CS230799B1 - Saponification resistent softener for chemicaly resistent coating composition - Google Patents

Abstract

The invention relates to the field of coating and solves carcinogenic substitution chlorinated diphenyl. SUMMARY OF THE INVENTION is a method of softening non-saponifiable polymeric binder coatings increased resistance to water, acids and bases using low molecular weight condensation products of cycloaliphatic ketones and / or alcohols containing two up to three cycles per molecule. For softening up using 1 to 100 wt. related to polymernl binder. Use is particularly preferred distillation of dehydrogenation residues cyclohexanol or methylcyclohexanols, from catalytic hydrogenation of phenols and from refining cyclohexanone obtained by oxidation cyclohexane. The invention can be used in manufacturing paints with increased durability water, acids and bases.

Description

The subject of the invention are unsaponifiable plasticizers for chemically resistant paints suitable for softening macromolecules! ch lacquer binders.

At present, non-saponifiable plasticizers such as chlorinated polyphenyls, such as chlorinated diphenyl and triphenyl, chlorinated paraffins, dimethylthianthrene, polyvinylmethyl ether, diphenoxyethylformal, optionally, are used to soften coatings that are intended to resist the effects of various acidic or alkaline chemicals in the form of vapors or liquids. and triaryl phosphates. It has recently been found that chlorinated polyphenyls are carcinogenic and have therefore been banned. The saponifiable plasticizers cannot be used in those cases where high water, alkali and acid resistance requirements are imposed.

It found _{(unsaponifiable} that as a plasticizer for chemically resistant coatings can be preferably used a low molecular weight condensation products, cycloaliphatic ketones and / or alcohols having two to three cycles per molecule.

“The advantage of these compounds over the prior art is that they are well-miscible with the macromolecular binders used for paints with enhanced chemical resistance such as chlorinated rubber, cyclo-rubber, polystyrene, vinyl chloride-vinyl acetate or vinylisobutyl ether copolymers, chlorinated polyvinyl chloride, polyvinyl chloride and the like. of cycloaliphatic ketones and / or alcohols are poorly volatile, physiologically harmless at normal temperature, and non-hydrolysable by acidic and alkaline agents.

Suitable low molecular weight condensation products of cycloaliphatic ketones and alcohols include, for example, products obtained by acid or alkali catalysed 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., Nakladatelství ČSAV, Praha 1960, p. 233):

-> o- (5 ⁺ θ 'όθ.)

-ch ₃ c ₆ h ₄ s ₃ h

Catalytic hydrogenation of phenols and catalytic dehydrogenation of cyclohexanol and its methyl derivatives produce by-products of dicyclohexyl ether (I), o-cyclohexenylcyclohexanol (II), o-cyclohexylcyclohexanol (III) and o, o-dicyclohexylc (III) tri-nucleus compounds. dicyclohexylcyclohexanol (V):

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

These bivalent and trinuclear compounds can be used in isolation or in mixtures as they arise in the above reactions. Preferably, distillation residues may be used resulting from the industrial catalytic dehydrogenation of cyclohexanol or methylcyclohexanols, the catalytic hydrogenation of phenols or the rectification of C-cyclohexanone from the catalytic oxidation of cyclohexane. For many applications, phenolic compounds and hydrocarbons also do not matter.

230 799

Similar products resulting from the condensation of cyclopentanone, cycloheptanone and cyclooctanone can also be used.

As binders, polymers resistant to both acidic and alkaline hydrolysis can be advantageously used, e.g.

Coating compositions within the meaning of the present invention may be solvent-containing or solvent-free. The plasticizers of the present invention may also be combined with known plasticizers. The plasticizers of the invention can also be used for thick-film plastics coatings. salts, in particular polyvinyl chloride, or organosols containing only a low amount of solvents. For their application in coatings with increased chemical resistance, the usual formulation principles apply as with the use of commonly known plasticizers.

The invention is further illustrated by the following non-limiting examples.

24% wt n n 32 n 15 Dec II 4 II 8 n or mixture

Example 1

The chlorinated rubber lacquer was prepared from the following components: chlorinated rubber (chlorine content 67.1%) plasticizer xylene aromatol (a mixture of high-boiling aromatic hydrocarbons) turpentine cyclohexanone resin m.p. 85 ° C

The plasticizer used was chlorinated diphenyl or cyclohexenylcyclohexanone / dicyclohexyl ether 1: 1 mol. (labeled CC-DCE).

Properties of lacquer films: plasticizer of stress on coated paper hardness by pendulum ČSN 67 3076 digging resistance ČSN 67 3081 drying ČSN 67 3053 to stage A to stage B 3 chlorine, diphenyl 1%

mm min.

h chemical resistance (cap method) complies

CC-DCE%

mm min. 24 h compliant

Example 2 230 799 Polymeric primer for based on copolymers of vinyl chloride rid vinyl acetate (87 / L3) was prepared from the following components: vinyl chloride-vinyl acetate copolymer K-value 77 15 wt. a plasticizer 5 ethylmethylketone 20 May acetone 15 ” xylene 30 rutile titanium white 7,5 ^w talc 7.4 ” ferric black 0.1 Chlorinated diphenyl or the residual from the boiler distillation of cyclohexanone prepared by catalytic dehydrogenation of cyclohexanol (containing dicyclohexyl ether, cyclo hexenylcyclohexanone, hydrocene and tricyclics viscosity 15 Pa.s at 20 ° C), indicated by abbreviation , ZB. Characteristics of coating films: a plasticizer chloro, diphenyl ZB stress on coated paper 1 1 digging resistance ČSN 67 3081 9 mm 9 mm pendulum hardness ČSN 67 3076 22% 27% Drying ČSN 67 3053 to stage A 25 min. 20 min. to stage B 5 2 h 2 h Grip adhesion 2 1 Example 3 Polystyrene lacquer was ready of the following Ingredients: polystyrene, K-value 82 22nd % wt. a plasticizer 11 M xylene 67 n

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

The properties of the paint films are shown on the next page.

230 799

a plasticizer chloro, diphenyl CT stress on coated paper 1 1 digging resistance ČSN 67 3081 7 mm 7 mm pendulum hardness ČSN 67 3076 24% 30% Drying ČSN 67 3053 to stage A 45 min. 30 min. to stage B 1 3 h 2,5 h chemical resistance (hat method) compliant compliant

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,