CN1179419A

CN1179419A - Process for manufacture of alkylimidazolidone (methyl) acrylates

Info

Publication number: CN1179419A
Application number: CN 97121380
Authority: CN
Inventors: M·艾斯赫; A·里安德尔
Original assignee: Elf Atochem SA
Current assignee: Arkema France SA
Priority date: 1996-09-16
Filing date: 1997-09-16
Publication date: 1998-04-22

Abstract

The present invention provides a process for the manufacture of a compound of formula (I) by reaction of at least one (meth) acrylate of formula (II) with a heterocyclic alcohol of formula (III) in the presence of sodium methoxide as catalyst, characterized in that the sodium methoxide is gradually introduced, as a solution, throughout the synthesis: R[1]=hydrogen or methyl; A and B each independently represent a straight or branched hydrocarbon chain having from 2 to 5 carbon atoms; R[2] =C[1] -C[4] alkyl group.

Description

The method for preparing alkyl imidazole ketone (methyl) acrylate

The present invention relates to prepare the method for the following compound of molecular formula:

Wherein: R ¹Represent hydrogen or methyl;

A and B respectively independently representative the hydrocarbon chain of straight or branched of 2-5 carbon atom is arranged, this compound is by following (methyl) acrylate of at least a molecular formula:

Wherein: R ¹Meaning as previously mentioned; With

R ²Represent C ₁-C ₄Alkyl, the heterocyclic alcohol reaction following with molecular formula,

Wherein the meaning of A and B as previously mentioned.

These compounds of known molecular formula (I) are as the effect in the polymer formulators of the coating of treatment paper and textiles and tackiness agent, special in U.S. Pat-A-2,871,223 is described, and as leather treatment and the effect in the production of emulsion paint.Ethyl imidazol(e) ketone methacrylic acid (EIOM) uses in coating mainly as the promotor of wet binder.

Synthesize the theme that EIOM has constituted many patents by transesterify, its mutual difference only is the character of employed catalyzer.Found solid or part solid catalyst,, can make to operate in to be lower than 100 ℃ and to carry out, obtained good effect simultaneously from the productive rate of EIOM and the transformation efficiency of EIOH (1-(2-hydroxyethyl) imidazolidyl-2-ketone [SiC]).If but the liquid catalyst that obviously will produce same advantage is applied to during this reacts, can make synthesize under process scale more easy to operate.

European patent application EP-A-0,236,994 have mentioned and can use sodium methylate as this catalyst for reaction, but suggestion is not used it, because it has the tendency (particularly Michael reaction) of impelling side reaction to increase.But the application company is surprised to find now, use this catalyzer to be highly profitable, effect is all fine aspect EIOM productive rate and EIOH transformation efficiency, and do not produce the shortcoming of the promotion side reaction of expection, this is not so long as once add it when synthetic beginning, but is distributed in the entire synthesis process its adding.

Therefore theme of the present invention is to prepare the method for the compound of the molecular formula (I) of definition as mentioned in the presence of as the sodium methylate of catalyzer, and the feature of this method is progressively to add sodium methoxide solution in whole synthesizing.

According to the particularly preferred example of the present invention, a part of sodium methylate is to add when synthetic the beginning, and remaining is continuous or substep adding in whole synthesizing.The best initial part sodium methylate that adds is the 2-40% weight of employed relatively sodium methylate total amount, preferred 4-20% weight.

Usually the solution that adds sodium methylate 1-30% weight of (as methyl alcohol) in solvent.

The amount of the sodium methylate that the heterocyclic alcohol of every mole of molecular formula (III) is used in finishing according to method of the present invention is generally 1 * 10 ^-4Mol and 2 * 10 ^-3Between the mol, preferred 5 * 10 ^-4Mol and 1 * 10 ^-3Between the mol.

The reagent example of the molecular formula that can mention especially (II) is methyl esters, ethyl ester, n-propyl, positive butyl ester and the isobutyl ester of vinylformic acid and methacrylic acid.

The example of [SiC] heterocyclic alcohol of the molecular formula that can mention (III) is EIOH.

Reaction according to method of the present invention can be carried out in the presence of excessive one or another kind of reagent.But the mol ratio of the heterocyclic alcohol of (methyl) acrylate/molecular formula (III) of molecular formula (II) is about 2-5, preferred 2.5～3.5th, and is suitable.Under with respect to heterocyclic alcohol (methyl) acrylate serious offense molar weight, react, reaction obtains the solution of compound in (methyl) acrylate of molecular formula (I) when finishing, can directly use in some applications, for example in the paint and the preparation of coating or on the other hand in the processing at leather.

Reaction according to the inventive method is preferably carried out in the presence of at least a employed polymerization retarder, and for example with respect to the heterocyclic alcohol of molecular formula (III), polymerization retarder exists with the ratio of 300-1800ppm, preferred 600-1300ppm.The example of the polymerization retarder that can use that can mention especially is thiodiphenylamine, Resorcinol methyl ether, two-four-butyl-catechol, Resorcinol, to the mixture of aniline phenol, Ursol D and their arbitrary proportions.

Preferably carry out being no more than under the atmospheric pressure according to the reaction of the inventive method, for example at the pressure of 0.3-1 crust.In order to improve the effect of stablizer, make air bubble when reacting therefrom by being favourable.The heterocyclic alcohol of (methyl) acrylate of mixed molecules formula (II) and molecular formula (III), reaction mixture generally are heated to about 60-90 ℃, preferably about 70-85 ℃, react.This temperature obviously depends on the character of pure and mild (methyl) acrylate itself.

In finishing according to method of the present invention, at utmost dehydration is favourable before adding catalyzer, can prevent like this because moisture content makes catalyst deactivation.Following method can reach this purpose: for example when therefrom separating, under refluxad heat (methyl) acrylate of molecular formula II, the heterocyclic alcohol of molecular formula (III) and the starting mixt of polymerization retarder, its thing that boils of dissolving (methyl) acrylate and water when forming the azeotrope of (methyl) acrylate and water.In this step, after distillment separates, start catalysts is added in the thermal reaction mixture step by step.

Obviously depend on reaction conditions according to reaction process of the present invention, as temperature, pressure and catalyst consumption, but generally between 5-10 hour.It also obviously depends on the character of employed reagent.

When forming azeotrope, reacting by heating mixture under refluxing, (methyl) acrylate and the molecular formula that reach reaction formation up to top temperature (headtemperature) are R ₂The distillation temperature of the azeotrope of the alcohol of OH.

Remove excessive (methyl) acrylate as far as possible with method of evaporating then, the compound of isolated molecular formula (I) generally is solid-state from reaction mixture like this: so the acrylate of 1-(2-hydroxyethyl)-imidazolidyl-2-ketone [SiC] is a white crystalline solid, 43 ℃ of melting temperatures, in ketone, alcohol, aromatic hydrocarbon and water, be soluble under the cold condition, and be that [SiC] is insoluble in stable hydrocarbon under cold condition, under 0 ℃, from ethyl propenoate, be settled out.The methacrylic ester of 1-(2-hydroxyethyl) imidazolidyl-2-ketone [SiC] is a white crystalline solid, 47 ℃ of melting temperatures and have the solvability same with the aforesaid propylene acid esters.After the evaporation operation, product is by filtering, with petroleum ether and drying solid crystal being further purified then.

Compound (I) also can separate by the part evaporation of (methyl) acrylate, under enough low temperature, (preferably be less than or equal to 0 ℃) then the crystallization quite a long time (being 15 hours), filter then, carry out foregoing purification step subsequently.

At last, the third from the solution of the compound that contains molecular formula (I) with its minute isolation process be its extraction of water, thereafter by clarification, concentrating and separating (methyl) acrylate, and by the above-mentioned steps purifying.

The following examples have been narrated the present invention, but without limits it.Except other explanation was arranged, per-cent was weight percentage in these embodiments.Embodiment 1

With 1458gEIOH, 1.823g[SiC] thiodiphenylamine (PTZ) stablizer and 3827g methyl methacrylate (MMA) be added in 5 liters of jacketed glass reactor, and this reactor has been equipped the filled insulation post that the reflux ratio head is arranged at a detector of measuring temperature, variable-ratio mechanical stirrer and top.The top of post is stable with 0.1% MEHQ hydroquinone monomethyl ether (HQME) in MMA.

As air bubble by and under reduced pressure, inclusion reaches boiling point in the reactor, 75 ℃ following 1 hour, carry out component distillation with MMA then and remove moisture content.

Then 2.12g sodium methylate (MeONa) is made into 1% methyl alcohol (MeOH) solution, once adds in the reactor.Remaining 40.82g MeONa is made into the solution among 1% the MeOH, adds with volume pump in 7 hours.Regulating pressure is 75 ℃ with the temperature of keeping in the reactor.Equal the boiling temperature of azeotrope by the column cap fixed temperature, consider pressure, add 3 ℃ again, regulate MMA/MeOH azeotropic thing and extract.When amount that the amount of the methyl alcohol that extracts is equivalent to expect, reaction prolongs 1 hour, up to the formation of no longer observing MeOH (the column cap temperature of measuring in the whole backflow=boiling temperature of MMA under the pressure of design).

After cooling, reclaim thick no solid EIOM.

The turnover ratio of EIOM productive rate and EIOH is determined by the liquid chromatography analysis (HPLC) of reacting coarse product, the equation below using

Report the result in the table below, also comprised the data and the result of comparing embodiment 2.Comparing embodiment 2

Except synthetic beginning once adds all MeONa catalyzer, repeat and experiment that embodiment 1 is same.

Table 1

Embodiment	The HPLC of the crude product that obtains analyzes (%)			?????Y ????(％)	?????C ????(％)
	The HPLC of the crude product that obtains analyzes (%)					??MMA	??EIOH	??EIOM
	1 (of the present invention)	??43.58	??1.44			??MMA	??EIOH	??EIOM	??41.66	?????77	????95.9
2 (comparing embodiments)	1 (of the present invention)	??43.58	??1.44	Do not analyze: mixture is divided into two-phase, the transformation efficiency less than 50%				????＜50	??41.66	?????77	????95.9

Claims

1, the method for preparing following formula: compound:

Wherein: R ¹Represent hydrogen or methyl;

A and B respectively independently representative the hydrocarbon chain of straight or branched of 2-5 carbon atom is arranged, by (methyl) acrylate of at least a following formula:

Wherein: R ¹Meaning as above; With

R ²Represent C ₁-C ₄The heterocyclic alcohol of alkyl and following formula: Wherein A and B meaning are as above reacted in the presence of as the sodium methylate of catalyzer, it is characterized in that in entire synthesis process sodium methylate progressively adds with the solution form.

2, according to the method for claim 1, it is characterized in that beginning to add the part sodium methylate synthetic, remaining in building-up process continuously or substep add.

3,, it is characterized in that initial adding is with respect to 240% weight of all wts of employed sodium methylate, the sodium methylate of preferred 4-20% weight according to the method for claim 2.

4, according to each method among the claim 1-3, it is characterized in that adding in the solution of sodium methylate in a kind of solution of 1-30% weight, for example the solution in methyl alcohol.

5,, it is characterized in that the heterocyclic alcohol of every mole of molecular formula (III) uses 1 * 10 according to each method among the claim 1-4 ^-4-2 * 10 ^-3Mole, preferred 5 * 10 ^-4-1 * 10 ^-3The mole sodium methylate.

6,, it is characterized in that being reflected under 60-g0 ℃, preferred 70-85 ℃ of temperature and carry out according to each method among the claim 1-5.

7,, it is characterized in that the mol ratio of the heterocyclic alcohol of (methyl) acrylate of the molecular formula (II) used and molecular formula (III) is 2-5, preferred 2.5-3.5 according to each method among the claim 1-6.

8, according to each method among the claim 1-7, it is characterized in that being no more than under the atmospheric pressure, the time that reaction is carried out is 5-10 hour.

9,, it is characterized in that being reflected at and at least aly be selected from thiodiphenylamine, quinhydrones methyl ether, two-four-butyl-catechol, quinhydrones, carry out under existing to anilino phenol, to the polymerization retarder of the mixture of phenyl diamines and their arbitrary proportions according to each the method among the claim 1-8.

10, according to the method for claim 9, it is characterized in that heterocyclic alcohol with respect to molecular formula (III), the polymer inhibitor that uses or the amount of multiple inhibitor are 300-1800ppm, preferred 600-1300ppm.