JP2862933B2 - Method for producing N-alkenyl-N-glycidyl (meth) acrylamide compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel method for producing an N-alkenyl-N-glycidyl (meth) acrylamide compound.

[Technical background of the invention and its problems]

N-alkenyl-N-glycidyl (meth) acrylamide compounds such as N-allyl-N-glycidyl methacrylamide, N-allyl-N-glycidyl acrylamide, N-allyl-N-2-methylglycidyl methacrylamide and the like are known compounds. It has been shown to be useful as a reactive diluent such as an epoxy resin, a cross-linking agent, and a resin modifier (JP-A-58-88373, JP-A-59-16883). However, according to additional tests by the present inventors, when manufacturing methods described in these publications, for example, when manufacturing N-allyl-N-glycidyl methacrylamide, epichlorohydrin, allyl chloride and methacrylamide are reacted at once. This method has the disadvantage that the reactivity of the methacrylamide is too low compared to the reactivity of the other two raw materials, or it is actually difficult to obtain the desired product, and even if it is obtained, the yield is extremely poor. Was.

[Object of the Invention] An object of the present invention is to provide a method for industrially and advantageously producing N-alkenyl-N-glycidyl (meth) acrylamide.

[Configuration of the invention]

The present inventors have conducted intensive studies to achieve the above object, and as a result, firstly, an aminoalkene was reacted with epihalohydrin to form an addition reaction product in which an epoxy ring was opened,
Next, (meth) acryloyl chloride is reacted with the addition reaction product, and finally, an alkali compound is added to regenerate the epoxy ring, whereby N-alkenyl-N-glycidyl (meth) acrylamide is industrially obtained at a high yield. And found that the present invention was achieved.

That is, in the present invention, an aminoalkene is reacted with epihalohydrin to synthesize N-alkenyl-2-hydroxy-3-chloroalkylamine, and then reacted with (meth) acryloyl chloride to produce N-alkenyl-N- (2- A hydroxy-3-chloroalkyl) (meth) acrylamide compound is synthesized, and finally an alkali compound is added to regenerate the epoxy ring, and the N-alkenyl-N- compound is synthesized.
The present invention relates to a method for producing a glycidyl (meth) acrylamide compound.

The aminoalkene used in the present invention has a _C2-18 hydrocarbon having a primary amino group and an aliphatic C = C bond. The amino group is reacted with epihalohydrin and (meth) acryloyl chloride. Aliphatic C = C bonds have been chosen to increase the utility of the target compound. Such aminoalkenes include, for example, allylamine, 1-amino-3-butene, 1-amino-
4-pentene, 1-amino-2-methyl-2-propene, 1-amino-2-butene-4-vinylaniline, 4
-Allylaniline, 4-aminomethylstyrene and the like.

On the other hand, examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, 2-methylepichlorohydrin and the like, and epichlorohydrin is most preferable in terms of availability.

The reaction between the aminoalkene and epihalohydrin proceeds only by mixing the two, but it is preferable to add water as a catalyst for the purpose of shortening the reaction time and increasing the yield. The amount of water is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 2.0% by weight, based on the total amount of the charged aminoalkene and epihalohydrin. The charged molar ratio of aminoalkene to epihalohydrin (aminoalkene / epihalohydrin) is preferably 1.0 to 2.0 from the viewpoint of yield and economy.
The reaction can be carried out at a temperature in the range of -30 to 150 ° C, preferably in the range of 20 to 60 ° C. The pressure during this reaction is generally at normal pressure, but may be increased or reduced if necessary.

The solvent used in the reaction is not particularly required, but may be used, and examples thereof include toluene, xylene, cyclohexane, n-hexane, n-heptane, naphtha, mineral spirit, and petroleum benzine. Hydrocarbon solvents; halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, 1,1,1-trichloroethane; ether solvents such as ethyl ether, tetrahydrofuran, and ethylene glycol diethyl ether Ester solvents such as ethyl acetate, butyl acetate, amyl acetate;
Methanol, ethanol, propanol, butanol,
Examples include alcohol solvents such as ethylene glycol and ethylene glycol monomethyl ether; aprotic polar solvents such as dimethylformamide and dimethylacetamide.

The reaction time varies depending on the starting material used, the amount of the catalyst, the reaction temperature, etc., and is not particularly limited.
Conditions are set so that the reaction is completed in time.

Next, the reaction proceeds with the above reaction product and (meth) acryloyl chloride. Before the reaction, it is preferable to protect the hydroxy group generated by the reaction between the amino group and epihalohydrin for improving the yield. Even without protection, the amino group has higher reactivity with (meth) acryloyl chloride than the hydroxy group, and the amide formed is more stable than the ester, so there is no particular problem, but the hydroxy group and (meth) acryloyl chloride This is because some reaction occurs.

Any protecting group may be used as long as it protects the hydroxy group. However, in view of availability, stability to the next reaction, and ease of removal, it is preferable to protect with a triorganosilyl group. Such silyl groups include trimethylsilyl, triethylsilyl,
Examples thereof include a methyldiethylsilyl group and a dimethylethylsilyl group. The silylation method may be carried out simply by reacting the corresponding silazane with the compound obtained by the above-mentioned method under a water-free condition. It is preferable that the charged amount of silazane is in excess of the adduct. The reaction time, reaction temperature, pressure, and solvent used may be the same as those described above. However, since alcohol solvents react with silazane, they are not suitable for this reaction.

The reaction with (meth) acryloyl chloride is achieved by reacting the aminoalkene obtained as described above with an adduct of epihalohydrin, more preferably a silylated product thereof, in the presence of a suitable dehydrochlorinating agent. Is done. As the dehydrochlorination agent used in this reaction, tertiary amines such as trimethylamine, triethylamine, tributylamine and benzyldimethylamine, and cyclic amines such as pyridine are used. The amount of the amine may be at least the equivalent of the (meth) acryloyl chloride used.

The charge ratio of the (meth) acryloyl chloride to the aminoalkene / epihalohydrin adduct or the silylated product thereof ((meth) acryloyl chloride / aminoalkene / epihalohydrin adduct) may be any, but the amount of unreacted raw material is minimized. To do
1.0 to 1.2 is preferred. The reaction temperature, reaction time, pressure, and solvent used may be the same as those for the above-mentioned reaction between aminoalkene and epihalohydrin.

The reaction is achieved by mixing an adduct of aminoalkene and epihalohydrin or a silylated product thereof, and an amine which is a dehydrochlorinating agent with a solvent, and adding (meth) acryloyl chloride dropwise thereto. The salt formed by the reaction is removed by filtration.

Finally, the epoxy ring is regenerated. Usually, an alkali compound such as sodium hydroxide or potassium hydroxide is used for this purpose, and is added in the form of an aqueous solution for the purpose of easy addition and dissolution of the generated salts. Even when the hydroxy group is protected with a silyl group, it is deprotected under these conditions, so that the step of deprotection is unnecessary. The amount of the alkali to be added is used in an equivalent amount to an excess of 200% with respect to the equivalent of HCl to be dehydrochlorinated from the methacrylamide derivative, and preferably an excess of 10 to 50%. If it is less than this, a compound in which the epoxy ring is not regenerated remains, and if it is more than this, the formed epoxy ring is easily attacked by the hydroxy group, and the amide bond is easily cleaved, which is not preferable. The reaction temperature, reaction time and reaction pressure are not particularly limited, but the reaction is usually carried out at 0 to 40 ° C under normal pressure for 0.5 to 6 hours. The reaction is achieved by stirring the methacrylamide derivative in an aqueous alkaline solution.

As described above, the final target product can be obtained in four steps including the silylation step, but the product can be isolated in any of the steps. However, usually, the final target compound can be obtained in high yield without isolation in each step.

The obtained compound can be purified by a known technique such as distillation, gas chromatography, liquid chromatography, column chromatography and the like. In addition, the addition of a known antioxidant or polymerization inhibitor for the purpose of increasing the stability of the raw material or the product during the reaction or during the distillation is no problem at all.

 Hereinafter, an example of the flow of the manufacturing method of the present invention will be described.

[Effects of the Invention] According to the method of the present invention, epoxy resins, reactive diluents for various resins including unsaturated polyester resins, crosslinking agents, useful as resin modifiers, or as raw materials for various organic compounds It has become possible to industrially obtain useful N-alkenyl-N-glycidyl (meth) acrylamide in high yield.

〔Example〕

Hereinafter, the present invention will be described with reference to Examples. In the examples,
Parts represent parts by weight.

Example 1 A flask equipped with a thermometer, a cooling tube, and a dropping funnel was charged with 92.5 parts (1.0 mol) of epichlorohydrin and 85% of allylamine.
5 parts (1.5 mol) and 1.0 part of water were charged and stirred. During the reaction,
Since an exotherm was observed, the reaction was cooled so that the reaction temperature did not exceed 40 ° C. After the reaction for 4 hours, unreacted allylamine was removed under reduced pressure (40 ° C./20 Torr), and 200 parts of tetrahydrofuran and 85 parts of hexamethyldisilazane were added to give 3 parts.
Stirred at room temperature for hours. Further, 200 parts of tetrahydrofuran and 110 parts of triethylamine were added, and then 104.5 parts (1.0 mol) of methacryloyl chloride was dropped from the dropping funnel over 1 hour. At this time, care was taken that the reaction temperature did not exceed 30 ° C. After further stirring at room temperature for 2 hours, the formed salt was separated by filtration, and low boiling components were removed under reduced pressure (40 ° C./20 Torr).

To the obtained reaction product, 48 parts of sodium hydroxide was added to water 15
The solution dissolved in 0 parts was added at 20 ° C. or lower, and the mixture was stirred in a flask at room temperature for 1 hour. Then, the aqueous layer was removed by liquid separation, and dried over anhydrous sodium sulfate. Subsequently, 100-1 by vacuum distillation
103 parts of a fraction at 03 ° C./3 Torr were obtained. The theoretical yield was 57%. The fraction was analyzed by NMR, IR, Mass and elemental analysis, and it was confirmed that N-allyl-N-glycidyl methacrylamide was obtained.

NMR (CCl ₄ , δ) 1.93 (s, 3H, C-CH ₃ ) IR (cm ^-1 ) 3080 (olefinic CH), 2930 (CH), 1630 (C = 0, C = C) Mass (M ⁺ ) 181 Elemental analysis (calculated values in parentheses) C 66.01 (66.27) H 8.49 ( 8.34) N 7.65 (7.73) Comparative Example 1 14 parts of methacrylamide, 23 parts of allyl chloride, 37 parts of epichlorohydrin, 20 parts of sodium hydroxide and 150 parts of dimethyl sulfoxide were put in a flask and stirred at 40 ° C. for 5 hours. Thereafter, the reaction mixture was analyzed by gas chromatography, and it was found that a large amount of methacrylamide remained. Also, no peak indicating the production of N-allyl-N-glycidyl methacrylamide obtained in Example 1 was detected.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C07D 303/36 C07D 301/27 C07C 211/21 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. An N-alkenyl-2-hydroxy-3-chloroalkylamine is synthesized by reacting an aminoalkene with epihalohydrin and then reacting with (meth) acryloyl chloride to produce N-alkenyl-N- (2- A method for producing an N-alkenyl-N-glycidyl (meth) acrylamide compound, comprising synthesizing a hydroxy-3-chloroalkyl) (meth) acrylamide compound and finally adding an alkali compound to regenerate the epoxy ring.