JPS6058758B2 - Liquefaction treatment method for chain triene maleate having 10 carbon atoms - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for liquefying a linear triene maleate having one carbon atom.

A compound corresponding to the addition reaction product of a linear triene having a number of carbon atoms such as alloocimene and maleic anhydride,
That is, the chain triene maleate having 101 carbon atoms can be used as an epoxy resin curing agent and the like.

However, many of these chain triene maleates having a carbon number of 1 are solid at room temperature, and in order to use them for the above-mentioned purposes, it is desirable to liquefy them. As described above, it is necessary to liquefy the chain triene maleate having m 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 a linear triene maleide having a carbon number of 1, which is solid at room temperature.

That is, the present invention provides a method for liquefying a chain triene maleate having m carbon atoms, which is characterized by heat-treating the chain triene maleide having m carbon atoms, which is solid at room temperature, in the presence of an alkali metal iodide. This is a processing method. In this way, a chain triene maleide having a carbon number of 1 is solid at room temperature (hereinafter referred to as a "chain triene maleide").

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

(i) Alloocymene CH3CH3 (11 CH3--1-C CH-CFI---CH-C2-CH--CH3i (ii) Myrcene CH3CH2 CH3-℃=CH--CH2--CH2--C- -1-CH■-CH2 (Y) 2,7-dimethynole 1,3,7
-octatriene (Iv) 2,6-dimethyl-1,3,
6-Octatriene A particularly desirable linear triene maleate in the present invention is the addition reaction product of allooocimene and maleic anhydride, ie, maleated allooocimene.

Maleated alloocimene will be described in detail as a representative example of the linear triene maleate used in the present invention.

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: trans-cis and trans-trans, and commercially available products usually contain 50-70% trans-cis and trans-trans isomers. −
Contains 30-50% trans isomer. If maleic anhydride is added to such alloocimene by the Diels-Aldahl reaction, maleated alloocimene can be easily obtained.

The maleated alloocimene 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 iodide used as the isomerization catalyst in the method of the present invention includes lithium iodide, sodium iodide, potassium iodide, rubidium iodide and cesium iodide.

In particular, sodium iodide and potassium iodide are preferred because they are easily available and inexpensive. The amount of alkali metal iodide used is 0.00 per linear triene maleate.
It is 5% by weight or more, preferably 0.01 to 3.0% by weight. The alkali metal iodide may be added directly to the heated and melted chain triene maleide, or may be added by other methods such as dissolving the alkali metal iodide in a solvent such as water or acetone. It's okay. Furthermore, a packed column may be filled with an alkali metal fluoride iodide supported on a carrier, and the vapor of the linear triene maleate may be passed through the packed bed at a desired reaction temperature to cause the reaction. The heat treatment conditions in the present invention are that if the heating temperature is too low, it will take a long time to liquefy, and if the heating temperature is too high, decomposition reactions and resinous product formation reactions will increase, reducing the yield of the desired liquefied product. .

The reaction temperature is usually 100 to 250°C, preferably 14°C.
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 1 hour to 10 hours, preferably 0.5 hours.
~3 hours. As mentioned above, the isomerization catalyst, alkali metal iodide, is supported on a carrier such as pumice, activated carbon, diatomaceous earth, silica gel, molecular sheep, etc., and a chain-like structure is placed in a column packed with this supported catalyst. Heat treatment can be carried out continuously by passing the vapor of triene maleide at a predetermined reaction temperature.
Heat treatment is performed at a high temperature of 250° C. for a short time.

If the amount of catalyst is small, the product obtained by treatment according to the method of the present invention may be purified by distillation as it is, but since it may be colored by free iodine, Preferably, it is washed with a 10% aqueous solution of sodium sulfate (Hypo) and then distilled.

Alternatively, the product may be subjected to activated carbon treatment for decolorization, addition of a t-superior agent such as diatomaceous earth, and further treatment with a suitable dehydrating agent to remove water, followed by filtration and distillation. In the liquefaction treatment of the present invention, it is not necessarily clear why the linear triene maleide, which is solid at room temperature, becomes liquid, but several types of geometric and structural isomers are produced, and their It is presumed that the coexistence of isomers lowers the freezing point (melting point). For example, regarding maleated alloocimene, the (1) type isomer and (■) type isomer described above partially produce the following (■) type isomer and (■) type isomer, and furthermore, Double bond isomerization reaction also occurs,
It is thought that an extremely large number of isomers coexist in the treated product, lowering 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.

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 can be used for various epoxy resins, such as those described in Chapters 3 and 4 of 1 Epoxy Resins, edited by Hiroshi Kakiuchi, September 30, 1927, published by Shokodo. 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 15 parts by weight, preferably 100 to 130 parts by weight per 10 parts by weight of 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, methylnadic anhydride, phthalic anhydride, pyromellitic anhydride, dodecynylsuccinic anhydride, nadicic 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, trialkylamines, N-dimethylbenzylamine, triethanolamine, piperidine, dimethylaminomethylphenol, tris(dimethylaminomethyl)phenol, hexoates 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 10 parts by weight of the epoxy resin. In addition, British Patent No. 906017 describes that maleated alloocymene 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 long-term heating causes thermal decomposition even when carried out in a nitrogen stream, so it has the disadvantage that the yield of liquid maleated allocimene obtained after distillation purification is low. In addition, even if the distilled product is temporarily in a liquid state, crystals often precipitate after 2 to 3 days, and even if it is in a liquid state at room temperature, it crystallizes at a low temperature of about 0 to 10'C. become Example 6 of the same specification states that the product obtained by heating maleated allocimene at 210 to 220'C for 2 hours crystallizes if left to stand;
It is stated that heating at ~220° C. for 5 hours yielded a liquid material that did not crystallize even if left at room temperature. A method in which liquefaction can only be achieved by such a long heat treatment is extremely disadvantageous industrially. Further, US Pat. No. 3,078,235 proposes an epoxy resin curing agent that is liquefied by blending maleated allocimene, maleated myrcene, and hexahydrophthalic anhydride. Blending and liquefying materials requires a melt-mixing process, which has the drawback of increasing costs.

Next, production examples, examples, and experimental examples of maleated alloocimene will be given and explained.

Maleated alloocimene production example 1 Maleic anhydride 686y (7.0 mol) was placed in a four-bottle flask with a capacity of 3e equipped with a stirrer, a thermometer, a condenser, a dropping load, and a nitrogen inlet pipe, and then benzene 10
Added 0cc.

While stirring at room temperature, 1000 q (0.735 mol) of alloocimene (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. Approximately 1
After some time I finished instilling 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 was completed, excess alloocimene and the solvent benzene were distilled off by suction with an aspirator at a temperature below 100°C (degree of vacuum 20W).
r! ! THg). The maleated allocimene produced had a melting point of 75-80°C. Maleated alloocimene production example 2 The reaction temperature was 130 to 140°C, the reaction time was 1 hour,
Maleated alloocimene was produced in the same manner as in Production Example 1 above using xylene as a solvent.

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

Example 1 The maleated alloocymene 60y obtained in Example 1 above was placed in a four-hole flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube, and was heated to about 100° C. to dissolve it.

To this was added 1.8y of sodium iodide, and the mixture was stirred at 200°C for 2 hours. Sodium iodide does not dissolve completely;
It was finely dispersed. After the reaction was completed, 50 cc of methyl isobutyl ketone was added*8, and the mixture was washed with 50 cc of 10% sodium thiosulfate aqueous solution.

After washing with water, the aqueous layer was removed, and the oil layer was dehydrated by adding sodium sulfate as a dehydrating agent, followed by simple distillation at a reduced pressure of 0.5 W&Hg. 160～
185℃/0.5wr! A pale yellow liquid maleated allocimene 56y (yield 93%) was obtained as a fraction of NHg.

This liquid maleated alloocimene was stored in a refrigerator at 5°C.
Although it was left in a refrigerator at -20°C and at room temperature (20 to 25°C) for more than two months, no crystallization occurred.

Its viscosity (E-type viscometer) was 125 CpS at 25°C. Examples 2 to 14 Produced in Production Example 1 or 2 according to the method described in Example 1, except that the type of catalyst, amount of catalyst, reaction time, reaction temperature, and catalyst addition method were changed as shown in Table 1. The solid maleated alloocimene was heat treated.

The viscosity and yield of the obtained liquid maleated allocimene were as shown in Table 1.

Note that in Examples 9 to 14, the catalyst was uniformly dissolved, but in other Examples, the catalyst was partially dispersed without being dissolved.

In addition, all of the liquid maleated alloocymenes (distilled purified products) obtained in each example had excellent liquid stability, and
℃, -20℃, and 20 to 25℃ for more than 2 months, but no crystals were precipitated in any case.

▼2 νFV ~ -VV Experimental Example 1 Epicoat 828 [Product name of Shell Chemical Co., Ltd., epoxy equivalent weight 189, glycidyl ether of 2,2-bis(4-hydroxyphenyl)propane] 100 parts (parts by weight, same hereinafter), carried out 115 parts of liquid maleated alloocymene obtained in Example 1 and 1 part of benzyldimethylamine as a hardening accelerator were uniformly stirred and mixed at room temperature, and the mixture was stirred and mixed under reduced pressure (27 WL
Hg or less) to prepare an epoxy resin composition.

The viscosity of this composition is about 20 poise at 25°C,
Casting etc. were extremely easy. This resin composition was heated at 80°C.
When the resin was pre-cured for 3 hours at 120° C. and then post-cured for 6 hours at 120° C., a strong cured resin was obtained as shown in Table 2.

For comparison, Table 2 also includes the formulations of epoxy resin compositions containing known curing agents and the physical properties of the cured resins.

Claims (1)

[Claims] 1. A liquid form of a chain triene maleate having 10 carbon atoms, which is obtained by heat-treating a linear triene maleide having 10 carbon atoms, which is solid at room temperature, in the presence of an alkali metal iodide. chemical treatment method. 2. The method according to claim 1, wherein the linear triene maleide having 10 carbon atoms that is solid at room temperature is maleated alloocymene. 3. The method according to claim 1 or 2, wherein the amount of alkali metal iodide present is 0.005% by weight or more based on the linear triene maleide having 10 carbon atoms. 4. The method according to claim 1, 2 or 3, wherein the heat treatment temperature is 120 to 250°C.