JPH0417951B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing tris(2-hydroxyethyl)isocyanurate modified with ε-caprolactones. Tris (2-hydroxyethyl) isocyanurate has a rigid skeleton and further contains N in the skeleton, so it can be used as one of the glycol components of polyester, polyurethane, urethane acrylate, etc. In addition to imparting hardness to materials such as the like, improvement in adhesion can also be expected. Therefore, tris(2-hydroxyethyl)isocyanurate is an important compound widely used in the urethane elastomer field, coating field, etc. However, the primary hydroxyl group of tris(2-hydroxyethyl)isocyanurate has a rigid skeleton and has a drawback of poor reactivity with acids, isocyanates, etc. Therefore, the present inventors conducted intensive research to improve the drawbacks of tris(2-hydroxyethyl)isocyanurate and further expand the possibilities of using tris(2-hydroxyethyl)isocyanurate. By polymerizing ε-caprolactone to all or part of the primary hydroxyl groups of hydroxyethyl) isocyanurate, tris(2-hydroxyethyl)isocyanurate, which is rigid and has poor reactivity, can be given appropriate flexibility. At the same time, the solid tris (2-hydroxyethyl) isocyanurate becomes liquid, improving workability. Furthermore, the hydroxyl group, which is close to the rigid isocyanurate ring and has poor reactivity due to steric hindrance, etc. ,ε
- It becomes a highly reactive primary hydroxyl group at the end of the side chain of caprolactones, and since the primary hydroxyl group is located far away from the rigid isocyanurate ring, its reactivity with acids, isocyanates, etc. is improved. They discovered this and completed the present invention. That is, the present invention combines 95 to 5% by weight of tris(2-hydroxyethyl) isocyanurate and 5 to 95% by weight of ε-caprolactones with a titanium compound of the group consisting of tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, and octyl titanate. organotin compounds of the group consisting of tin acid, dibutyltin oxide and dibutyltin dilaurate;
and one or more compounds selected from the group of tin halide compounds consisting of stannous chloride, stannous bromide, and stannous iodide at 100 to 240°C under a nitrogen atmosphere. The viscosity at 30℃ is characterized by polymerization at a temperature of
Modified Tris (2
-Hydroxyethyl)isocyanurate. Conventionally, the reaction between tris(2-hydroxyethyl)isocyanurate and ε-caprolactones has been known, but by reacting with a small amount of a catalyst consisting of the titanium compound or tin compound used in the present invention, Modified tris(2-hydroxyethyl) with excellent fluidity, flexibility, reactivity, etc.
There was nothing known about the method for obtaining isocyanurate. Examples of the ε-caprolactones used in the present invention include ε-caprolactones, ω-hydroxycaproic acid, ω-hydroxycaproic acid esters, and particularly preferred is ε-caprolactone. ε-caprolactone is produced industrially by oxidizing cyclohexanone with peracetic acid by the Baeyer-Villiger reaction. Modified tris(2-hydroxyethyl) of the present invention
When producing isocyanurate, the reaction ratio of tris(2-hydroxyethyl)isocyanurate and ε-caprolactones is 95:5 to 5: by weight.
95, preferably 80:20 to 20:80. If the amount of tris(2-hydroxyethyl) isocyanurate is too much than the above range, the desired sufficient flexibility cannot be imparted to the final resin, and if it is too little, the resin will become too soft, which is undesirable. . In the present invention, when 1 mol of ε-caprolactones is reacted with 1 mol of tris(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)
- The (addition) reaction rate of ε-caprolactones to the hydroxyl group of hydroxyethyl isocyanurate and the (addition) reaction rate of ε-caprolactones to the hydroxyl group of the caprolactone terminal of the product are almost unchanged, and the reaction occurs at any position of the hydroxyl group, so the reaction product actually has the formula (In the formula, n ₁ , n ₂ , and n ₃ are each 0 or a positive number.) From the unreacted substances where n ₁ = n ₂ = n ₃ = 0, n ₁ , n ₂ , and n ₃ are arbitrary. It is a mixture that is statistically distributed down to the number of polycaprolactones. This mixture does not need to be further separated or purified, and can be used as it is in the synthesis of the final resin. The polymerization reaction of ε-caprolactone to the primary hydroxyl group of tris(2-hydroxyethyl) isocyanurate of the present invention is carried out at 100 to 240°C under a nitrogen atmosphere.
Preferably it is carried out at a temperature of 120 to 200°C. 100
The reaction rate is low when the temperature is lower than 240℃.
If the temperature is higher, ε-caprolactones will boil;
This is because they escape out of the reaction system. The amount of the catalyst used in the reaction of the present invention is 0.01 to 1000 ppm, preferably 0.2 to 500 ppm, based on the total amount charged. The reaction may be carried out without a solvent, or with toluene,
The reaction may be carried out in a solvent having no active hydrogen such as xylene, methyl ethyl ketone, methyl isobutyl ketone or the like. However, solvents having ester bonds are not preferred. This is because a transesterification reaction with the ester group of polycaprolactone may occur during the reaction, resulting in the production of polycaprolactone that is not bonded to tris(2-hydroxyethyl)isocyanurate. The tris(2-hydroxyethyl) isocyanurate modified with ε-caprolactones of the present invention has improved workability and excellent reactivity with crosslinking agents, etc. when synthesizing the target resin, and thereby A highly flexible final resin such as polyester, polyurethane, urethane acrylate, etc. can be provided. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. In addition, parts in the examples mean parts by weight. Example 1 7308 parts (28.0 mol) of tris(2-hydroxyethyl)isocyanurate and 3192 parts (28.0 mol) of ε-caprolactones were placed in a 4-neck flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, and a stirring device. , 0.105 parts of tetrabutyl titanate was added as a catalyst,
When the reaction was carried out at 170° C. for about 7 hours in a nitrogen atmosphere, the amount of unreacted ε-caprolactone was 0.6% or less. In addition, the amount of tetrabutyl titanate was reduced from 10ppm to 1ppm and 0.5ppm with respect to the total amount charged above.
When the amount of ε-caprolactones was changed to less than 0.6 ppm, it took 9 hours and 13 hours, respectively. The obtained lactone-modified tris(2-hydroxyethyl) isocyanurate had the properties shown below. Appearance (Gardner) 5 Acid value (mgKOH/g) 0.822 OH value (mgKOH/g) 440.4 Viscosity (cp/at 30°C) 65600 Examples 2 to 4 Tris (2-hydroxyethyl) isocyanurate (abbreviated as THEiC) and ε A polymerization reaction was carried out in the same manner as in Example 1, except that the charging ratio of -caprolactones (abbreviated as ε-CL) was changed. The results are shown in Table 1.

[Table] Application example (A) In a 55-necked flask equipped with an air introduction tube, thermometer, cooling tube, stirring device, and dropping funnel,
2220 parts (10.0 mol) of isophorone diisocyanate and 9.05 parts of dibutyltin laurate were added and kept at 60°C under an air atmosphere. Next, while maintaining the reaction temperature (below 60°C), 1160 parts (10.0 mol) of 2-hydroxyethyl acrylate was added dropwise from the dropping funnel over a period of about 2 hours.
The reaction was continued at 60°C for a period of time, and the reaction was stopped after confirming the absence of hydroxyl groups in the reaction product by IR analysis. 3380 parts of ethylenically unsaturated monoisocyanate were obtained as a product. (B) Next, in a similar apparatus, ε synthesized in Example 3
- 1206 parts (2.0 mol) of caprolactone-modified tris(2-hydroxyethyl)isocyanurate
was prepared and heated to 80℃. In this case, the reaction mixture had appropriate fluidity, and the solvent methyl ethyl ketone was not used. Furthermore, ethylenically unsaturated monoisocyanate 2712 synthesized in (A)
part (6.0 mol) in an air atmosphere at a reaction temperature of (80
The mixture was added dropwise from the dropping funnel over a period of about 4 hours while maintaining the temperature at 80°C or below, and the reaction was continued at 80°C for about 5 hours after the dropping was completed. The reaction was stopped after confirming that NCO% was 0.1% or less. 3918 parts of photocurable oligomer was obtained as a product. This photocurable oligomer 70
When part by weight is dissolved in 30 parts by weight of diluent tetrahydrofurfuryl acrylate, the dissolution viscosity is
It was 20000cp/at25℃. Control example Methyl ethyl ketone was prepared in the same manner as in applied example (B).
Tris(2-hydroxyethyl) dissolved in 500 parts
Ethylenically unsaturated monoisocyanate synthesized using 522 parts (2.0 mol) of isocyanurate in application example (A)
2,028 parts (6.0 mol) of the photocurable oligomer was reacted to obtain 2,550 parts of a photocurable oligomer. The same dissolution viscosity of this photocurable oligomer as above was 200,000 cp/at 25°C. Next, the photocurable oligomers obtained in the above application examples and control examples were combined with 1.9 parts of tetrahydrofurfuryl acrylate (THFA) as a diluent and 1.9 parts of Irgakiure 651 (manufactured by Ciba Geigy) as a photosensitizer, and the coating was cured by UV irradiation. I got it. The results are shown in Table-2.

【table】 Curing conditions High pressure mercury lamp 80W/cm Irradiation distance 6cm Irradiation time 10sec Film thickness approximately 100μ

Claims (1)

[Claims] 1 Tris(2-hydroxyethyl)isocyanurate 95-5% by weight and ε-caprolactones 5
~95% by weight of titanium compounds of the group consisting of tetrabutyl titanate, tetrapropyl titanate and tetraethyl titanate, organotin compounds of the group consisting of tin octylate, dibutyltin oxide and dibutyltin dilaurate, and stannous chloride.
Polymerization is carried out at a temperature of 100 to 240°C under a nitrogen atmosphere using as a catalyst one or more compounds selected from the group of tin halide compounds consisting of tin, stannous bromide, and stannous iodide. A method for producing modified tris(2-hydroxyethyl) isocyanurate exhibiting a fluid state with a viscosity of 500,000 cp or less at 30°C, characterized in that: