ITRM930705A1 - PRODUCTION PROCESS FOR KETONIC RESINS. - Google Patents

Description

Description of the industrial invention entitled:

PROCEDURE FOR THE PRODUCTION OF KETONE RESINS

SUMMARY

Homopolymerization and / or copolymerization process of cyclic aliphatic ketones by means of basic catalysts.

DESCRIPTION

The ketone resins available on the market and produced both in Italy and abroad generally consist of products of poly-condensation between an aliphatic ketobe (generally cyclohexanone) and the form1dehyde. commercially available ketone resins based on aromatic monomers (see G.V.Villavecchia et al., New Dictionary of Commodity and Applied Chemistry, Vol.6 Utet, Milan 1983). These resins are used in the formulation of inks, varnishes, paints, hot melts etc ... (cfr. Vi11avecchia, Op. Cit.).

In the past, ketone resins have also been described based on the homopolymerization of cyclohexanone and the copolymerization of cyclohexanone with a mixture of methylcyclohexanone isomers (A. Hill, Modern Plastics p.119, 1948). based on cyclohexanone-formaideide vi? the total absence of formaldehyde vapor emission. Essentially the process described by A. Hill (Op. Cit.)? still in use in European industry and consists in condensing cyclohexanone with metallic potassium (notoriously a very difficult material to handle as it tends to ignite spontaneously in the air) and therefore requires special ancillary infrastructures for its handling. Furthermore, said process requires polymerization under pressure in an inert atmosphere (nitrogen).

It has now surprisingly been found and therefore forms the object of the present invention that solutions of an alkaline hydroxide in an alcohol or solutions of an alkaline, alkaline-earth and earthy alkoxide in alcohol are effective catalysts for polymerization and copolymerization without the application of pressure and without the use of inert atmospheres, of cyclohexanone, of all the isomers of methylcyclohexanone, of 3,3,5-trimethylcyclohexanone, and of the whole series of cyclic alitatic ketones that can be described with the following general formula

with n integer between 3 and 24 used alone or mixed together. On the other hand ? It is interesting to note that the Chemical Abstract from 1950 to 1992 under the heading "Cyclohexanone" summarizes works and patents that almost exclusively concern condensation reactions between cyclohexanone and formaideide. other words, in recent years the research on ketone resins has? almost exclusively oriented on the synthesis of cyclohexanone / formai deide resins while? The research on the homopolymerization of cyclohexanone or other alitatic ketones (and their copolymerization) was practically completely neglected, in the absence of formaldehyde with the exception of the Italian Patent N 1230434 and the Italian Patent Applications N 47989A90 and N RM91A000052 all filed by Franco Cataldo and in which the discovery of a process suitable for homopolymerizing acetone in the absence of other modifiers or comonomers is reported for the first time and in which methods for the chemical modification of polymers are described. obtained from acetone. The present invention will come now described according to its preferred embodiments but? it is to be understood that in no case should they be construed as limiting this, therefore variations and modifications can be made by experts in the art without thereby departing from the relative scope of protection.

EXAMPLE 1

A mixture of 0.597 kg of cyclohexanone and 0.200 kg of methanol is heated under stirring with 0.208 kg of potassium hydroxide in an oil bath at 125 C for about 17 hours. The mixture is then left to cool to 105 C and dissolved in 2.5 liters of xylene (mixture of isomers). The solution is then washed with 0.9 liters of water, then with an equal volume of a 65% acetic acid solution and then with two portions of water (0.9 liters each). Most of the methanol used in the reaction and the potassium hydroxide in concentrated aqueous solution can be recovered by distillation.

The xylene solution is steam distilled and the solvent is recovered quantitatively. A completely white and solid resin is recovered which is ground and dried. Yield 0.550 kg, approximately 92% of the initial monomer.

Capillary melting point of the resin: 95-100 C

UV-VIS spectrum in cyclohexane (nm): 220 (m), 26G (m), 300 (m), 345 (sh).

IR film spectrum on KBr tablet (in cm-1):

EXAMPLES 2-8

One proceeds in general as described in example 1, operating with pure cyclohexanone and potassium hydroxide or sodium hydroxide in methanol; the IR spectra of the resins are comparable to that described in example 1

EXAMPLES 9-11

The cyclohexanone? been polymerized with a general procedure similar to that described in Example 1. used potassium methoxide or sodium methoxide in methanolic solution.

EXAMPLES 12-24

Cyclohexanone was co-polymerized with methylcyclohexanone (mixture of isomers), with 3,3,5-trimethylcyclohexanone, with cyclooctanone and - with cyclododecanone following the general procedure of example 1. In the following table A = cyclohexanone, B = methylcyclohexanone, C = 3,3,5-trimethylcyclohexanone, D = cyclooctanone, E

cyclododecanone.

EXAMPLES 25-28

Cyclopentanone and cyclododecanone were polymerized according to what described in Example 1 both by using KOH and potassium methoxide (MeOK) in the usual molar ratios (2: 1 monomer / catalyst).

Claims (1)

CLAIMS 1. Homopolymerization and copolymerization process of cyclic alitatic ketones having general formula with n integer between 3 and 24 by using as polymerization catalysts any basic condensation agent belonging to the class of alkaline hydroxides and / or alkoxides, or alkaline earth, or even earthy, alone or in an alcoholic solution. 2. Process according to claim 1 carried out in batch and in continuous at atmospheric pressure and with temperatures between 40 and 1 350 C. 3. Process according to claim 1 carried out in batch and in continuous under autogenous pressure between 1 and 100 atmospheres and temperatures between 40 and 350 C. 4. Process according to claim 1 carried out in an inert gas atmosphere with an overpressure between 1 and 100 atmospheres and temperatures between 40 and 350 C. 5. Process according to claims 1,2,3,4 wherein the cyclic aliphatic ketone? cyclopentanone. 6. Process according to claims 1,2,3,4 wherein the cyclic aliphatic ketone? the cyclohexanone. 7. Process according to claims 1,2,3,4 wherein the cyclic alitatic ketones are mixtures of cyclohexanone and methylcyclohexanone in any molar ratio to each other. 8. Process according to claims 1,2,3,4 wherein the cyclic alitatic ketones are mixtures of cyclohexanone and 3,3,5 trimeth? 1cyclohexanone in any molar ratio to each other. 9. Process according to claims 1,2,3,4 wherein the cyclic alitatic ketones are mixtures of cyclohexanone and cyclododecanone in any molar ratio to each other. 10. Process according to claims 1,2,3,4 wherein the cyclic alitatic ketones are mixtures of cyclohexanone and cyclooctanone in any molar ratio to each other. 11. Process according to claims 1 to 10 inclusive, wherein the polymerization catalyst consists of methanolic solutions of anhydrous potassium hydroxide. 12. Process according to claims 1 to 10 inclusive, wherein the polymerization catalyst consists of methanolic solutions of anhydrous sodium hydroxide. 13. Process according to claims 1 to 10 inclusive, wherein the condensation catalyst consists of potassium methoxide alone or in a methanolic solution. 14. Process according to claims 1 to 10 inclusive, wherein the polymerization catalyst consists of sodium methoxide alone or in a methanolic solution. 15. Process according to claims 1 to 10 inclusive, wherein the condensation catalyst? lithium methoxide alone or in methanolic solution. 16. Process according to claims 1 to 10 inclusive, wherein the catalyst? the ethox? do d? potassium alone or in methanolic solution. 17. Process according to claims 1 to 10 inclusive, wherein the condensation catalyst? Sodium ethoxide alone or in methanolic solution. 18. Process according to claims 1 to 10 inclusive, wherein the condensation catalyst? ethoxide of lithium alone or in methanolic solution. 19. Process according to claims 1 to 10 inclusive, wherein the condensation catalyst? 1 aluminum isopropoxide alone or in methanolic solution. 20. Process according to claims 11 to 19 inclusive, wherein the solvent? The anhydrous ethanol instead? methanol. 21. Process according to claims 11 to 19 inclusive wherein the solvent? ethylene glycol instead of? methanol. 22. Process according to the preceding claims, substantially as illustrated and described.