Manufactoring process of catalysts for polymerization acaline of lactams.

PATENT AS AFRICAN AND MALAGASY

INDUSTRIAL PROPERTY

P. 887

yaounde (Cameroon) International Patent Classification: 01 C.

NO. 02452

O A>M-I-P

17 June 1967 request 11 hr 40 min to

to ro.A.M.p. 1. (g.P. no. 52,973) by

the company called: the VED CESKOSLOVENSKA akademy

residing in Czechoslovakia.

5 May 1970 delivered

Publishes official ballot № L of 1970

PRIORITY:

Patent application deposited in Czechoslovakia r° 4128/66 20 June 1966 under the trade name ZbynekBUKAC and Jan SEBVEN Dato

Method of making catalysts for alkaline polymerization of lactams.

The present invention relates to a method of making catalysts for polymerization of lactams which alkaline catalysts are of the one-component type or mono body and have the general formula:

^R 1

N-CO c CO.Ri

THE I 4

THE R -,

THE R.

The mth

or

X

N-CO C. CO

^R 1^2 ^ 3

2

The mth₂

wherein r1, the R2, and r4 r3, represent hydrogen, an alkyl, an aryl and oyclo-alkyl, respectively where Me is a TiN alkali metal cation or alkaline earth metal, and wherein X is a bivalent organic radical.

A alkaline polymerization of lactams is, as a rule, initiated using strong bases, such as for example, hydrides of alkali metals and amides as well as organometallic compounds. However, in the presence of such substances the polymerization is not reproducible with difficulties. A alkaline polymerization of lactams may be substantially accelerated by adding some sort acyllyctami - _ er of sensitizing agents (gustatory thereof to 93,016 Czechoslovak Patent no. 10), and it is the reason why two-component catalyst systems are currently used. Despite many advantages due namely at speeds and high polymerization, the polymerization catalyzed by such two-component systems also has certain drawbacks. The polymerization takes place very rapidly even at temperatures of the order of 100 °c, so fitting it in¹ after that a solution of sodium salt of caprolactam has been blended with the activator, the polymerization is carried out at a relatively high speed. The disadvantage mentioned above is by the process described in Patent deposited by the applicant in ' has * m P. the I, I-_I under No. 1966 grams of gG ggg for: "method for polymerizing alkaline fast lactams using catalysts to a single component", so that for a rapid polymerization catalysts to a single component of the general formula:

R

2

N C0 .C-TO-C0

The mth

wherein:

Me is an alkali metal cation or alkaline earth, while Rl, r2, r3 r4 and each represent hydrogen, an alkyl, a cyclo alkyl or aryl.

Effective catalysts a monocomponent or mono body of the type mentioned above can be very easily prepared from the corresponding metals hydrides, for example by a method in accordance with that has been described in the application mentioned above.

This method however has some drawbacks due to the fact that the manipulation of metal hydrides requires a relatively high tech, and, furthermore, this method is far from being economical. Further, the catalysts prepared with hydride form heterogeneous systems in nature so that the quality of such catalysts is subject to fluctuations.

Above-mentioned disadvantages, as well as other, that present prior, are discarded by a dispenser for applying a single body having the general formula:

where ri, r2, r3 and r4, represent hydrogen, an alkyl, a cyclo alkyl and aryl respectively, where Me is an alkali metal cation or aiealino earth, and wherein, X is a bivalent organic radical, method according to which, according to the invention, an amide of an bétacétonique is dissolved in an alcoholic solution of the corresponding metal alkoxide.

Other features of the above process are that the solvent is removed from the solution, thereby obtaining a solid catalyst suspended in an inert medium such qu'hydro cemented carbide aliphatic, aromatic, cycloaliphatic, or ethers.

The alcoholic solution of catalyst obtained has a quality sufficient for polymerization of lactams.

The solutions of catalyst produced are stable, so that they may be prepared for storage. In this case they are preferably stored in containers that the preserve of air humidity and carbon monoxide contained in the latter. The opportunity to prepare solutions of storable one-component catalysts for the polymerization of lactams in alkaline greatly facilitates manipulation. It is only necessary to remove the solvent in an inert atmosphere under vacuum, after which the precipitated solid after ' evaporation is dissolved in a lactam to form a mixture polymerizing.

According to the present invention, catalysts single body of the type mentioned above can also be prepared in suspension in an inert organic solvent, such as, for example hydro-aromatics, aliphatic or cyeloaliphatiques, or ethers, or mixtures thereof, the total solid precipitated from the alcoholic solution of the catalyst being kept in suspension by means of an agitator effective. A suspension prepared in this manner can be stored and handled in a manner similar to alcohol solutions of the salts of beta-keto.

According to the present invention, it is further possible to dispense the solid obtained by evaporating the alcohol solution in inert media of various types, such as for example heavy aliphatic cemented carbide or the like, to scatter more or less uniform. The number of catalyst pastes obtained using the above method are also relatively stable and capable of carrying the catalysts

it is shielded from the ambient atmosphere. Further, they may for example be stored in bottles of conventional type to the emery-slugs without the catalyst activity is reduced, which enables dosing easy. After the necessary quantity of pulp has been weighed, the dispersing agent is removed from the pulp by means of suitable solvent and after that the lactam has been added, is prepared, the well-known, by polymerizing the mixture.

The present invention and its implementation will become better understood upon reading of the non-limiting examples exposed below.

Example 1

Introduced acid anilide 2.33 g of 2 ethyl 3 a-oxohexane carboxylic dry in a reaction chamber, is added in an inert gas stream 20 ml of sodium ethoxide to 0.5 m in methanol and dissolved with stirring. The solvent is distilled under vacuum of 3 mm of mercury at a temperature of 30 to 40 °c after evaporation of most of the methanol the vacuum is urged to 0.5 mm Hg and the vaporization is continued for a further une.heure. This results in a vaporization residue to which is added 20 to 30 ml of xylene or ether dry inert gas stream and the mixture is stirred intensively. After filtration the solvent and drying in the inert atmosphere, the catalyst is recovered as a white powder, thin and lightweight.

Example 2

An amount of u, 62 g of powdered catalyst is dissolved in 96 g of caprolaetame and the polymerization mixture is charged into vials. By the polymerization at a temperature of 70 °c during 60 min, an equivalent content of the obtained polymer. The polymerization mixture is heated for ten minutes to 210 °c and repolymerized to 170 °c, thereby achieving a conversion of 97 * 5 after storage of JiO days at room temperature in sealed ampules the mixture is heated for sixty minutes to 170 °c with the same result.

Example 5

A magnesium salt is prepared analogously

to the example 1, namely by action of the methanolate magnesium on the amides diamides alpha-butyryl butyric acid which has been derived from the methylamine, of 1' ethylamine, aniline, P-phenylenediamine in the form of a white powder with a thin polymerization activity lower than in the case of the alkali metal salt thereof.