JPH0154352B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel and useful chemical substances 2
-Allyloxymethyl-1,4,6-trioxa-spiro-[4,4]-nonane.

This compound contains an allyl double bond and a trioxa-spiro-[4,4]-nonane ring in the molecule. Allyl double bonds have radical polymerizability, and trioxa-spiro-[4,4]-nonane rings are cationic polymerizable, so after radical copolymerization with other monomers or homoradical polymerization, ,
By polymerizing the trioxa-spiro-[4,4]-nonane ring in the presence of a cationic polymerization catalyst,
It is possible to obtain a cured product. Or, on the contrary,
After cationic polymerization, it is possible to cure by radical polymerization, or it is also possible to simultaneously polymerize both functional groups in the coexistence of a radical polymerization catalyst and a cationic polymerization catalyst. Furthermore, this compound is air-drying due to its allyl ether group and also contains trioxa-spiro-[4,4]
- It has the feature that no volume contraction occurs during cationic polymerization of nonane rings.

Therefore, this compound can be used in the production of paints, adhesives, inks, molded products, etc. by making it into a vinyl copolymer. In addition, when this compound itself is used as a diluent for radical catalyst-curing or photo-curing paints, inks, unsaturated polyester resins, etc., it is not inhibited by air and has low shrinkage and excellent adhesion. A composition is obtained.
Furthermore, it can be used as a diluent for epoxy resins, a reactive plasticizer, a raw material for polyacetal resins, etc.

This compound can be obtained, for example, by an addition reaction between γ-butyrolactone and allyl glycidyl ether. The addition reaction is carried out in an inert solvent, for example a chlorinated hydrocarbon such as carbon tetrachloride, dichloromethane, etc., or a nitro compound such as nitrobenzene. There is no particular restriction on the amount of these solvents used, but it is preferable to use them so that the amount of γ-butyrolactone is 10 to 35% by weight. Allyl glycidyl ether is 0.8 to 1.5 times mole relative to γ-butyrolactone, especially 0.8 to 1.2
It is preferable to use twice the molar amount. There is no particular restriction on the reaction temperature, but it is usually -20 to 50°C, preferably
It is appropriate to carry out the reaction at 10-35°C.

As a catalyst, boron trifluoride etherate,
A Lewis acid such as tin tetrachloride, titanium tetrachloride, or aluminum chloride is used, and the appropriate amount of the catalyst is 0.04 to 0.15 mol per mol of γ-butyrolactone. Note that boron trifluoride etherate is obtained by reacting boron trifluoride with known ethers such as dimethyl ether, diethyl ether, and the like. The reaction is generally carried out by dropping allyl glycidyl ether into a mixture of γ-butyrolactone, catalyst and solvent, but is not limited to this method.

The reaction can be stopped using basic substances, such as alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.; amines such as triethylamine, diethanolamine, ethylenediamine, pyridine, etc.; Or by adding a solid base such as Al ₂ O ₃ , 2.5MgO.Al ₂ O ₃ and the like. The amount of the alkali metal hydroxide, alkaline earth metal hydroxide or amine used is 0.2 to 100 times, preferably 1 to 2 times, the amount of the catalyst used in the synthesis. The appropriate amount of the solid base to be used is 5 to 25 times the weight of the catalyst, preferably 10 to 15 times the weight of the catalyst.

After the reaction has stopped, it can be washed with water and fractionated, or
Alternatively, by directly performing fractional distillation, the desired 2-allyloxymethyl-1,4,6-trioxa-spiro-[4,4]-nonane can be obtained.

The present invention will be explained below with reference to Examples.
The present invention is not limited to such examples.

Example 1 4.3 g (0.5 mol) of γ-butyrolactone, 150 c.c. of carbon tetrachloride and 3 c.c. of BF ₃ diethyl etherate.
While keeping the mixture of (0.024 mol) at 25-30℃, add 68.4 g (0.6 mol) of allyl glycidyl ether to about 1
Drip over a period of time, and then add another 25 to 35 minutes after the drip is finished.
The reaction was carried out at ℃ for 2 hours. After adding 150 c.c. of 10% NaOH aqueous solution and shaking well, washing with water, adding a small amount of hydroquinone to the organic layer and distilling under reduced pressure, the
The product (colorless transparent liquid) was obtained with a yield of %.

The identification data for this substance was as follows.

(1) Boiling point: 71-74℃/0.40-0.45mmHg (2) Infrared absorption spectrum: See Figure 1 (3) Elemental analysis (as C ₁₀ H ₁₆ O ₄ ): C H Theoretical value 59.99 7.99 Actual value 60.11 7.95 (4) Mass spectrometry: See Figure 2 From the above analysis results, it was confirmed that this product was 2-allyloxymethyl-1,4,6-trioxa-spiro-[4,4]-nonane. .

Example 2 43 g (0.5 mol) of γ-butyrolactone, 150 c.c. of carbon tetrachloride and 3 c.c. of BF ₃ diethyl etherate.
While keeping the mixture of (0.024 mol) at 25-30℃, add 68.4 g (0.6 mol) of allyl glycidyl ether to about 1
Drop it over a period of time, and after the drop is finished, 2.5MgO・
After adding 30 g of Al ₂ O ₃ and treating at 40°C for 3 hours,
Fractionate. 42% based on raw material γ-butyrolactone
The product (colorless transparent liquid) was obtained with a yield of .

The analysis results confirmed that this product was the same as that of Example 1.

[Brief explanation of drawings]

Figure 1 shows 2-allyloxymethyl-1,4,
Figure 2 is an infrared absorption spectrum (IR) diagram (liquid film, NaCl cell) of 6-trioxa-spiro-[4,4]-nonane, and Figure 2 shows 2-allyloxymethyl-
FIG. 2 is a mass spectrum (MS) diagram of 1,4,6-trioxa-spiro-[4,4]-nonane.

Claims (1)

[Claims] 1 2-allyloxymethyl-1,4,6-trioxa-spiro-[4,4]-nonane.