JPH11246541A - Multifunctional oxetane compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new multi-functional oxetane compound giving a light- curing or a thermosetting resin having excellent heat resistance, mechanical properties and adhesiveness, by reacting a respective specific oxetane with a multifunctional isocyanate. SOLUTION: This compound is expressed by the formula R is H or a 1-6C alkyl; (n) is 2 or 3; X is a bifunctional or three-functional aromatic residue or a bifunctional aliphatic residue}, e.g. bis(3-ethyloxetan-3-ylmethyl)-2,4-tolylene dicarbamate. Preferably, the compound of the formula is obtained by reacting 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane with a multifunctional isocyanate in e.g. a solvent such as benzene in the presence of a catalyst such as triethylamine at a temp. of 20-200 deg.C reaction temperature under the atmosphere of an inert gas such as helium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyfunctional oxetane compound obtained from 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane and a polyvalent isocyanate, and a method for producing the same. The photocurable or thermosetting resin derived therefrom has excellent heat resistance, mechanical properties and adhesion, and is used for paints and adhesives.

[0002]

2. Description of the Related Art Oxetane compounds are attracting attention in recent years as monomers capable of photoinitiated cationic polymerization or curing, and many monofunctional and polyfunctional oxetane compounds have been reported. These monomers have advantages that epoxy monomers do not have, such as little environmental pollution, no influence of oxygen at the time of polymerization, high polymerization rate, and reduction of process cost. Utilizing these advantages, development of various electronic materials, paints, adhesives and coating materials is planned. There are the following known documents regarding these oxetane compounds. For example, Pure Appl.Chem., A29 (10), pp.915 (1992) and Pur
e Appl. Chem., A30 (2 & 3), pp. 189 (1993) describes a method for synthesizing various oxetane derivatives.

[0003] DE 1,021,858 also has the general formula (2)
The oxetane compound represented by is disclosed.

Embedded image (In the formula, R is an aromatic residue having a valence of 2 or more, and n is 1 or 2.)

Further, JP-A-6-16804 describes an oxetane compound represented by the general formula (3).

Embedded image (Wherein, R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, an allyl group, an aryl group, a furyl group or a thienyl group, or a fluorine atom. R ² is a chain or branched poly A (alkyleneoxy) group, a xylylene group, a polyvalent group selected from the group consisting of a siloxane bond and an ester bond, Z is an oxygen atom or a sulfur atom, and m is
2, 3, or 4. )

[0005] Japanese Patent Application Laid-Open No. 8-245783 discloses 2,2 '
There are many oxetane compounds, including bifunctional oxetanes having a vitriylene diyl skeleton.
JP-A-7-17958 describes a method for synthesizing an oxetane compound by reacting allyl chloride with hydroxymethyloxetane. However, none of these known documents describes the compounds of the present invention, and no specific examples of the synthesis methods are described.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyfunctional oxetane compound and a method for producing the same.

[0007]

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

[0008]

Embedded image (Wherein, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is 2 or 3, X is a divalent or trivalent aromatic residue or a divalent aliphatic residue. Is solved by a polyfunctional oxetane compound represented by the formula:

[0009] The present invention is further solved by a process for producing a polyfunctional oxetane compound, which comprises reacting a 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane with a polyvalent isocyanate.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, X of the polyfunctional oxetane compound represented by the aforementioned general formula (1) is 2
A trivalent or trivalent aromatic residue or a divalent aliphatic residue,

[0011]

[Formula 5] And so on.

In the present invention, a novel polyfunctional oxetane compound represented by the general formula (1) is obtained by reacting a 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane with a polyvalent isocyanate. Can be obtained.

The raw material oxetane compound used in the present invention is the aforementioned 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane. 3-
The alkyl group in the alkyl-3-hydroxymethyloxetane is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.

The raw polyisocyanate used in the present invention includes 1,2-benzene diisocyanate,
1,3-benzene diisocyanate, 1,4-benzene diisocyanate, 2-chloro-1,4-benzene diisocyanate,
2,3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- Dimethoxybiphenyl-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, bis (4-isocyanatophenyl) methane,
Bis (3-methyl-4-isocyanatophenyl) methane, tris (4-isocyanatophenyl) methane, and tris (4-isocyanatophenyl) phosphine are exemplified.

In the present invention, a solvent may be used when reacting 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane with a polyvalent isocyanate. Examples of the solvent used include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aprotic polar solvents such as dimethylacetamide, dimethylformamide, and N-methyl-2-pyrrolidone; Is preferably used. The amount of the solvent used is 3-alkyl-3-hydroxymethyloxetane or 3-alkyl-3-hydroxymethyloxetane.
The amount is preferably from 500 to 20,000 ml, more preferably from 1,000 to 10,000 ml, per 1 mol of hydroxymethyloxetane.

In the present invention, polyvalent isocyanate (or a solution of the above-mentioned solvent) is gradually added dropwise to 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyl-oxetane (or a solution of the above-mentioned solvent). The method is desirable.

The reaction temperature in the above reaction is preferably
The temperature is 20 to 200 ° C, more preferably 50 to 150 ° C. The reaction time depends on the reaction temperature, but 2 to 6 hours after the polyhydric isocyanate is completely dropped is sufficient. The reaction is carried out in an atmosphere of an inert gas such as helium, nitrogen, argon or the like under normal pressure or under pressure.

If necessary, a catalyst can be used in the present invention. Examples of the catalyst used include amines such as triethylamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylguanidine, triethylenediamine; tin octylate, dibutyltin diacetate, dibutyltin dimaleate, octylic acid Metal salts of organic acids such as lead are mentioned, and triethylamine is particularly preferably used. The amount of the catalyst used is preferably 0.02 to equimolar, more preferably 0.05 to 1 mol of the oxetane compound.
~ 0.5 mol.

After the completion of the reaction, the reaction mixture is cooled to room temperature, washed with water and / or a weakly basic aqueous solution, dried, or, if necessary, distilled off the solvent. Oxetane compounds can be obtained. This is a novel compound that can be confirmed by FD-MS and ¹ H-NMR (CDCl ₃ ).

[0020]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 100 ml equipped with a thermometer, a cooler, a stirrer and a dropping funnel
2.33 g (20 mmol) of 3-ethyl-3-hydroxymethyloxetane, 0.50 g of triethylamine (5
mmol) and 40 ml of toluene, and the mixture was heated and stirred at 110 ° C. under a nitrogen atmosphere. To this, 2,4-tolylene diisocyanate
A solution obtained by dissolving 1.74 g (10 mmol) in 20 ml of toluene was dropped from the dropping funnel over 100 minutes. After completion of the dropwise addition, the mixture was heated and stirred at 110 ° C for 2 hours, and further at 120 ° C for 2 hours. After the completion of the reaction, the reaction mixture is cooled to room temperature, and a 5% aqueous sodium hydrogen carbonate solution is added.
Washing was performed twice with 50 ml, and twice with 50 ml of water. The oil phase was separated, dried over anhydrous magnesium sulfate, and filtered. The toluene in the filtrate was distilled off under reduced pressure to obtain 3.18 g of a white solid as a residue. FD-MS measurement of this compound confirmed that the molecular weight was 406. Further, from the measurement result of ¹ H-NMR (CDCl ₃ ) shown in FIG. 1, the obtained compound was represented by the formula (4)

[0022]

[Formula 6] Represented by, bis (3-ethyloxetane-3-ylmethyl)-
It was identified as a 2,4-tolylene carbamate.

Example 2 Into the same reaction vessel as in Example 1, 2.04 g (20 mmol) of 3-methyl-3-hydroxymethyloxetane and 0.5% of triethylamine were added.
0 g (5 mmol) and 40 ml of toluene were added, and under a nitrogen atmosphere, 120
The mixture was heated and stirred at ℃. A solution prepared by dissolving 1.74 g (10 mmol) of 2,4-tolylene diisocyanate in 20 ml of toluene was added dropwise from a dropping funnel over 25 minutes, and the mixture was further heated and stirred at 120 ° C. for 5 hours. After completion of the reaction, cool the reaction mixture to room temperature, and add 5%
Wash twice with 50 ml of aqueous sodium bicarbonate solution, then add 50 ml of water
And washed twice. The oil phase was separated and toluene was distilled off under reduced pressure until the volume was reduced to about 1/3. Then, a solid was precipitated, and it was filtered and dried to obtain a white solid 2.
80 g were obtained. From the FD-MS measurement of this compound, the molecular weight was 37.
It was confirmed to be 8. Further, ¹ H-NMR (CD
From the measurement results of Cl ₃ ), the obtained compound was represented by the formula (5)

[0024]

Embedded image Represented by, bis (3-methyloxetane-3-ylmethyl)-
It was identified as a 2,4-tolylene carbamate.

EXAMPLE 3 2.32 g (20 mmol) of 3-ethyl-3-hydroxymethyloxetane and 0.5% of triethylamine were placed in the same reaction vessel as in Example 1.
0 g (5 mmol) and toluene 40 ml were added, and under a nitrogen atmosphere, 110 g
The mixture was heated and stirred at ℃. A solution in which 1.68 g (10 mmol) of 1,6-hexamethylene diisocyanate was dissolved in 20 ml of toluene was added dropwise from the dropping funnel over 120 minutes, and the mixture was further heated and stirred at 110 ° C. for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and washed twice with 50 ml of water. The oil phase was separated, dried over anhydrous magnesium sulfate, and filtered. The toluene in the filtrate was distilled off under reduced pressure to obtain 2.68 g of a viscous colorless and transparent liquid as a residue. FD-MS measurement of this compound confirmed that the molecular weight was 400. Further, from the measurement result of ¹ H-NMR (CDCl ₃ ) shown in FIG. 3, the obtained compound was represented by the formula (6)

[0026]

[Formula 8] Represented by, bis (3-ethyloxetane-3-ylmethyl)-
It was identified as 1,6-hexamethylene dicarbamate.

Example 4 Into the same reaction vessel as in Example 1, 2.04 g (20 mmol) of 3-methyl-3-hydroxymethyloxetane and 0.5% of triethylamine were added.
0 g (5 mmol) and 40 ml of toluene were added, and under a nitrogen atmosphere, 120
The mixture was heated and stirred at ℃. A solution in which 1.68 g (10 mmol) of 1,6-hexamethylene diisocyanate was dissolved in 20 ml of toluene was added dropwise from a dropping funnel over 60 minutes, and the mixture was further heated and stirred at 120 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and washed twice with 50 ml of a 5% aqueous sodium hydrogen carbonate solution.
The oil phase was separated, dried over anhydrous magnesium sulfate, and filtered. When toluene in the filtrate was distilled off under reduced pressure, 2.75 g of a viscous colorless and transparent liquid was obtained as a residue. FD-MS measurement of this compound confirmed that the molecular weight was 372. Further, from the measurement result of ¹ H-NMR (CDCl ₃ ) shown in FIG. 4, the obtained compound was represented by the formula (7)

[0028]

[Formula 9] Represented by, bis (3-methyloxetane-3-ylmethyl)-
It was identified as 1,6-hexamethylene dicarbamate.

[0029]

According to the present invention, a novel polyfunctional oxetane compound and a method for producing the same can be provided. Photocurable or thermosetting resin derived from this, heat resistance,
Excellent mechanical properties and adhesion, and can be used for paints and adhesives.

[Brief description of the drawings]

FIG. 1 shows the bis (3-ethyloxetane-3) obtained in Example 1.
^1- H-NMR of (-ylmethyl) -2,4-tolylenedicarbamate (CD
Cl ₃₎ is a diagram showing a.

FIG. 2 shows the bis (3-methyloxetane-3) obtained in Example 2.
^1- H-NMR of (-ylmethyl) -2,4-tolylenedicarbamate (CD
Cl ₃₎ is a diagram showing a.

FIG. 3 shows the bis (3-ethyloxetane-3) obtained in Example 3.
- ylmethyl) -1,6-hexamethylene dicarbamate ¹ H-
Is a diagram showing an NMR (CDCl _3).

FIG. 4 shows the bis (3-methyloxetane-3) obtained in Example 4.
- ylmethyl) -1,6-hexamethylene dicarbamate ¹ H-
Is a diagram showing an NMR (CDCl _3).

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is 2 or 3, X is a divalent or trivalent aromatic residue or a divalent aliphatic residue. A) a polyfunctional oxetane compound represented by the formula: 2. The polyfunctional oxetane compound according to claim 1, wherein in the general formula (1), R is a methyl group or an ethyl group. 3. The process for producing a polyfunctional oxetane compound according to claim 1, wherein 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane is reacted with a polyvalent isocyanate.