CS230799B1 - Non-saponifiable plasticizers for chemically resistant paints - Google Patents

Abstract

The invention relates to the field of paints and solves the problem of replacing carcinogenic chlorinated diphenyl. The invention is a method of softening unsaponifiable polymer binders of paints with increased resistance to water, acids and alkalis using low molecular weight condensation products of cycloaliphatic ketones and/or alcohols containing two to three cycles in the molecule. For softening, 1 to 100% by weight is used, based on the polymer binder. The use of distillation residues from the dehydrogenation of cyclohexanol or methylcyclohexanols, from the catalytic hydrogenation of phenols and from the refining of cyclohexanone obtained by the oxidation of cyclohexane is particularly advantageous. The invention can be used in the production of paints with increased resistance to water, acids and alkalis.

Description

The subject of the invention are unsaponifiable plasticizers for chemically resistant coatings, suitable for softening macromolecular paint binders.

Currently, unsaponifiable plasticizers such as chlorinated polyphenyls, e.g. chlorinated diphenyl and triphenyl, chlorinated paraffins, dimethylthianthrene, polyvinylmethyl ether, diphenoxyethylformal, and possibly also triaryl phosphates, are used to soften coatings that are to withstand the effects of various acidic or alkaline chemicals in the form of vapors or liquids for a longer period of time. It has recently been found that chlorinated polyphenyls are carcinogenic and their use has therefore been prohibited. Saponifiable plasticizers cannot be used in cases where high requirements are placed on resistance to water, alkalis and acids.

It has been found _that low molecular weight condensation products of cycloaliphatic ketones and/or alcohols containing two to three cycles in the molecule can be used advantageously as unsaponifiable plasticizers for chemically resistant coatings.

"The advantage of these compounds over the known state of the art lies in the fact that they are well miscible with macromolecular binders used for coatings with increased chemical resistance, such as chlorinated rubber, cyclorubber, polystyrene, copolymers of vinyl chloride with vinyl acetate or vinyl isobutyl ether, chlorinated polyvinyl chloride, polyvinyl chloride, etc. These condensation products of cycloaliphatic ketones and/or alcohols are of low volatility at normal temperatures, physiologically harmless, and cannot be hydrolyzed by acidic or alkaline agents."

Suitable low-molecular condensation products of cycloaliphatic ketones and alcohols include, for example, products obtained by acid- or alkali-catalyzed condensation of cyclohexanone and its methyl derivatives. Cyclohexanone and substituted cyclohexanones

230 799 undergo smooth aldol condensation in both alkaline and acidic environments (Preparative reactions in organic chemistry. Volume V., Czechoslovak Academy of Sciences Publishing House, Prague 1960, p. 233):

—> o-(5 ⁺ θ“όθ

-ch ₃ c ₆ h ₄ sa ₃ h

Catalytic hydrogenation of phenols and catalytic dehydrogenation of cyclohexanol and its methyl derivatives produce binuclear by-products of the type dicyclohexyl ether (I), o-cyclohexenylcyclohexanol (II), o-cyclohexylcyclohexanol (III) and trinuclear compounds of the type o,o-dicyclohexylcyclohexanone (IV) and o,o-dicyclohexylcyclohexanol (V):

Similar products are also formed during the rectification of cyclohexanone obtained by catalytic oxidation of cyclohexane.

These di- and trinuclear compounds can be used isolated or in mixtures, as they are formed in the above reactions. Preferably, distillation residues from the industrial catalytic dehydrogenation of cyclohexanol or methylcyclohexanols, from the catalytic hydrogenation of phenols or from the rectification of c-cyclohexanone from the catalytic oxidation of cyclohexane can be used. For many applications, contamination with phenolic compounds and hydrocarbons is not a problem.

230,799

Similar products formed during the condensation of cyclopentanone, cycloheptanone and cyclooctanone can also be used.

Polymers resistant to both acid and alkaline hydrolysis can be advantageously used as binders, e.g. chlorinated rubber, cyclorubber, polystyrene and styrene copolymers, polyvinyl chloride and its copolymers and terpolymers with vinyl acetate, dibutyl maleate, monobutyl maleate, acrylates, vinyl isobutyl ether, chlorinated polyvinyl chloride, etc.*

The coatings according to the invention may be solvent-containing or solvent-free. The plasticizers according to the invention may also be combined with known plasticizers. The plasticizers according to the invention may also be used for thick-layer coatings of the plastisol type, especially with polyvinyl chloride, or organosols containing only a small amount of solvents. For their application in coatings with increased chemical resistance, the usual formulation principles apply as for the use of commonly known plasticizers.

The subject matter of the invention is further illustrated by examples of embodiments, which, however, do not limit its scope in any way.

24% mass n n 32 n 15 II 4 II 8 n or mixture

Example 1

Chlorinated rubber varnish was prepared from the following components: chlorinated rubber (chlorine content 67.1%) plasticizer xylene aromatol (mixture of higher-boiling aromatic hydrocarbons) turpentine cyclohexanone resin b.t. 85 °C

Chlorinated diphenyl or a 1:1 mol mixture of cyclohexenylcyclohexanone and dicyclohexyl ether (abbreviated as CC-DCE) was used as a plasticizer.

Properties of varnish films: plasticizer tension on coated paper pendulum hardness ČSN 67 3076 resistance to pitting ČSN 67 3081 drying ČSN 67 3053 to stage A to stage B 3 chlorine, diphenyl 1%

mm min.

h chemical resistance (hat method) complies

CC-DCE %

mm min. 24 h suitable

Example 2 230,799 Polymer base paint on based on vinyl chloride copolymers rid-vinyl acetate (87/L3) was prepared from the following components: vinyl chloride-vinyl acetate copolymer K-value 77 15% by weight plasticizer 5 ethyl methyl ketone 20 acetone 15 ” xylene 30 titanium white rutile 7.5 ^watts slipper 7.4” iron black 0.1 Chlorinated diphenyl or the rest was used as a plasticizer flow from the boiler distillation of cyclohexanone prepared by catalytic by dehydrogenation of cyclohexanol (containing dicyclohexyl ether, cyclo hexenylcyclohexanone, hydrocumene and tricyclic substancesj viscosity 15 Pa.s at 20 *C), denoted by the abbreviation , ZB. Properties of paint films: plasticizer chlorine, diphenyl ZB tension on coated paper 1 1 excavation resistance ČSN 67 3081 9mm 9mm pendulum hardness ČSN 67 3076 22% 27% drying ČSN 67 3053 to stage A 25 minutes 20 minutes to stage B 5 2 hours 2 hours grid cut adhesion 2 1 Example 3 The polystyrene varnish was prepared of the following ingredients: polystyrene, K-value 82 22 % wt. plasticizer 11 M xylene 67 n

Chlorinated diphenyl or a reaction mixture obtained by condensation of cyclohexanone with the addition of 3% p-toluenesulfonic acid with azeotropic separation of water and subsequent distillation of unreacted cyclohexanone (viscosity 24 mPa.s at 20 ^° C nj“° 1.5154), designated CT, was used as a plasticizer.

The properties of the paint films are listed on the following page.

230,799

plasticizer chlorine, diphenyl CT tension on coated paper 1 1 excavation resistance ČSN 67 3081 7mm 7mm pendulum hardness ČSN 67 3076 24% 30% drying ČSN 67 3053 to stage A 45 minutes 30 minutes to stage B 1 3 hours 2.5 hours chemical resistance (hat method) conforms conforms

Claims (3)

SUBJECT OF THE INVENTION 230 799 A non-saponifiable plasticizer for chemically resistant coating compositions, characterized in that it consists of low molecular weight condensation products of cycloaliphetic ketones and / or alcohols containing two to three cycles per molecule. 2. A saponification plasticizer according to claim 1, characterized in that it is formed by the products of the non-pressurized condensation of cyclohexanone or methylcyclohexanone in the presence of acid-base catalysts. 3. A saponification plasticizer according to claim 1 _f, characterized in that it consists of distillation residues from the catalytic dehydrogenation of cyclohexanol or methylcyclohexanols, the catalytic hydrogenation of phenols or the rectification of cyclohexanone obtained by the catalytic oxidation of cyclohexane. Printed by Moravian Printing Works,