DE2042082A1 - Release agent for elastomers - Google Patents

Description

Henkel & Cie GmbH Düsseldorf, August 24th

_. . _ "Henkelstrasse 67

Patent department

New patent application

D 42o6
"Release agent for elastomers"

The subject of the invention is the use of disalts'

of sulfosuccinic acid half-esters as a release agent for natural and synthetic elastomers.

For example, in the production of rubber goods from natural and synthetic rubber, release agents are required, Once after the manufacture of the unvulcanized rubber mixture, the skin or blanks are glued together Prevent until further processing and on the other hand, the adhesion of the unvulcanized rubber mixture in the vulcanization mold prevent and thus enable easy removal of the vulcanizate.

A large number of different products have already become known as release agents for elastomers A rough classification can be assigned to two classes, the powdery and the liquid release agents. As the most famous representative Powder release agents are e.g. talc or zinc stearate. Main disadvantages of these powder products are their dust development in the manufacturing plant, as well as the sometimes poor weldability of those with talc or paint powder treated blanks during vulcanization.

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Tried the disadvantageous dust generation of the powder agent to counteract that one slurries the powder composition in an aqueous phase, through which then the unvulcanized Rubber compound heads are pulled.

Another way to counteract the disadvantages mentioned is that you dispense with powdering agents and completely liquid release agents are used, among which those based on fatty acids due to their economic efficiency and the possibility of to be used in aqueous solution, still have the greatest importance. In many cases where Fatty acid-based release agents will not develop an adequate release effect, e.g. as mold coating agents mainly silicone oils and fluorinated hydrocarbons are used as release agents. Besides the higher prices own However, these products have the disadvantage that the release agent fractions transferred to the vulcanizate impair the adhesion of subsequently adversely affect the applied finish or paintwork and also prevent the vulcanizate from sticking together to form a composite article.

The present invention is therefore based on the object of finding release agents which have a very good release effect have, but do not have the disadvantages outlined above.

This object is achieved by using disalts of alkyl sulfosuccinic acid half esters the general formulas

ROOC - CH - CH ₂ - COOMe, ROOC - CH ₂ - CH - COOMe tt

SO ^ Me SO ^ Me

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in which R is a saturated or unsaturated, straight or branched-chain aliphatic hydrocarbon radical Chain length of 8-26 carbon atoms, which can optionally be interrupted by ether groups, and Me stands for alkali metals, magnesium, ammonium, short-chain aliphatic amines or short-chain aliphatic alkanolamines, as Release agent used for natural and synthetic elastomers.

The preparation of the alkyl sulfosuccinic acid half-ester disalts to be used according to the invention can be carried out according to well-known methods, e.g. in the following manner. A corresponding, long-chain alcohol or an alkylene oxide addition product one of these is made with maleic acid ·? anhydride converted to the maleic acid half ester. This maleic acid half ester left with a corresponding salt of sulfurous acid, for example with sodium or ammonium bisulfite, to the corresponding disalt of the alkyl sulfosuccinic acid half ester react.

As alcohols that can be reacted with maleic anhydride to form the corresponding maleic acid half-ester in order to obtain the er ™ alkylsulfosuccinic acid half-ester disalts to be used according to the invention The following compounds should be mentioned, for example: Octyl-, nonyl-, decyl-, dodecyl-, myristyl-, palmltyl-, Stearyl, oleyl alcohol, alcohol mixtures produced by hydrogenation of coconut oil, soybean oil, peanut oil, rapeseed oil, palm kernel, tallow fatty acids, synthetically produced fatty acids or their esters as well as unsaturated alcohol mixtures obtained by hydrogenation of Coconut oil, soybean oil, peanut oil, rapeseed oil, palm kernel, tallow fatty acid or their esters can be obtained. Furthermore, synthetic

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higher alcohols, such as so-called Ziegler alcohols, Oxo alcohols, secondary alcohols from paraffin oxidation and ethylene oxide or propylene oxide addition products to natural or synthetic fatty alcohols with 1-15 moles of attached alkylene oxide as esterification components, Find use.

The cation components of the disalts used according to the invention are the alkali metals sodium, potassium, lithium, also magnesium, ammonium, short-chain aliphatic amines with 1 - k carbon atoms such as methyl, ethyl, propyl, isopropyl and butylamine, and short-chain aliphatic alkanolamines such as mono -, diethanolamine and triethanolamine. The disalts of the alkali metals sodium and potassium are of particular importance.

As both technically and economically The di-sodium and di-potassium salts of the alkylsulfosuccinic acid half esters and their alkyl radicals are particularly important has a chain length of 12-18 carbon atoms. They include primarily products, their Precursors by reaction of maleic anhydride with fatty alcohols were obtained, which are different from naturally occurring Derive fats and oils.

According to the invention as mold coating or layer release agents disalts of alkyl sulfosuccinic acid half esters to be used for natural or synthetic elastomers are expediently in aqueous solution and a concentration of 0.1 to 10 wt .- #, preferably 0.2 to 2 Wt .- ^, used.

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To achieve certain effects, it is possible in a known manner to use water-soluble polymers to improve film formation and add to increase the viscosity of the solutions. Carboxymethyl cellulose, hydroxyethyl cellulose, for example, are suitable and methyl cellulose. The products are commonly used individually in technical purity, but mixtures of the compounds with one another and with Emulsions of silicone oils and fluorocarbons can be used.

In order to achieve a good separating effect between unvulcanized rubber sheets, these are expedient brushed, sprayed or immersed in the solution with the release agent solution. For use as a mold coating the forms made of steel, aluminum or chrome-plated steel are coated with the aqueous solutions or sprayed and the water evaporates.

Albeit usually water as the solvent for the release agent to be used according to the invention is preferable, on the other hand it is for certain forms of application, e.g. in spray cans, also possible, additional organic solvents such as methylene chloride or lower alcohols alone or to be used in a mixture.

The following examples are intended to explain the subject matter of the present invention in more detail without restricting it thereto.

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Examples

1) In these experiments, the separating effect of the dipalts of alkylsulfosuccinic acid to be used according to the invention was investigated semi-esters and various other release agents on cast polyurethane elastomers. There were the following Polyurethane products used.

Mixture a)

Soft polyester polyurethane.

loo g of linear polyester (commercial product Desmophen 2ooo * 'from Farbenfabriken Bayer AG)

g of naphthylene-1,5-diisocyanate (commercial product Desraodur 15 of the paint factories Bayer AG)

2.3 g of a mixture of 8o % crosslinker B and 2o % crosslinker TR (commercial product from Farbenfabriken Bayer AG)

Mixture b)

Hard polyester polyurethane.

loo g linear polyester (commercial product Desmophen 2ooo ^ 'of the paint factories Bayer AG) g of naphthylene-1,5-diisocyanate (commercial product Desmodur 15 of the paint factories Bayer AG) g Crosslinker H (commercial product of paint factories Bayer AG)

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Mixture c)

Polyether polyurethane.

loo g reaction product of polytetramethylene ether glycol with excess toluene diisocyanate (commercial product Adiprene L 111 from Du Pont) 12.5 g ^ i ^ -Methylene bis - ^ - chloraniline (commercial product Moca from Du Pont)

The above-mentioned raw materials were converted into the specified mixing ratios in the customary manner Mixtures produced at elevated temperatures according to the raw material supplier's instructions and poured into steel molds, previously cleaned intensively and after cleaning twice with the solutions listed in the table below had been painted. Before filling, the molds were preheated to 100 to 100 ° C. The temperature in the Polyurethane compositions in the case of mixtures a) and b) was about 110 ° C., in the case of mixture c) 110 ° C. at the time of Filling. The curing of the polyurethane compositions took place in the case of mixture a) and mixture c) for 3 hours at llo ° C, whereas the mixture b) was cured for 24 hours at llo ° C. Subsequently, each was removed from the mold and the force required for demolding is subjectively determined. The results of the experiments are shown below Table reproduced.

The products listed below were used as mold release agents in the form of an 0.5 # aqueous solution used.

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Release agent A) alkali salt of a fatty acid derivative,

Commercial product Levaform K ^ '

B) Ammonium ΑIky1-phosphate, commercial product Aquarex ΙΛ '

C) Sodium alkyl sulfate, commercial product Aquarex

D) Sodium lauryl ether sulfate, commercial product Texapon N

E) Ammonium lauryl ether sulfate, commercial product Texapon NA * '

F) triethanolamine lauryl ether sulfate, Commercial product Texapon NT ^ '

G) triethanolamine lauryl sulfate, commercial product Texapon TH ^ '

H) Xylene sulfonate, commercial product Eltesol '' I) cumene sulfonate

K) Turquoise oil, degree of sulfation approx. 5o %, commercial product Sykanol ^ ^R ^

L) Turkish red oil, degree of sulfation approx. 65 $>, commercial product Sykanol DKM extra ^ '

M) sec. Alkanesulfonate, commercial product Hostapur SAS 3o ^ ^R ^

N) Alkylbenzenesulfonate, commercial product Arlicon paste ^

O) Fatty alcohol polyglycol ether, commercial product Eutnulgin Io92

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P) Ethoxylated fatty amine, commercial product Araphs K ^

Q) Cetyl-trimethyl-ammonium chloride, commercial product Dehyquart A

R) coconut fatty acid poly-diethanolamide, commercial product Comperlan pd ''

S) disodium salt of octyl-sulfosuccinic acid half-ester

T) Lauryl Sulpho Amber 'Dl Ammonium Salt

acid half-ester

U) Disodium salt of the myristile sulfosuccinic acid half-ester

V) DI sodium salt of oleyl sulfosuccinic acid half-ester

W) Disodium salt of stearyl sulfosuccinic acid half ester

X) Di-sodium salt of coconut fatty alcohol sulfosuccinic acid half-ester

Y) disodium salt of tallow fatty alcohol-sulfobern- *

stinic acid half-ester

Z) Disodium salt of hydrogenated rapeseed oil fatty alcohol sulfosuccinic acid half-ester

X) Di-sodium salt of the C _lo _ _1I -0xoalcohol-sulfosernstelnsäuremalbesters

Jf) Di-Natriurnrjalz des C. ^^^^ - AlfoL-sulfosuccinic acid half-rectcra

Jl) disodium salt of C _11-15 brine. Alcohol (paraffin oxidation) sulfosuccinic acid half-ester

J - Io -

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Coconut fatty alcohol + disodium salt

2 Äthylenoxidanlagungsverb «-sulfobernstein-

acid half-ester

Disodium salt of C »,, j-sec. Alcohol (paraffin oxidation) + 3 Ä0 ⁺ '-sulfosuccinic acid half-ester

Table I.
Demoulding tests of cast polyurethanes

Release agent Mixture a) Mixture b) Mixture c) A. Well Well Well B. Well Well Well C. bad bad D. bad bad E. bad bad F. bad bad G bad bad H satisfied
gend satisfied
gend Well I. satisfied
gend satisfied
gend Well K bad L. very moderate M. satisfied
gend satisfied
gend-good satisfied
gend-good N bad 0 bad bad P. bad bad Q bad bad

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Release agent Mixture a) Mixture b) Mixture c) R. bad bad S. Well Well Well T Well Well U very good
Well very good very good
Well V very good very good very good W. very good very good very good X Well very good very good
Well Y very good very good very good Z very good very good very good τ very good
Well very good very good
Well T very good
Well very good very good
Well very good
Well very good
Well very good
Well f Well Well Well A, Well Well Well

2) In a further experiment, a "self-adhesive" styrene-butadiene rubber mixture was used The following composition is used to investigate the release effect.

loo parts by weight of styrene-butadiene chewing material SBR 15000 stearic acid zinc oxide

Phenyl- oC - naphthylamine Precipitated silica Aromatic oil black lead secondary amine

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1.5 ti Il 5 Il Il 1 It It 5ο Il ti 2 It η 2 Il Il 1.8 It It

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1 , 6 η Il 1 It Il 1 Il Il 1 ,8th Il η

6 parts by weight of a 1: 1 mixture of precipitated silica and resorcinol

Hexamethylenetetramine

N-Cyclohexyl-2-benzthiazylsulfenamide Di-o-tolylguanidine

sulfur

This mixture is so special, that it can be used without Use of rubber / metal binders on metal surfaces adheres and with a conventional press vulcanization vulcanized for 10 minutes at 153 ° C. Before vulcanization the vulcanization mold made of steel was intensively cleaned and with a 0.5 # solution already in the example 1 of the ^ release agents listed once coated. In the The mold prepared in this way became panels made from the mixture mentioned above without having to treat the mold again with release agents, until there are significant demolding difficulties revealed. The number of pressings is therefore a measure of the productivity and effectiveness of the used release agent. The results are shown in Table II below.

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Table II

Release agent Number of presses sings A. 2 D. 1 E. 1 F. 1 G 1 H 1 I. 2 M. 1 O 1 I- P 2 R. 1 S. 2 T 4th U 4th V 6th W. 6th X 4th Y 6th Z 6th τ 5 V 4th JX f 2 A- 2

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3) A very sticky, soft natural rubber mixture with the following composition was used for the following experiment used.

loo parts by weight of natural rubber NR-RSS 1

Io 11 π zinc oxide 2 It η Stearic acid 1 ti η Phenyl- fh -naphthylamine 2 η η Spruce tar 25th η η EPC carbon black o, 33 η η Zinc dimethyl dithlocarbamate o, 58 η It Dibenzothiazyl disulfide 2.75 η η sulfur

First, mixing plates according to the above recipe were placed in 0.5 # solutions of the various Release agent dipped according to the list in example 1. Two plates treated in this way were each after the evaporation of the water placed on top of each other and loaded with weights, so that a pressure of about 2oo g / cm resulted. After 24 hours, a check was carried out to determine whether the two plates could easily be separated. Thereafter the two plates were placed on top of one another and in a vulcanization press for 10 minutes 153 ° C pressed. The vulcanizate was then examined to determine whether both plates were during the vulcanization process have been flawlessly welded together, i.e. the separating effect of the separating agents applied again was repealed. The results of the experiment are in. shown in Table III below.

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Table III

Layer separating agent Layer separation Welding D. moderate very good E. moderate very good F. moderate very good G moderate very good H moderate very good I. moderate very good M. moderate very good O moderate very good R. moderate very good S. Well very good T ^ Well very good U Good Excellent very good V very good very good W. very good very good X Good Excellent very good Y very good very good "C Well very good T Well very good i moderately good very good moderate very good

When using the disalts of alkylsulfosuccinic acid half esters according to the invention Alkyl chain length of 8-26 carbon atoms as Release agent for elastomers resulting advantage is that both an excellent layer and can also achieve mold separation without the later

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Gluing the vulcanizate to a composite article is worth seeing or the subsequent application of a Painting is adversely affected.

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Claims (4)

Henkel & CIe GmbH S.It. 17 iur patent application D 4206 patent claims 1) Use of disalts of alkyl sulfosuccinic acid half esters the general formulas ROOC - CH - CH ₂ - COOMe, ROOC - CH ₃ - CH - COOMe t 1 SO ₃ Me SO ₃ Me in which R is a saturated or unsaturated, straight or branched chain, aliphatic hydrocarbon radical a chain length of 8-26 carbon atoms, which can optionally be interrupted by ether groups and Me for alkali metals, magnesium, ammonium, short-chain aliphatic amines or short-chain aliphatic alkanolamines stands as a release agent for natural and synthetic elastomers. 2) Use of di-sodium or di-potassium salts of alkyl sulfosuccinic acid half esters according to claim 1. 3) Use of di-sodium or di-potassium salts of alkyl f sulfosuccinic acid half-esters with an alkyl chain length of 12-18 carbon atoms according to claims 1 and 2. 4) Use of disalts of alkyl sulfosuccinic acid half esters according to claim 1 - 3 in o, l - Io #iger, preferably 0.2-2 # aqueous solution. .209810 / 0778