JPH01306408A - Novel dibasic acid diallyl ester and prepolymer thereof - Google Patents

Abstract

NEW MATERIAL:A dibasic acid diallyl ester expressed by formula I or II (R1 is lower alkyl; n is 1-3). EXAMPLE:Diallyl methyltetrahydrophthalate. USE:Readily curable with a radical polymerization initiator, capable of holding performances (e.g., dimensional stability, mechanical and electrical characteristics and heat resistance) comparable to those of conventional diallyl phthalate resins and providing three-dimensional crosslinked substances having flexibility and suitable as molding materials, powder coatings, various hinders and optical materials. PREPARATION:The corresponding dibasic acid anhydride is preferably reacted with allyl alcohol to afford the compound expressed by formula I or II.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention relates to a novel dibasic acid diallyl ester and its prepolymer, and furthermore, a novel dibasic acid diallyl ester thermosetting resin composition having flexibility. Regarding. The prepolymer referred to herein refers to an initial polymer having an average degree of polymerization of 10 to 30 and capable of further polymerization (curing).

"Problems to be solved by conventional techniques and inventions" Conventionally,
Diaryl phthalate resin, which is a thermosetting resin, has excellent mechanical properties such as dimensional stability and rigidity under heat, heat resistance, and electrical properties, and is widely used in fields that require high reliability. This resin tends to be brittle and has insufficient toughness, and in recent years, as molded products have become smaller, the problem of cracking and chipping in thin parts and small protrusions of molded products has increased. .

In order to overcome these technical problems, many proposals have been made to improve the brittleness of diallyl phthalate resins by improving compounding techniques and polymer blends. For example, methods of reinforcing with fillers such as glass fibers, and methods of modifying with flexible polyester or rubber-like polymers are known. However, although all of these methods were intended to impart toughness to the diallyl phthalate resin without impairing its excellent properties, it is difficult to say that these methods have achieved the objective.

On the other hand, there has been remarkable progress in thermoplastic resins such as polybutylene terephthalate and polyphenylene sulfide.
Resins and compounding techniques with excellent heat resistance and electrical properties have been developed, and due to their high productivity, they have come to be adopted in a wide range of fields, including fields where thermosetting resins were traditionally used. It's here.

However, since it is a thermoplastic, there are problems with deformation due to creep and heat resistance, and its reliability is not as high as that of thermosetting resins, especially when used for long periods of time under high temperature and high humidity conditions.

"Means and actions for solving the problem" The present inventors,
In order to achieve the above object, the present invention was completed through intensive research into improving diallyl phthalate resin from a new angle. This is a novel thermosetting resin composition characterized by containing an acid diallyl ester, its prepolymer, and the prepolymer and a curing agent.

R1 represents a lower alkyl group, and n is an integer of 1-3.

The above-mentioned dibasic acid diallyl ester and its prepolymer change the rigid benzene skeleton of the conventional diallyl phthalate resin to a flexible skeleton, so that the prepolymer has a molecular weight equivalent to that of the conventional diallyl phthalate prepolymer. An extremely useful new thermosetting resin has been obtained which has a low viscosity and has properties comparable to diallylphthalate prepolymers, but in addition exhibits improved flexibility after curing. This is what we discovered.

In producing the dibasic acid diallyl ester of the present invention, examples of the dibasic acid anhydride as a raw material include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, trialkyltetrahydroheptalic anhydride. etc., and known methods can be used for the production of the nanatsuma. However, in consideration of use in the field of electrical and electronic components, it is preferable to use allyl alcohol as the allyl source in order to reduce the chlorine content derived from allyl chloride.

The dibasic acid diallyl ester prepolymer of the present invention can be produced, for example, by reaction in the presence of a known organic peroxide or azo compound catalyst. Examples of usable organic peroxide catalysts and azo compound catalysts include the following compounds.

Dialkyl peroxides and diaryl peroxides such as di-tert-butyl peroxide, di-sec-butyl peroxide, tert-butyl-5ec-butyl peroxide, and dicumyl peroxide;
Ketone peroxides such as methyl ethyl keto/beroxide, cyclohexanone peroxide; 1,1-bis(
peroxyketals such as tert-butylperoxy)-3,3,5-)limethylcyclohexane; hydroperoxides such as cumene hydroperoxide; peroxides such as benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide; sialoyl and diacyl peroxide;
tert-butyl peroxyacetate, tert-butyl peroxy bivalet);
Examples include peroxy esters such as tert-butylperoxyoctoate and tert-butylperoxybenzoate, and azo compounds such as azobisin butynitrile other than the above-mentioned organic peroxides can also be used.

After polymerization, the prepolymer is separated using, for example, aliphatic hydrocarbons or alcohols, and dried to produce the dibasic acid diallyl ester of the present invention, which is thermosetting and has improved flexibility. A prepolymer can be obtained.

Examples of aliphatic hydrocarbons to be used include hexane and heptane, and examples of alcohols include methanol, ethanol, isopropyl alcohol,
Examples include tart-7'' alcohol.

The novel dibasic acid diallyl ester of the present invention and its prepolymer can be easily cured with a radical polymerization initiator such as an organic peroxide, and the resulting novel dibasic acid diallyl ester of the present invention The cured product, whose main component is the prepolymer, maintains performance comparable to conventional diallyl phthalate resin and becomes a flexible two-dimensional crosslinked product, so it can be used as a molding material, powder coating, and various binders. , suitable for optical materials.

Taking advantage of its properties, the dibasic acid diallyl ester prepolymer of the present invention can be applied to various molding and casting methods, and can also be used as a molding material with a low resin content, which was difficult to achieve with conventional diallyl phthalate resins. can be prepared, exhibiting excellent moldability and good dimensional stability. The molded product has excellent impact resistance, water/moisture resistance, chemical resistance, and adhesion, and has little deterioration over time. Therefore, it has excellent mechanical strength and electrical properties, and is extremely reliable.

Hereinafter, the present invention will be explained in detail based on examples.

"Examples, Comparative Examples" Example 1 Methyltetrahydrophthalic anhydride (hereinafter referred to as MT) IPA) 332y in a 1/separable flask with an oil/water separation neck,
290.5 y of allyl alcohol, 234 y of benzene, and 9.0 y of 65% sulfuric acid were charged, and the temperature was raised to 90"C without stirring. After the start of reflux, reaction water produced by the esterification reaction was removed from the system for 8 hours. The allyl esterification reaction was then completed.Excess allyl alcohol and residual benzene were removed under reduced pressure (120°C, 5flHg).
, to obtain 504.8y of a crude monomer (methyltetrahydrophthalic acid diallyl ester) as a dark brown liquid.

When the obtained crude monomer was purified by distillation, a pale yellow and transparent Nanatsummer-445y was obtained, and the acid value of the monomer was 2.
．． It was 0 v9KOH/y.

Add the same amount of toluene as the monomer and heat to 70°C.
14.4 y of a 0.0% NaOH aqueous solution was added to neutralize and separate the layers. After washing with water, remove toluene under reduced pressure (120'C15Hg
] The purified monomer 420y was obtained.

Table 1 shows the quality of the obtained monomer.

Example 2 MTI in 11 separable flasks with reflux condenser
(PA 199.29, sodium carbonate 144.0
y1 Sodium iodide 4.8y,) ethylamine 5.
2y, 1201 nl of xylene was charged all at once and heated. When the internal temperature reached 140° C., 2.4 g of water and 218.4 g of allyl chloride were added dropwise. However, the dropwise addition of water was at the beginning of the reaction and completed in about 15 minutes, while the dropwise addition of allyl chloride took 6.5 hours.

After cooling to 40°C, 450y of water was added and stirred to separate the layers. The organic layer was filtered, and excess aryl al;
I got 2y.

When the obtained crude monomer was purified by distillation, a pale yellow purified monomer 219y was obtained.

Table 1 shows the quality of the obtained monomer.

Example 3 Trialkyltetrahydrophthalic anhydride (Mw 234) 351.11 separable flask with oil/water separation neck.
0y, allyl alcohol 217.9y, ) luene 207
．． Oy and 65 sulfuric acid 6,2 were added, and the temperature was raised to 100° C. with stirring. After the reflux started, the reaction was continued for 26 hours while removing the reaction water generated by the esterification reaction from the system to complete the allyl esterification reaction. Subsequently, excess allyl alcohol and toluene as a solvent were removed under reduced pressure (120°C,
5 tllHg), and the crude monomer (triple-kyltetrahydrophthalic acid diallyl ester) was recovered as a dark brown liquid.
I got 592.

When the obtained crude monomer was purified by distillation, a pale yellow transparent monomer 378y was obtained, and the acid value of this monomer was 1.
It was 5.2111P KOH/7.

Add the same amount of toluene as the monomer and heat to 70°C.
A 2nd y of 0% NaOH aqueous solution was added to neutralize and separate the layers. After washing with water, toluene was recovered under reduced pressure (120° C., 5 flHg) to obtain purified monomer 346y.

Table 1 shows the quality of the obtained monomer.

Below is the blank space Example 4 1 with catalyst supply pipe! Separable 7: Methyltetrahydrotetralyl phthalate obtained in Example 1) 5
50y was charged, and the temperature was raised to 120°C with stirring. 120℃
At the point when this is reached, a mixture of tert-7'' methylberoxypenzoate tomethylteto2hydrodiallyl phthalate at a molar ratio of 0.014=1 is added at a rate of 0.6 P/min. The reaction temperature was maintained at 150″CK, and the refractive index of the polymerization liquid was 1.4995.
(30° C.) When the temperature reached K, the supply of the catalyst was stopped and the reactor was cooled.

Three times the amount of methanol was added to the obtained polymerization liquid and stirred to precipitate a prepolymer. The precipitated prepolymer was thoroughly washed with the same amount of methanol, dried, and then ground to obtain a white powdery prepolymer.

Table 2 shows the yield and physical properties of the prepolymer.

Comparative Example 1 600y of (orundialyl phthalate) was charged into a 11 separable flask, and the mixture was stirred and heated. When the temperature reached 150°C, air was supplied at a rate of 30 c c/ml n to 170° C.
It was kept at ℃. When the refractive index of the polymerization reaction solution reached 1.5264, the supply of air was stopped and the solution was cooled.

Three times the amount of methanol was added to the obtained polymerization liquid and stirred to precipitate a prepolymer. The precipitated prepolymer was thoroughly washed with the same amount of methanol, dried, and then ground to obtain a white powdery prepolymer.

Table 2 shows the yield and physical properties of the prepolymer.

Margin Table 2 Below: In Clothing 2 above, *1 is the value measured with a Cannon Fenske viscometer using a 50% methyl ethyl ketone solution.

*2: rMP-214 melting point measuring device manufactured by Yamato Scientific Co., Ltd. was used.

*3 is the polystyrene equivalent value determined by gel permeability chromatography, rA-802 manufactured by Showa Denko Co., Ltd.
803,805'' column set was used.

*4 is Shimadzu flow tester rCFT-500J
was used.

Example 5.6 and Comparative Example 2 a) Preparation of Fully Conbound The prepolymers obtained in Example 4 and Comparative Example 1 were blended as shown below to produce a fully combined.

*1 Manufactured by Asahi Fiberglass Co., Ltd. b) Take 20 to 407 of the full compound obtained by compression molding the full compound and use a mold to manually press it into a nearly disc-shaped tablet with a diameter of 50 fl and a thickness of 10 cod. After preheating to approximately 80°C using a high-frequency preheater, it was immediately placed in the center of the cavity of a compression molding mold that had been adjusted to a predetermined temperature, and molded using an automatic press at a pressure of 100 Ky/i for a predetermined time. , diametric iQQ
A disc-shaped molded product with a thickness of about 2 to 44 mm was obtained.

The compression molding temperature, time, and physical properties of the molded product are summarized in Table 4. The methods for measuring the physical properties of the molded products are as described after Table 4.

10 spaces below. Test method for physical properties of molded products (1) Rockwell hardness Measured at room temperature using a Rockwell hardness tester (M scale), and is expressed as the arithmetic mean of the three measured values.

(2) Thickness of test piece Measure the thickness at the center of the molded product sample using a micrometer.

(3) Dimensional shrinkage rate The diameter of the molded product sample was actually measured using a micrometer,
The difference from the mold cavity diameter (100 fl) is determined, divided by the mold cavity diameter, and multiplied by 100, and the result is shown as the value.

(4) Bending strength test pieces: Nine test pieces with a width of about 10 fl were cut out from three molded products using a diamond cutter.

Testing machine: AUTOGRAPH DC3-5000 (manufactured by Shimadzu Corporation) Measurement conditions: Load cell 50 kg Supporting 60 fl Crosshead speed 20/min Calculations are shown as the arithmetic mean value of 6 points according to the formula described in JIS K 6918.

(5) DSC reaction rate The calorific value of the test sample obtained by finely crushing the molded product sample and the full compound before molding was measured using a differential scanning calorimeter (DuPont Co., Ltd., 910 DSC System). In the formula, A is the heat generation amount of the full compound i (J/y) B (d the heat generation amount of the finely pulverized molded product (J
/y) (6) Boiling water absorption test Determine according to JIS K 6918, except that the specimen dimensions are a disk sample with a diameter of 100101 and a thickness of 2H.

(7)! Negative characteristics volume resistivity, dielectric constant, dielectric loss tangent, and arc resistance are JIS
K 6918, dielectric breakdown strength (step method) is Tl5I (
6911.

"Effects of the Invention" According to the present invention, by changing the benzene skeleton of the conventional diallyl phthalate resin to another skeleton, it has excellent fluidity and flexibility, and maintains the characteristics of the conventional diallyl phthalate resin. A novel dibasic acid diallyl ester and its prepolymer were obtained, and the cured product thereof has improved the drawbacks of the conventional diallyl phthalate resin, and has enormous industrial utility value.

Claims (3)

[Claims] (1) Dibasic acid diallyl ester represented by the following general formula [I] or [II]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] R^1 represents a lower alkyl group, and n represents an integer from 1 to 3. (2) A dibasic acid diallyl ester prepolymer obtained by polymerizing the dibasic acid diallyl ester described in item 1. (3) A novel thermosetting resin composition containing the dibasic acid diallyl ester prepolymer described in item 2 and a curing agent.