JPS5924986B2 - Liquefaction treatment method of anhydrous maleic acid of chain triene having 10 carbon atoms - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for liquefying an anhydrous maleate of a chain triene having 10 carbon atoms.

Compounds corresponding to the addition reaction products of chain trienes having 10 carbon atoms such as alloocimene and maleic anhydride, that is, maleic anhydrides of chain trienes having 10 carbon atoms, are used as epoxy resin curing agents. Can be used. However, many of these anhydrous maleates of chain trienes having 10 carbon atoms are solid at room temperature, and in order to use them for the above-mentioned purposes, it is desirable to liquefy them. in this way,
It is necessary to liquefy the maleic anhydride of a chain triene having 10 carbon atoms which is solid at room temperature. An object of the present invention is to provide a processing method for easily and industrially advantageously liquefying an anhydrous maleate of a chain triene having 10 carbon atoms, which is solid at room temperature. That is, the present invention provides an anhydrous maleic product of a linear triene having 10 carbon atoms, which is characterized in that anhydrous maleic acid of a linear triene having 10 carbon atoms, which is solid at room temperature, is heat-treated in the presence of an alkali metal bromide. This is a method for liquefying chemical substances.

As described above, an anhydrous maleate of a chain triene having 10 carbon atoms is solid at room temperature (hereinafter referred to as an "anhydride maleate of a chain triene").

) can be easily liquefied by simply heating it in the presence of an alkali metal bromide. It is assumed that this liquefaction is caused by the isomerization reaction of the linear triene maleic anhydride to produce several geometric and manufacturing isomers, and the coexistence of these several isomers lowers the freezing point. Many of the details are unclear. Examples of the linear maleic anhydride of triene that is solid at room temperature and used in the method of the present invention include compounds that are solid at room temperature that are obtained by a Diels-Alder reaction between the following compound and maleic anhydride.

(1) Allooocimene CH3CH3 CH3-C=CH-CH=CH-C=CH-CH3 In the present invention, a particularly desirable linear triene maleic anhydride is an addition reaction product of allooocimene and maleic anhydride, that is, maleated allooocimene anhydride. .

As a representative example of the linear maleic anhydride used in the present invention, maleic anhydrous alloocimene will be described in detail.

Alloocimene is easily obtained by thermal isomerization reaction of α-pinene and the like. Alloocimene obtained by the thermal isomerization reaction of α-pinene exists in two types of isomers: the trans-cis form and the trans-trans form.Generally available products usually contain 50-70% of the trans-cis form and the trans-trans form. Contains 30-50% trans isomer. If maleic anhydride is added to such alloocimene by a Diels-Alda reaction, maleic anhydride alloocimene can be easily obtained. The anhydrous maleated allocimene obtained by this method is usually a mixture of the following two types of isomers, has a melting point of 70°C or higher, for example 83 to 84°C, and is, of course, solid at room temperature. The alkali metal bromide used as an isomerization catalyst in the method of the present invention includes:
Examples include lithium bromide, sodium bromide, potassium bromide, rubidium bromide and cesium bromide.

In particular, sodium bromide and potassium bromide are easily available;
It is preferable because it is also inexpensive. The amount of alkali metal bromide used is 0.005% of the linear triene maleic anhydride.
weight? The above content is preferably 0.01 to 3.0% by weight. The alkali metal bromide may be added directly to the heated and melted linear triene anhydride maleic anhydride, or may be added by other methods such as dissolving the alkali metal bromide in a solvent such as water or acetone. You may. Furthermore, a packed tower may be filled with an alkali metal bromide supported on a carrier, and the vapor of the linear triene anhydride may be passed through the packed bed at a desired reaction temperature to cause the reaction. Regarding the heat treatment conditions in the present invention, if the heating temperature is too low, liquefaction will take a long time, and if the heating temperature is too high, decomposition reactions and reactions to produce resinized products will increase, reducing the yield of the desired liquefied product.

The reaction temperature is usually 100 to 250°C, preferably 12
The temperature is 0 to 220°C. In addition, the heat treatment time varies depending on the amount of catalyst and the reaction temperature, and cannot be generally specified, but it is usually 10 minutes to 10 hours, preferably 0.5
~3 hours. As mentioned above, the isomerization catalyst, alkali metal bromide, is supported on a carrier such as pumice, activated carbon, diatomaceous earth, silica gel, molecular sieve, etc., and linear triene anhydride is placed in a column packed with this supported catalyst. Continuous heat treatment can be carried out by passing maleide vapor at a predetermined reaction temperature;
Heat treatment is performed at a high temperature of 250° C. for a short time.

When the amount of the catalyst is small, the product obtained by processing according to the method of the present invention may be purified by distillation as it is, or may be treated with activated charcoal, added with a filter aid such as diatomaceous earth, etc. may be treated with an appropriate dehydrating agent to remove moisture, filtered, and distilled.

In the liquefaction treatment of the present invention, it is not necessarily clear why linear triene maleic anhydride, which is solid at room temperature, becomes liquid, but several types of geometric and structural isomers are produced. It is presumed that the coexistence of isomers lowers the freezing point (melting point). For example, if we look at maleated anhydride alloocimene, as mentioned above (
1) From the type isomer and the () type isomer, the following (' type isomer and () type isomer, etc. are generated in part, and the double bond isomerization reaction also occurs, and the treated product contains It is thought that the coexistence of an extremely large number of isomers will lower the freezing point.Since the liquid product obtained by the method of the present invention is liquid at room temperature, it can be used as an epoxy resin curing agent or an acid component of an alkyd resin. can be used to advantage.

In addition, this product can be modified into amides, imides, esters, chlorine adducts, alkylene oxide adducts, etc. and used as rust preventive agents.It can also be used as a base oil for grease as magnesium and aluminum salts, and as a diester for rubber. It can also be used as a plasticizer for resins (especially vinyl chloride). In particular, this liquid product may contain various epoxy resins, such as those described in Chapters 3 and 4 of "Epoxy Resins" edited by Hiroshi Kakiuchi and published by Shokodo on September 30, 1970. It can exhibit excellent curing performance when used as a curing agent for various epoxy resins.

When this liquid product is used as an epoxy resin curing agent, the amount used is usually 70 to 150 parts by weight, preferably 100 to 130 parts by weight, per 100 parts by weight of the epoxy resin. Furthermore, when this liquid product is used as an epoxy resin curing agent, other curing agents such as acid anhydride curing agents may be used in combination as necessary.

Examples include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, phthalic anhydride, pyromellitic anhydride, dodecenylsacnic anhydride, nadic anhydride, and chlorendic anhydride. It will be done. Furthermore, when this liquid product is used as an epoxy resin curing agent, a curing accelerator can be used in combination, if necessary. for example,
Trialkylamine, N-dimethylbenzylamine, triethanolamine, piperidine, dimethylaminomethylphenol, tris(dimethylaminomethyl)phenol, hexoate of tris(dimethylaminomethyl)phenol, imidazoles (e.g. 2-ethyl-4
-methylimidazole), dicyandiamide, triphenylphosphine, etc. can be used in combination as a curing accelerator. The amount of the curing accelerator used is preferably 0.1 to 5 parts by weight per 100 parts by weight of the epoxy resin. In addition, British Patent No. 906,017 describes that anhydrous maleated allocimene is heat-treated at a temperature of 190 to 240°C for a long time to liquefy it by thermal isomerization.

However, such an isomerization method using prolonged heating causes thermal decomposition even when carried out in a nitrogen stream, and therefore has the disadvantage that the yield of liquid anhydrous maleated allocimene obtained after distillation purification is low. In addition, even if the distilled product is temporarily liquid, crystals often precipitate after 2 to 3 days, and even if it is liquid at room temperature, it crystallizes at a low temperature of about 0 to 10 degrees Celsius. do. Example 6 of the same specification states that the product obtained by heating anhydrous maleated allocimene at 210 to 220°C for 14 hours crystallizes if left to stand, but if this is further heated at 210 to 220°C for 5 hours, It is stated that a liquid product was obtained that did not crystallize even when left at room temperature. A method in which liquefaction can only be achieved by such a long heat treatment is extremely disadvantageous industrially. Further, U.S. Patent No. 3,078,235 proposes an epoxy resin curing agent that is liquefied by blending anhydrous maleated allocimene, anhydrous maleic myrcene, and hexahydrophthalic anhydride. Blending and liquefying materials that are solid at room temperature requires a melt-mixing process, which has the drawback of increasing costs.

Next, a description will be given of production examples, examples, and experimental examples of linear triene maleic anhydride.

Chain triene maleic anhydride production example 1 686 g (7.0 mol) of maleic anhydride was placed in a 31-capacity four-bottle flask equipped with a stirrer, thermometer, condenser, dropping load, and nitrogen inlet tube, and then 10 mol of benzene was added.
Added 0ec.

While stirring at room temperature, 10009 (7.35 mol) of alloocymene (manufactured by Yasushi Oil Industries Co., Ltd.) was gradually added dropwise. Since the temperature rose due to the heat of reaction, the reaction temperature was maintained at 70 to 80°C by cooling with a water bath. After about an hour, I finished instilling the alloocimene. Further, in order to complete the reaction, the mixture was stirred at 70 to 80°C for about 1 hour. The reaction solution was red when alloocimene was added dropwise, and turned light brown as the reaction was completed. After the reaction is completed, excess alloocimene and benzene as a solvent are distilled off by suction using an aspirator at a temperature below 100°C (degree of vacuum: 20 mmHg).
.

The anhydrous maleated alloocimene produced has a melting point of 75-80°C.
It was hot.

Chained triene anhydride maleic anhydride production example 2 The reaction temperature was 130 to 140°C, the reaction time was 1 hour,
Anhydrous maleated allocimene was produced in the same manner as in Production Example 1 above using xylene as the solvent.

The melting point of the product was 70-80°C.

Chain triene maleic anhydride production example 3 2,6-dimethyl-1,3,6- instead of alloocimene
Methylbutenyltetrahydrophthalic anhydride (hereinafter referred to as "MBPA") was obtained in the same manner as in Production Example 1 above, except that octatriene was used.

The melting point of the MBPM produced was about 60°C. Example 1 The anhydrous maleated alloocimene 609 obtained in Production Example 1 above was placed in a four-bottle flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube, and was heated to about 100° C. to dissolve it.

Add 0.069 lithium bromide monohydrate to this, and add 200
Stirred at ℃ for 1 hour. . Sodium bromide was not completely dissolved and was finely dispersed. After the reaction, the degree of vacuum is 0.9m
Simple distillation was carried out at mHg.

150-165 pressure C/0.9m7! A light yellow liquid anhydrous maleated allocimene 559 (yield 92%) was obtained as a fraction of LHg. This liquid anhydrous maleated allocimene was stored in a refrigerator at 5°C, in a freezer at -20°C, and at room temperature (
Although the samples were allowed to stand at a temperature of 20 to 25° C. for more than two months, no crystallization occurred.

Its viscosity (E-type viscometer) was 176 cps at 25°C. Examples 2 to 10 The above Production Example 1 was carried out according to the method described in Example 1, except that the type of catalyst, amount of catalyst, reaction time, reaction temperature, and linear triene as raw material were changed as shown in Table 1. The solid acid anhydride produced in steps 3 to 3 was heat-treated.

The viscosity and yield of the obtained liquid acid anhydride were as shown in Table 1. In addition, all of the liquid acid anhydrides obtained in these examples had excellent liquid stability, and although they were kept at temperatures of 5°C and 120°C to 25°C for more than 2 months, they all precipitated crystals. Nakatsuta.

Experimental Example 1 100 parts (parts by weight, the same applies hereinafter) of Epicote 828 [trade name, Siel Kagaku Co., Ltd., epoxy equivalent weight 189, glycidyl ether of 2,2-bis-(4-hydroxyphenyl)propane] obtained in Example 1. 120 parts of liquid anhydrous maleated alloocymene and 1 part of benzyldimethylamine as a hardening accelerator were uniformly stirred and mixed at room temperature, and then heated under reduced pressure (2 m
77! Hg or less) to prepare an epoxy resin composition.

The viscosity of this composition was about 23 poise at 25°C, and casting etc. were extremely easy. This resin composition was heated at 80°C for 3
When the resin was pre-cured for an hour and then post-cured at 120° C. for 6 hours, a strong cured resin was obtained as shown in Table 2.

Experimental Example 2 A test was conducted in the same manner as in Experimental Example 1 except that the liquefied MBPA obtained in Example 8 was used.

The results are shown in Table-2. For comparison, Table 2 also includes the formulation of epoxy resin compositions containing known curing agents and the physical properties of the cured resins.

As is clear from the results in Table 2, the epoxy resin composition of the experimental example exhibits a high heat distortion temperature even though the side chain of the curing agent is a short butenyl group or methylbutenyl group.

That is, compared to the heat distortion temperature of Comparative Example Composition 2, which used a curing agent having a long alkyl group in its side chain, Experimental Example 1
The heat distortion temperature of the composition of Experimental Example 2 is about 50°C higher. Further, the composition of Experimental Example 1 has a higher crack resistance value than Composition 1 of Comparative Example, which uses methyltetrahydrophthalic anhydride as a curing agent. This is presumably because the liquid acid anhydride of the present invention has increased flexibility because it has a butenyl group and a methylbutenyl group in the side chain. Furthermore, Experimental Example 1
The compositions of Experimental Example 2 and Comparative Example Composition 1 using methyltetrahydrophthalic anhydride as a curing agent showed no change in the mechanical properties and electrical properties of the cured product. On the contrary, it has an excellent dielectric constant.

Claims (1)

[Claims] 1. Anhydrous anhydride of a linear triene having 10 carbon atoms, which is characterized by heat-treating an anhydrous maleide of a linear triene having 10 carbon atoms, which is solid at room temperature, in the presence of an alkali metal bromide. Liquid treatment method for maleides. 2 Anhydrous maleated product of chain triene having 10 carbon atoms which is solid at room temperature is anhydrous maleated alloocimene, or 2,6
- The method according to claim 1, wherein the anhydrous maleate of dimethyl-1,3,6-octatriene is used.