MXPA94008284A

MXPA94008284A - Process for the preparation of alkylimidazolidone (meth)-acrylates

Info

Publication number: MXPA94008284A
Application number: MXPA/A/1994/008284A
Authority: MX
Inventors: Riondel Alain; Herbst Gilles; Esch Marc
Original assignee: Elf Atochem Sa
Priority date: 1993-10-27
Filing date: 1994-10-26
Publication date: 2002-03-05

Abstract

A process for the production of a compound of formula:in which:R@1 represents hydrogen or methyl;and A and B each independently represent a straight or branched hydrocarbon chain having from 2 to 5 carbon atoms, by reaction of at least one (meth)acrylate of formula:in which:R@1 has the above meaning;and R@2 represents a C1 -C4 alkyl group, with a heterocyclic alcohol of formula:in which A and B have the above meanings, in the presence of a catalytic quantity of at least one magnesium alkoxide.

Description

PROCESS FOR THE PREPARATION OF (MET) ALOYLIMIDAZOLIDONE ACRYLATES INVENTORS: ALAIN RIONDEL of French nationality, resident in: 74, Rue Nationale, 57600 Forbach, France. GILLES HERBST of French nationality, resident in: 24, rue St Laurent, 57350 Spicheren, France. MARC ESCH of French nationality, resident in: 23, rue Goethe, 57800 Freyming-Merlebach, France.

APPLICANT: ELF ATOCHEM S. A. French entity, domiciled at: 4 & 8, Cours Michelet, La Défense 10, 92800 * Puteaux, France SUMMARY OF THE INVENTION The present invention relates to a compound (I) which is prepared by reacting at least one (meta) acrylate (II) with a heterocyclic alcohol (III) in the presence of at least one catalyst chosen from the alkoxides : Magnesium Mg (OR) 2.

O B O B / \ / \ H2C-C-C-0-A-N NH H2C-C-C-0-R 'H N-A-OH \ / \ / R1 R C I O or (I): ID (III) where R = C? P R1 = H, CH3; A, B = straight or branched chain C2-C5 hydrocarbon; R2 = C1 - C4. The present invention relates to a process for the production of a compound of the formula: 0 B 1 / \ H2C- -C- -c- 0- -A- -N NH (I) 1 \ / R- 1 C 1 0 wherein: R1 represents hydrogen or methyl; and A and B independently represent a straight or branched chain hydrocarbon having from 2 to 5 carbon atoms, by reacting at least one (meta) acrylate of the formula: R1 has the aforementioned meaning; R2 represents a CX-C4 alkyl group, with a heterocyclic alcohol of the formula: B / HN-A-OH (III) /C or wherein A and B have the meanings mentioned above. These compounds of the formula (I) are known for their role in the manufacture of the polymers which are useful as coatings and adhesives, for the treatment in papers and textiles, in particular by the American Patent A-2,877,232, also as by their uses as agents for the treatment of skins, and in the production of emulsion paints. Ethylimidazolidone methacrylate (EI0M) is mainly used in paints and as an activator of moisture adhesion. In the process defined in the foregoing, known from European Patent Application EP-A-0, 236, 944, the catalysts are chosen from the titanium alkoxides, for example the tetralkyl titanates and the chelates of Ti, Zr, Fe or Zn with the 1,3-dicarbonyl compounds, for example the acetylacetonates of Ti, Zr, Fe or Zn. It should also be mentioned that, in this European Patent Application EP-A-0, 236, 944, the already known use of the basic catalysts KOH, K2C03 and NaOMe and the basic catalysts derived from pyrimidine is reported, with the recommendation of that these should not be used taking into account their strong tendency to favor secondary reactions. It is also known, from the European Patent Application EP-A-0, 433, 135, the use of the dialkyltin oxides, the dialkistano dialkoxide and the dialkyltin di ethers as catalysts for this same reaction. The di-n-butyltin oxide (DBTO) among others is mentioned. However, in the case of the EIO synthesis, the largest possible conversion of hydroxyethylimidazolidone (HEIO) was attempted, which, in the case of DBTO catalysis, requires a high level of temperature. In the same way a different type of catalyst has been sought, which allows in particular a good production, efficiency and good selectivity at lower reaction temperatures. Surprisingly it has now been discovered that the use of a magnesium alkoxide makes it possible for this to operate at a temperature below 100 ° (in particular 95 ° C to 96 ° C), while at the same time "it leads to good results from the point of view of the efficiency of the EIOM and conversion of the HEIO the objective of the present invention is the process for the production of a compound of the formula (I) as described above of at least one magnesium alkoxide as a catalyst Examples of magnesium alkoxides Mg (0R) 2 which may be mentioned are those for which R represents a linear C?-C4 alkyl group, such as methyl, ethyl, n-propyl and n-butyl. The alkoxides for which R represents ethyl or n-propyl can be mentioned in? more particular way. The use of magnesium diethoxide is preferred. Examples of the reagents of the formula (II) which can be mentioned in particular are the methyl, ethyl, n-propyl, n-butyl and isobutyl acrylates and methacrylates. In particular, the compound l- (2-hydroxyethyl) -2-imidazolidone (HEIO) can be mentioned as an example of a < > heterocyclic alcohol of the formula (III). The amount of catalyst used for carrying out the process according to the invention is generally between about 0.5 and 4 mol% and preferably between about 1 and 2.5 mol% relative to the heterocyclic alcohol of the formula (III). The reaction of the process according to the invention can be carried out in the presence of an excess of one or * another of the reagents. However, it is advisable that for the (meta) acrylate of the formula (II) -heterocyclic alcohol of the formula (III) the molar ratio is between 1.1 and 7.0 approximately, preferably between 2.0 and 6.0. When working with a large molar excess of (meta) acrylate in relation to the heterocyclic alcohol, a solution of the compound of the formula (I) in (meta) acrylate is obtained at the end of the reaction, whose solution can be used directly for certain applications , as to obtain paints and coatings or alternatively for the treatment of skins or leathers. The reaction of the process according to the invention is preferably carried out in the presence of at least one polymerization inhibitor used, for example, in an amount of 0.05 to 0.5% by weight based on the weight of the heterocyclic alcohol of the formula (III). As examples of the polymerization inhibitors that can be used, mention may be made in particular of phenothiazine, hydroquinone methylether, di-tert-butylcatechol, hydroquinone, p-anilino enol, p-phenylenediamine and mixtures thereof in all proportions. The reaction of the process according to the invention is preferably carried out at a pressure not exceeding atmospheric pressure, for example a pressure between 0.3 and one bar. The reaction is advantageously performed when air is bubbled through it, to improve the efficiency of the stabilizers. This is carried out by mixing the (meta) acrylate of the formula (II) and the heterocyclic alcohol of the formula (III), and by heating the reaction mixture to reflux, generally at a temperature between 85 and 105 ° C. , this temperature obviously depends on the exact nature of the alcohol and the (meta) acrylate, and on the catalytic system used.

In carrying out the process according to the invention, it is advisable to achieve a maximum dehydration before the addition of the catalyst, to avoid deactivation of the latter by water. This result can be achieved, for example, by heating the initial mixture of the (meta) acrylate of the formula (II), the heterocyclic alcohol of the formula (III) and the reflux polymerization inhibitor, while it is separated by distillation the azeotrope of (meta) acrylate and water when an azeotrope of methacrylate and water is formed. In this step, after separation of the distillate, the catalyst is introduced into the hot reaction mixture. The duration of the reaction according to the invention obviously depends on the reaction conditions such as temperature, pressure and amount of the catalyst used, but generally it is between about 3 and 15 hours. Obviously it also depends on the nature of the reagents used. The reaction mixture is thus heated to reflux until the liquefaction temperature reaches the distillation temperature of the azeotrope of the methacrylate and the alcohol of the formula R2OH formed by the reaction when an azeotrope is formed. The possible access of methacrylate can subsequently be removed by evaporation, to isolate the compound of the formula (I) from the reaction medium, generally in the solid state: thus, the 1- (2-hydroxyethyl) -2-imidazolidone acrylate is a white crystalline solid of melting point equal to 43 ° C, which is soluble under cold conditions in ketones, alcohols, aromatic hydrocarbons and water, insoluble under cold conditions in saturated hydrocarbons and which precipitates at 0o the ethyl acrylate. The methacrylate of 1- (2-hydroxy-ethyl) -2-imidazolidone is a white crystalline solid of melting point equal to 47 ° C which * has the same solubility properties as the acrylate mentioned in the above. At the end of the evaporation step, the crystalline solid product can also be purified by filtration, followed by washing with petroleum ether, and drying. The isolation of the compound (I) can also be carried out by partial evaporation of the methacrylate, followed by the crystallization at a sufficiently low temperature (preferably less than or equal to 0 ° C) and for a sufficiently long period (which can be up to 215 hours ) and then the filtration, followed by the purification steps described in the above. Finally, a third method for isolating the compound of the formula (I) from the solution containing it consists in carrying out an extraction with water, followed by the separation of the phases after the sedimentation has been carried out, the methacrylate concentration and the purification steps described in the foregoing. The following examples illustrate the invention, however, without implying any limitation thereof. In these examples, the percentages are indicated by weight except when indicated otherwise.

EXAMPLES Example 1: 195 grams of HEIO and 565 grams of methyl methacrylate (MMA), together with 0.36 grams of phenothiazine (PTZ) as a stabilizing agent, are introduced into a jacketed glass reactor, equipped with a probe to measure the temperature, a variable speed mechanical agitator and a packed adiabatic column, crowned with a reflux head. The column head is stabilized with a 0.2% solution of hydroquinone methyl ether (HQME) in MMA. The reactor content J is boiled at atmospheric pressure for 1 hour, at a column head temperature of 98-100 ° C and at a column foot temperature less than or equal to 100 ° C and the water is removed by azeotropic distillation with methyl methacrylate. Subsequently 3.4 grams of magnesium ethoxide and MMA are introduced into the reactor, taking care that the molar ratio of MMA / HEIO is equal to 3.5 (after drying). The pressure is adjusted to maintain a temperature # T of 96 ° C in the reactor. The separation of the MMA / MeOH azeotrope is controlled by setting the temperature at the head of the column (equal to 65 °). When the amount of methanol removed corresponds to the expected amount, the reaction is continued until no greater methanol formation is observed (column head temperature = boiling point of MMA), at full reflux and even at the pressure of I tried. After cooling, the EIOM is removed without purifying the EIOM performance and the HEIO conversion is determined by the liquid chromatography (CLAP) analysis of the unpurified reaction product, using the following equation: Conversion C HEIO (%) = (Initial HEIO - Final HEIQ) x 100 Initial HEIO > Yield R EIOM (%) Number of moles EIQM formed x 100 Number of moles of initial HEIO The results are reported in the following table, which also includes the data and results of four other examples.

Picture The catalyst used in this example is magnesium propoxide (the catalyst used in Examples 2, 4 and 5 is the same as in Example 1).

Claims

NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and, therefore, the content of the following CLAIMS is claimed as property; A process for the production of a compound of the formula: ## STR2 ## wherein: R 1 represents hydrogen or methyl; and A and B independently represent a straight chain or "branched" hydrocarbon having from 2 to 5 carbon atoms, reacting with at least one (meta) acrylate of the * formula: RJ where: R1 has the aforementioned meaning; R2 represents an alkyl group of C? - C4, with a heterocyclic alcohol of the formula: HNN-A-OH (III) I / O wherein A and B have the meanings mentioned above, in the presence of at least one magnesium alkoxide catalyst.
2. The process according to claim 1, characterized in that a magnesium alkoxide is used R Mg (0R) 2, R represents the alkyl residue of Cx-C4.
3. The process according to claim 2, characterized in that R represents ethyl or n-propyl.
4. The process according to any of claims 1 to 4, characterized in that the catalyst is used in an amount of 0.5 to 4 mol% relative to the heterocyclic alcohol (III).
5. The process according to any of claims 1 to 4, characterized in that the reaction is carried out at a temperature of 85 and 105 ° C.
6. The process according to any of claims 1 to 5, characterized in that a molar proportion of the methacrylate of the formula (II) is used to the heterocyclic alcohol of the formula (III) is between 1.1 and 7.0. The process according to any of claims 1 to 6, characterized in that the reaction is carried out for a period of between 3 and 15 hours and at a pressure not exceeding atmospheric pressure. The process according to any of claims 1 to 7, characterized in that the reaction is carried out in the presence of at least one polymerization inhibitor selected from phenothiazine, hydroquinone, methyl ether, di-tert-butyl catechol, hydroquinone, p-anilinophenol, para-phenylenediamine and their mixtures in all proportions. In testimony of which I sign the present in this City of Mexico D. F. on October 26, 1994. P150694MX-