is no description of a simple synthesis method, and further no description is given of the bisoxetane ether compound of the present invention.

[0004]

The object of the present invention is to provide a 3-alkyl-3-hydroxymethyloxetane,
It is an object of the present invention to provide an industrially advantageous method for producing bisoxetane ether compounds, which can synthesize bisoxetane ether compounds in a high yield by a simple method without the need for complicated operations.

[0005]

The object of the present invention is to provide a compound of the general formula (1)

[0006]

Embedded image (In the formula, R represents an alkyl group having 1 to 6 carbon atoms, and X represents a methyl group, a phenyl group, or a p-tolyl group.)

A sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane represented by the general formula (2)

[0008]

Embedded image (In the formula, Y is a divalent aliphatic chain organic group having 2 to 16 carbon atoms, and may have a double bond, an ether bond, or a cyclic structure in the chain.)

Wherein the diol represented by the general formula (3) is reacted in the presence of a base.

[0010]

Embedded image (Wherein, R represents an alkyl group having 1 to 6 carbon atoms, Y is a divalent aliphatic chain organic group having 2 to 16 carbon atoms, and a double bond, an ether bond or a cyclic structure in the chain. May be included.)

The problem is solved by the method for producing bisoxetane ether compounds represented by the formula:

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION A sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane as a raw material used in the reaction of the present invention is represented by the above general formula (1). In the general formula (1), R is an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a propyl group (and its isomer), a butyl group (and its isomer), a pentyl group ( And its isomers) and hexyl group (and its isomers), preferably a methyl group and an ethyl group.

The sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane oxetane used as a raw material in the reaction of the present invention includes, for example, 2- (3-oxetane)
Propyl mesylate, 2- (3-oxetane) propylphenylsulfonylate, 2- (3-oxetane) propyl tosylate, 2- (3-oxetane) butyl mesylate, 2- (3-oxetane) butylphenylsulfonate Rate, 2- (3-oxetane) butyl tosylate, 2- (3-oxetane) pentyl mesylate, 2- (3-oxetane) pentylphenylsulfonylate, 2- (3-oxetane) pentyl tosylate, 2- (3-oxetane) hexyl mesylate, 2- (3-oxetane) hexylphenylsulfonylate, 2- (3-oxetane) hexyl tosylate and the like.

The sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane is, for example, Organic Synt
Hesis, Collective vol. 1, 145 pp. (1941).

The diol used in the present invention is represented by the above general formula (2). In the general formula (2), Y is a divalent aliphatic chain organic group having 2 to 16 carbon atoms, and may have a double bond, an ether bond or a cyclic structure in the chain.

The divalent aliphatic chain organic groups having 2 to 16 carbon atoms include, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene and the like. , Nonamethylene, decamethylene, undecamethylene and other divalent aliphatic hydrocarbon groups; 2-butenylene and 3-hexenylene groups and other divalent aliphatic chains having a double bond in the chain Hydrocarbon group; divalent aliphatic chain hydrocarbon group having an ether bond in the chain such as 3-oxypentylene group, 3,6-dioxyoctylene group; cyclohexane-1,4-bismethylene group, tricyclo [5.2.1.0 ^2,6 ] A divalent aliphatic chain hydrocarbon group having a cyclic structure in the chain, such as a decane-4,8-bismethylene group.

The diol used in the reaction of the present invention includes ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,
1,11-dodecanediol, 2-butene-1,4-diol, 3-hexene-1,6-diol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol,
4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ]
Decane and the like.

The base used in the reaction of the present invention includes alkali metals such as sodium and potassium; alkali metal hydrides such as lithium hydride and sodium hydride;
And alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

The reaction of the present invention is preferably performed in a solvent. Examples of the solvent used include ether solvents such as ethylene glycol diethyl ether and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide; Dimethyl sulfoxide, toluene, or a mixed solvent of dimethyl sulfoxide and toluene is used.

The amount of the solvent used depends on the starting material, 3-alkyl-3
-With respect to 1 mol of the sulfonic acid ester of hydroxymethyloxetane, preferably 300 to 5000 ml, more preferably 5 to 5 ml.
It is between 00 and 2000 ml. These solvents may be used alone or in combination of two or more.

In the reaction of the present invention, for example, a diol, a base and a solvent are mixed and heated and stirred in an inert gas atmosphere to synthesize an alkali metal alcoholate of a diol. The reaction is carried out at normal pressure or under pressure by a method such as adding a sulfonate of oxetane and further heating and stirring. The reaction temperature at that time is preferably 20 to 180 ° C., more preferably 50 to 1
50 ° C.

After completion of the reaction, the reaction mixture is cooled to room temperature, washed with water to remove impurities, and then subjected to extraction, column chromatography, distillation, recrystallization and the like to obtain the desired bisoxetane ether. Compounds can be obtained. These compounds were obtained by FD-MS, G
The structure can be confirmed by C-MS, ¹ H-NMR, ¹³ C-NMR, IR and the like.

In the present invention, the general formula (3)

[0024]

Embedded image (Wherein, R represents a methyl group or an ethyl group, and Y represents

[0025]

Embedded image Is a divalent group selected from )

The compound represented by is a bisoxetane ether compound whose structure can be identified by the above-mentioned analytical method.

[0027]

EXAMPLES The present invention will be described below in detail with reference to examples, but the scope of the present invention is not limited to these examples. Note that the purity in Reference Examples and Examples is a value calculated from the area percentage by gas chromatography analysis.

Reference Example 1 Internal volume equipped with thermometer, cooler, stirrer, and dropping funnel
95.33 g (0.50 mol) of p-toluenesulfonyl chloride, 5.69 g (0.025 mol) of benzyltrimethylammonium chloride and 500 ml of toluene were added to a 1000 ml three-necked flask, and the mixture was cooled to 5 ° C. with stirring. In addition, 3-ethyl-
After adding 58.08 g (0.50 mol) of 3-hydroxymethyloxetane, 75 ml of 35% aqueous sodium hydroxide solution was added through a dropping funnel.
It was dropped over 30 minutes. The temperature of the reaction rose to 10 ° C. After the dropwise addition, the mixture was stirred at the same temperature for 1 hour, and further stirred at room temperature for 3 hours. After completion of the reaction, 200 ml of water was added and the mixture was vigorously stirred, and then the aqueous phase and the oil phase were separated. The oil phase was washed with 200 ml of saturated saline and dried over anhydrous magnesium sulfate. Thereafter, magnesium sulfate was separated by filtration, and toluene was distilled off from the filtrate under reduced pressure, and as a residue, colorless transparent liquid 2- (3-oxetane) butyl tosylate 123.51 g was obtained.
Was obtained with a purity of 98.5% (yield 90%).

Example 1 16.00 g of sodium hydride was placed in the same reaction vessel as in Reference Example 1.
(Mineral oil dispersion (content 60-72%), 0.4 mol as 60% content) and 300 ml of ethylene glycol diethyl ether were added,
After replacing the inside of the reactor with nitrogen, the reactor was cooled to 5 ° C. while stirring. A solution prepared by dissolving 12.42 g (0.2 mol) of ethylene glycol in 100 ml of ethylene glycol diethyl ether was dropped from the dropping funnel over 30 minutes. After dropping,
The temperature was gradually raised to 50 ° C., and the mixture was stirred at the same temperature for 30 minutes.
Next, 110.55 g (0.4 mol) of 2- (3-oxetane) butyl tosylate having a purity of 98.5% synthesized in Reference Example 1 was added dropwise, and the mixture was stirred for 6 hours while refluxing. After 6 hours, the conversion of 2- (3-oxetane) butyl tosylate was 99.9%. After completion of the reaction, the reaction mixture was cooled to room temperature, and a small amount of water was added to completely consume sodium hydride. Thereafter, the precipitate was separated by filtration, and the filtrate and the precipitate were washed with 300 ml of toluene, and the obtained washings were combined and washed with 400 ml of a 5% aqueous sodium carbonate solution and 250 ml of brine. The oil phase was separated, anhydrous magnesium sulfate was added and dried, the solvent was distilled off under reduced pressure, and the bottom was distilled under reduced pressure (125 to 130 ° C, 1.5 mm
Hg), 73.0 g of a colorless transparent liquid was obtained. The purity of this compound was 97%.

The results of measuring the properties of the obtained compound are shown below. FD-MS: 258 (molecular weight) ¹ H-NMR (CDCl ₃ ): δ (ppm); 0.87 (t, J = 7.5 Hz, 6H), 1.74
(q, J = 7.5Hz, 4H), 3.60 (s, 4H), 3.65 (S, 4H), 4.37 (d, J =
5.9 Hz, 4H), 4.45 (d, J = 5.9 Hz, 4H) ¹³ C-NMR (CDCl ₃ ): δ (ppm); 7.53, 26.18, 42.83, 70.2
3, 73.32, 77.56 IR (neat): 982, 1115cm ^-1

The compound obtained from the above analysis results is
Equation (5)

[0032]

Embedded image

The compound was identified as 1,2-di [2- (3-oxetane) butoxy] ethane represented by the following formula: The isolation yield by distillation was 73%.

Example 2 Internal volume equipped with thermometer, cooler, stirrer and dropping funnel
Sodium hydride 57.60 g in a 3000 ml three-necked flask
(Mineral oil dispersion (content 60-72%), 1.44 mol as content 60%)
And 600 ml of dimethyl sulfoxide. The inside of the reactor was purged with nitrogen, and then heated to 60 ° C. with stirring. A solution prepared by dissolving 57.60 g (0.72 mol) of 2-butene-1,4-diol in 150 ml of dimethyl sulfoxide was dropped from the dropping funnel over 30 minutes. After completion of the dropwise addition, the mixture was stirred at the same temperature for 30 minutes. Next, 324.00 g (1.2 mol) of 2- (3-oxetane) butyl tosylate having a purity of 98.5% synthesized in Reference Example 1 was added dropwise,
The mixture was stirred at 60 ° C. for 6 hours. After 6 hours, the 2- (3-oxetane) butyl tosylate had been completely consumed. After completion of the reaction, the reaction mixture was cooled to room temperature, 300 ml of toluene was added, and then 300 ml of water, 300 ml of a 10% aqueous potassium carbonate solution, and
Washed twice with 0 ml. The oily phase was separated, anhydrous magnesium sulfate was added, and the mixture was dried.The solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure (160 to 172 ° C, 1.5 mmHg) to obtain 263.21 g of a colorless transparent liquid. Was done. 98% pure
Met.

The results of measuring the physical properties of the obtained compound are shown below. FD-MS: 284 (molecular weight) ¹ H-NMR (CDCl ₃ ): δ (ppm); 0.88 (t, J = 7.3 Hz, 6H), 1.75
(q, J = 7.3Hz, 4H), 3.55 (s, 4H), 4.02-4.11 (m, 4H), 4.36
~ 4.46 (m, 8H) 、 5.71 ~ 5.81 (m, 2H) IR (neat): 982、1107cm ^-1

The compound obtained from the above analysis results is
Equation (6)

[0037]

Embedded image

, Was identified as 1,4-di [2- (3-oxetane) butoxy] -2-butene. In addition, the isolation yield by distillation was 76%.

Example 3 A reaction vessel similar to that of Example 2 was charged with 40.00 g of sodium hydride.
(Dispersed mineral oil (content: 60 to 72%), 1.0 mol with a content of 60%) and 700 ml of toluene were added, and the inside of the reactor was purged with nitrogen, and then cooled to 5 ° C with stirring. To this, 53.06 g (0.5 mol) of diethylene glycol was added to 700 m of dimethyl sulfoxide.
The solution dissolved in 1 was dropped from the dropping funnel over 30 minutes. After dropping, slowly raise the temperature to 50 ° C.
Stir for 30 minutes. Then, the mixture was cooled to room temperature, and 270.35 g (1.0 mol) of 2- (3-oxetane) butyl tosylate having a purity of 98.5% synthesized in Reference Example 1 was added dropwise, and the temperature was gradually raised to 60 ° C. for 2 hours. The temperature was raised to 80 ° C., and the mixture was stirred for 4 hours. 6
After time, the 2- (3-oxetane) butyl tosylate had been completely consumed. After completion of the reaction, the reaction mixture was cooled to room temperature, and a small amount of water was added to completely consume sodium hydride. Thereafter, the precipitate was separated by filtration, and the filtrate and the precipitate were washed with 500 ml of toluene.
The mixture was washed twice with 500 ml of an aqueous sodium carbonate solution and 300 ml of a saline solution. The oil phase was separated, anhydrous magnesium sulfate was added and dried, and the solvent was distilled off under reduced pressure.
(154-171 ° C, 1.5mmHg), 116.55g of colorless and transparent liquid
was gotten. The purity of this compound was 96%.

The results of measuring the properties of the obtained compound are shown below. FD-MS: 302 (molecular weight) ¹ H-NMR (CDCl ₃ ): δ (ppm); 0.88 (t, J = 7.3 Hz, 6H), 1.74
(q, J = 7.3Hz, 4H), 3.59 (s, 4H), 3.62 (t, J = 3.7Hz, 4H), 3.
67 (t, J = 3.7Hz, 4H), 4.37 (d, J = 5.9Hz, 4H), 4.45 (d, J = 5.9
Hz, 4H) ¹³ C-NMR (CDCl ₃ ): δ (ppm); 7.16, 25.94, 42.50, 70.0
5, 70.24, 72.56, 77.00 IR (neat): 982, 1113 cm ^-1

The compound obtained from the above analysis results is
Equation (7)

[0042]

Embedded image

The compound was identified as di (2- [2- (3-oxetane) butoxy] ethyl) ether. The isolation yield by distillation was 74%.

Example 4 In Example 3, instead of diethylene glycol,
The reaction was carried out in the same manner as in Example 3, except that 71.11 g (0.5 mol) of 1,4-cyclohexanedimethanol (a mixture of the cis form and the trans form) was used as a raw material. As a result, vacuum distillation (175-
190 ° C., 1.5 mmHg) to give a translucent, waxy solid 177.3
4 g were obtained. The purity of this compound was 96%.

The results of measuring the properties of the obtained compound are shown below. FD-MS: 340 (molecular weight) ¹ H-NMR (CDCl ₃ ): cis-form δ (ppm); 0.87 (t, J = 7.3 Hz, 6H),
0.9-1.0 (m, 2H), 1.4-1.6 (m, 4H), 1.73 (q, J = 7.3Hz, 4
H), 1.65-1.90 (m, 4H), 3.25 (d, J = 6.3 Hz, 4H), 3.50 (s, 2
H), 4.36 (d, J = 5.9 Hz, 4H), 4.45 (d, J = 5.9 Hz, 4H) Transformer δ (ppm); 0.87 (t, J = 7.3 Hz, 6H), 0.9 to 1.0 (m ,
2H), 1.4-1.6 (m, 4H), 1.73 (q, J = 7.3Hz, 4H), 1.65-1.9
0 (m, 4H), 3.34 (d, J = 6.8 Hz, 4H), 3.51 (s, 4H), 4.36 (d, J =
5.9 Hz, 4H), 4.45 (d, J = 5.9 Hz, 4H) ¹³ C-NMR (CDCl ₃ ): δ (ppm); 7.85, 25.35, 26.49, 29.0
2, 35.00, 37.82, 43.12, 73.26, 74.45, 76.91, 78.04 IR (neat): 981, 1101 cm ^-1

The compound obtained as a result of the above analysis was
Equation (8)

[0047]

Embedded image

A novel compound represented by the formula: 1,4-bis [2- (3-
Oxetane) butoxymethyl] cyclohexane. The isolation yield by distillation was 66% (mixture of cis-form and trans-form; cis-form: trans-form = 1: 1.87).

Example 5 Internal volume equipped with thermometer, cooler, stirrer and dropping funnel
In a 200 ml three-necked flask, 9.81 g (50 mmol) of 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, 93
A 5.16 g (120 mmol) aqueous sodium hydroxide solution, 40 ml of methyl sulfoxide and 2 ml of water were added, and the inside of the reactor was purged with nitrogen, and then heated to 80 ° C and stirred for 2 hours. To this, 32.40 g (120 mmol) of 2- (3-oxetane) butyl tosylate having a purity of 98.5% synthesized in Reference Example 1 was added in 20 ml of dimethyl sulfoxide.
Was dissolved in a dropping funnel over 20 minutes.
Thereafter, the mixture was heated to 140 ° C. and stirred for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 200 ml of toluene and 150 ml of water were added, and the mixture was washed three times with 100 ml of water. The oil phase was separated, anhydrous magnesium sulfate and activated carbon were added, dried and decolorized, the solvent was distilled off under reduced pressure, then magnesium sulfate and activated carbon were filtered off, and the filtrate was concentrated under reduced pressure (60 ° C, 2 ° C).
mmHg), 18.89 g of a colorless and transparent liquid as a kettle
was gotten. The purity of this compound was 93%.

The results of measuring the physical properties of the obtained compound are shown below. GC-MS: 392 (molecular weight) ¹ H-NMR (CDCl ₃ ): δ (ppm); 0.88 (t, J = 7.6 Hz, 6H), 1.20-
1.80 (m, 8H), 1.74 (q, J = 7.6Hz, 4H), 1.90-2.20 (m, 4H),
2.20 to 2.50 (m, 2H), 3.10 to 3.40 (m, 4H), 3.50 (s, 4H), 4.
36 (d, J = 5.9Hz, 4H), 4.45 (d, J = 5.9Hz, 4H) IR (neat): 982,1107cm ^-1

The compound obtained as a result of the above analysis was
Equation (9)

[0052]

Embedded image

A novel compound represented by the following formula, 4,8-bis [2- (3-oxetane) butoxymethyl] tricyclo [5.2.1.0 ^2,6 ] decane, was identified. The isolation yield by distillation is 90
%Met.

[0054]

Industrial Applicability According to the present invention, a bisoxetane ether compound can be synthesized from a 3-alkyl-3-hydroxymethyloxetane in a high yield by a simple method without the need for complicated operations. It is possible to provide a method for producing bisoxetane ether compounds which is economically advantageous.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Riichi Machida 8-1 Goi south coast, Ichihara City, Chiba Prefecture Ube Industries, Ltd. Polymer Research Laboratory F term (reference) 4C048 TT02 4J005 AA07 AA09

Claims (4)

[Claims] 1. A compound of the general formula (1) (Wherein, R represents an alkyl group having 1 to 6 carbon atoms, and X represents a methyl group, a phenyl group or a p-tolyl group) and a sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane represented by the formula: General formula (2) (Wherein, Y is a divalent aliphatic chain organic group having 2 to 16 carbon atoms and may have a double bond, an ether bond or a cyclic structure in the chain). Is reacted in the presence of a base, characterized by the general formula (3) (Wherein, R represents an alkyl group having 1 to 6 carbon atoms, Y is a divalent aliphatic chain organic group having 2 to 16 carbon atoms, and a double bond, an ether bond or a cyclic structure in the chain. A process for producing bisoxetane ether compounds represented by the formula: 2. The method for producing bisoxetane ether compounds according to claim 1, wherein in the general formulas (1) and (3), R is a methyl group or an ethyl group. 3. The method for producing bisoxetane ether compounds according to claim 1, wherein the base is at least one base selected from alkali metals, alkali metal hydrides and alkali metal hydroxides. 4. A compound of the general formula (3) (Wherein, R represents a methyl group or an ethyl group, and Y represents Is a divalent group selected from A) bisoxetane ether compound represented by the formula: