DE2051479C2 - Process for the emulsion polymerization of ethylenically unsaturated monomers in the presence of an emulsion stabilizer - Google Patents

Description

or

represent,
is formed

4. The method according to claim 2, characterized in that as a monomeric emulsion stabilizer a compound is used in which V is acryloyloxy, methacryloyloxy, vinyloxy or 4-hydroxymaleoyl group means and the quaternary nitrogen group N + Ri R2R3 from

(a) aliphatic tertiary amines, in which Ri and R _{2 represent} alkyl groups having 1 to 4 carbon atoms, or

(b) Groups in which N, Ri and R ₂ together form part of a heterocyclic tertiary amine of the formulas

- N

R ₃

represent,
is formed

or -

be, for example an alkylammonium halide. the cationic agents are preferably used together with a nonionic agent in terms of a better behavior used The polymerization of monomeric materials is also often used in Presence of a water-soluble protective colloid or stabilizers listed

So far it has always been necessary to use an emulsion stabilizer in the emulsion polymerization of ethylenically unsaturated monomers. However, since the emulsion stabilizers used hitherto were sensitive to water, they remained unchanged during the polymerization and are consequently present in the polymer latex finally obtained. Thus, the use of a surfactant or a stabilizing agent results in the presence of water-sensitive constituents in the polymeric latex ultimately obtained. When the latex must be used under circumstances where wet strength and resistance to the influence desired by water, for example as a coating for paper or be: the production of non-woven cloths or random fiber nonwovens and certain pressure sensitive adhesive change, is the presence of water-sensitive ingredients in the polymeric mass undesirable

The object of the invention is to avoid the disadvantageous presence of soluble Emulsion stabilizer components in the polymer latex.

This object is achieved by the inventive method for emulsion polymerization of an ethylenic unsaturated monomers dissolved in the presence of an emulsion stabilizer, which is characterized is that as an emulsion stabilizer in an amount of 0.1 to 10.0 wt .-% an ethylenically unsaturated quaternary ammonium compound which is copolymerized to form part of the polymers, the following formula

45

50

Polymeric latexes derived from ethylenically unsaturated monomers are widely used for used a variety of purposes such as adhesives and binders for nonwoven fabrics Cloths or random fiber fleeces. The usual polymer latexes are produced by emulsion polymerization, i.e., by polymerizing monomeric materials while in an aqueous medium kept dispersed by a surfactant. The surfactant can be anionic be, for example a soap or sodium lauryl sulfate. So is z. B. the polymerization of styrene with Sodium lauryl sulfate as an emulsion stabilizer on the page of the book C. E. Schildknecht, Vinyl and related Polymers, John Wiley and Sons, Inc. (1952).

On the other hand, the emulsion stabilizer can be nonionic, for example an ethylene oxide derivative or a polyhydroxy compound, or it can be cationic R ₁ -N ⁺ XR ₂ Rs

is used, in which V is one of the following ethylenically unsaturated radicals:

a) Acid ester groups or acid amide groups accordingly the formulas

HO-CO-CH = CH-COO-HO - CO - CH = CH - CONH -
HO —CO —CH = (CH ₃ ) -COO-HO - CO-CH = C (CH ₃ ) - CONH -
HO-CO-CH ₂ -C-COO-

CH ₂

HO-CO-CH ₂ -C-CONH-

Il
CH ₂

b) Acrylic ester groups or acrylamide groups accordingly the formulas

CH ₂ = CR ₄ -COO- and
CH ₂ = CR ₄ -CONH-,

wherein R _{4 represents} a hydrogen atom or a methyl group,

c) allyl, methallyl, vinyloxy, allyloxy, methallyloxy, Vinylacetoxy, allylacetoxy or methallylacetoxy groups,

A, which is missing if V is an allyl, methallyl, vinylacetoxy, Allylacetoxy or Methallylacetoxygruppe represents and otherwise an ethylene, propylene, hydroxypropylene, Acetoxypropylene, isopropylene group or moiety

-0-CH ₂ -CHR ₄ - (O-CH ₂ -CHR ₄ ) ,, -,

wherein R _{4 represents} a hydrogen atom or a methyl group and π represents the numbers 0.1, 2, 3 or 4, indicates the quaternary nitrogen group N ⁺ Ri R ₂ R ₃

a) aliphatic tertiary amines, in which Ri is an alkyl or benzyl group having 1 to 7 carbon atoms and R _{2 is} either an alkyl or benzyl group having 1 to 7 carbon atoms or one of the groups

R ₅ -O-CO-CH ₂ - or R ₅ -NH-CO-CH-

represents wherein R ₅ denotes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or

b) Groups in which N, Ri and R ₂ together form part of a heterocyclic tertiary amine of the formulas

+
- N

or

R _{3 is} a lipophilic radical which contains an aliphatic hydrocarbon chain with 7 to 28 carbon atoms, chains with 9 to 18 carbon atoms being particularly preferred, this hydrocarbon chain L being covalently bonded to the nitrogen atom either directly or through one of the following intermediate bonds: a Benzyl group, an ester group, such as

-CH ₂ -CH ₂ -O-CO- L, a polyalkylene oxide group, for example

-0-CH ₂ -CHR ₄ - (O-CH ₂ -CHR ₄ J _n -OL,

. wherein R ₄ denotes a hydrogen atom or a methyl group and π denotes a number from 0 to 4, an alkylacetoxy or alkylacetamido group, such as

-CH ₂ -CO-OL and -CH ₂ -CO-NHL, an alkylalkylene ether group, such as

-CH ₂ -OL,
an alkyl amide group such as

-CH ₂ -CH (CH ₃ J-NH-CO-L, a hydroxysuccinyloxy group

R ₈ -O-CO-CH (L) -CH ₂ -COOH, a hydroxysuccinylamino group

R ₈ -NH-CO-CH (L) -Ch ₂ -COOH,

wherein R ₈ indicates a divalent radical, preferably ethylene, propylene, isopropylene, 2-hydroxypropylene, acetoxypropylene, or

-0-CH ₂ -CHR ₉ (O-CH ₂ -CHR ₉ J _n ,

where Rg denotes a hydrogen atom or a methyl group and η denotes the numbers 0, 1, 2, 3 or 4, or an isomer of the above hydroxysuccinyloxy or hydroxysuccinylamino groups, in which the hydrocarbon group L is bonded to the carbon atom adjacent to the carboxyl group, the aliphatic hydrocarbon chain L is linear or branched, saturated or unsaturated, and X- is one of the radicals (a) F- .C1-, Br-, 1-, CH ₃ SO ₄ -, C ₂ H ₅ SO ₄ -,

CHj-

or (b) an alkyl sulfate in which the alkyl moiety contains 7 to 28 carbon atoms, an alkyl benzene sulfonate, wherein the alkyl moiety contains 7 to 12 carbon atoms, a phenoxy (or alkylphenoxyJ-alkylene (or PolyalkyleneoxyalkyleneJ-sulfate of the formula

R "-C ₆ H4O- (CH ₂ -CHR"'- O) _n -CH ₂ -CHR "' SO ₄ -,

where R "represents a hydrogen atom or an alkyl group with 1 to 12 carbon atoms, R '" represents a hydrogen atom or a methyl group and π represents the number zero or an integer, a dialkyl sulfosuccinate group in which the alkyl groups contain 1 to 24 carbon atoms, or an alkyl phosphate group, wherein the alkyl group has 1 to 18 carbon atoms, where, if X- has the meaning (b), R _{3 is} a lipophilic radical with a hydrocarbon chain of 8 to 28 carbon atoms.

So there is a new method of emulsion stabilization through the use of Emulsion stabilizers that contain a quaternary nitrogen atom covalently with an ethylenically unsaturated radical bs and bonded to a lipophilic group and ionically bonded to an anionic group contain the at the same time as a stabilizer for the emulsion polymerization of the ethylenically unsaturated monomers and serve as a monomeric reactant in the polymerization, so that the salt is an integrated Part of the polymer v * ird, which is thereby stabilized by itself. So it doesn't have to be surface-active Means are used, and the polymer latex is free from water-sensitive components.

The monomeric emulsion stabilizer used is advantageously a compound in which X- is one of the radicals F-, Cl-, Br- or I-. The monomeric emulsion stabilizer used is preferably a compound in which V denotes an allyl, methallyl, vinyl acetoxy, allylacetoxy or methallylacetoxy group and the quaternary nitrogen group denotes ^{N +} _{RiR 2} R ₃
(a) aliphatic tertiary amines, in which Ri and R _{2 represent} alkyl groups having 1 to 4 carbon atoms, or

(b) Groups in which N, Ri and R2 are part of a heterocyclic tertiary amine of the formulas

-N

or

- N

represent,
is formed.

A compound is used very favorably as a monomeric emulsion stabilizer, in which V is a Acryloyloxy, methacryloyloxy, vinyloxy or 4-hydroxymaleoyl group means and the quaternary Nitrogen group N + Ri R2R3

(a) aliphatic tertiary amines, wherein Rt and R2 Represent alkyl groups having 1 to 4 carbon atoms, or

Groups where N, Ri and R2 together form the part of a heterocyclic tertiary amine of the formulas

- N

or

represent,
is formed.

More complicated acid residues X are conveniently prepared by first adding a suitable monomer is made with a simple portion X, for example a halide, and then the monomer is reacted with a suitable alkali or ammonium salt, as will be explained below.

The largely novel monomeric emulsion stabilizers used according to the invention accordingly of the formula above can be obtained by reacting a corresponding ethylenically unsaturated Alkylene halide with a tertiary amine containing a lipophilic group or with a suitable one Ring compound that contains the nitrogen atom in the ring, or by reacting a halogenated compound, which has activated halogen with an ethylenically unsaturated compound which has a tertiary amine group contains, are produced.

Illustrative manufacturing methods are the reactions between allyl chloride and dimethyldodecylamine or dimethylhexadecylamine, between allyl bromide and N-coconut morpholine, in which the nitrogen atom in the Morpholine ring covalently attached to a mixture of saturated alkyl groups with an average of 12 carbon atoms is bound between dimethylallylamine and Dodecyichioracetat and between Maieinsäureanhydrid and the reaction product of dimethylamine ethanol and lauryl bromide as used in the examples below are listed

example 1

Manufacture and use of the

Vinyloxyäthyl-dimethyltridecyloxycarbonyl-

methylammonium chloride

283 g of dimethylaminoethyl vinyl ether were in 98 g Acrylic acid nitrile dissolved. After the solution had been cooled to 15 ° C., 693 g of tridecyl chloroacetate were added with stirring Stirring was continued for 72 hours at 25 ° C. Analysis showed 100% Conversion to the quaternized ammonium chloride

6 g of the above solution were dissolved in 280 g of water and a mixture of 80 g of ethyl acrylate, 10 g of butyl acrylate and 7 g of acrylonitrile were added to this with stirring. The pH of the emulsion obtained was ■) between 5.0 and 5.5. The emulsion was cooled to 17 ° C, whereupon the polymerization was initiated and maintained using H ₂ O ₂ and a reducing agent as in Example 10 below. No coagulum was formed in the resulting polymeric emulsion and the yield was 92% of theory.

Example 2

Manufacture and use of the

Methacryioyioxyäthyidirnethyi-dodecyloxy-

carbonylmethylammonium chloride

15.9 g of dimethylaminoethyl methacrylate and 26.6 g of Dodecyichioracetat were stirred in 45 g of ethyl acetate at room temperature. After stirring for a short time, the white, crystalline, solid quaternary ammonium compound formed which was separated.
3.0 g of this quaternary compound was in 350 g

2 ", dissolved water and a mixture of 10 g of ethyl acrylate and 73.6 g of 2-ethylhexyl acrylate were added with stirring. The pH of the emulsion obtained was 6.0. It was cooled to 18 ° C and the polymerization as in Example 10 initiated and maintained. the

The polymer yield was about 90%.

Example 3

Manufacture and use of the
Allyloxycarbonylmethyldimethyl-hexadecyl- ³ 'ammonium chloride

13.5 g of allyl chloroacetate became 26.9 g with stirring Dimethylhexadecylamine in 40 g of dimethylformamide was added. At first two layers formed

■ in was, however, with continued stirring for 16 A clear, light yellow homogeneous solution is obtained at 25 ° C for hours. It was left for 6 days and the solvent is then removed under vacuum at 40.degree. The solid obtained was with > Ethyl ether washed and dried The product was somewhat fatty and the analysis showed a chloride content of 97% of the theoretical value.

55 g of vinyl acetate and 45 g of butyl acrylate were made using 3% by weight of the above monomer

-) 0 ren emulsifier, based on the weight of vinyl acetate and butyl acrylate dissolved in 280 g of water emulsified. The polymerization was _{initiated and maintained using H 2} O ₂ and the reducing agent. The polymer yield was 83%.

Example 4

Manufacture and use of
Allyl dodecylmorpholinium bromide

913 N coconut morpholine and 45 g allyl bromide were made stirred in 306 g of water at 25 ° C. for 24 hours. The clear, colorless solution contained 96% of the theoretical yield of the quaternized ammonium salt.

5 g of the above 30% aqueous solution was dissolved in 1000 g of water and a mixture of 160 g of ethyl acrylate, 20 g of acrylonitrile and 20 g of butyl acrylate were added with stirring

Emulsion was made using 0.3 g of t-butylperoxymaleic acid and 4.1 g of a ferrous ammonium sulfate ascorbic acid reducing solution polymerized. The yield of the polymer was 96% of theory.

Example 5

Manufacture and use of
3- (4-hydroxymaleoyl) aminopropyI-dimethyltridecyloxycarbonylmethylammonium chloride

This quaternary connection was established in two stages. 20.4 g of dimethylaminopropylamine were mixed with 55.4 g of tridecyl chloroacetate in 75.8 g of acrylonitrile. After 72 hours at 25 ° C, 90% of the theoretical chloride content found in the quaternized Saiz. The solution was cooled and 19.6 g Crushed maleic anhydride added, cooling to keep the exothermic reaction below To keep 22 ° C. The analysis showed chloride ions in an amount of 100% of theory.

6 g of the above solution were dissolved in 280 g of water and a mixture of 80 g of ethyl acrylate, 10 g of butyl acrylate and 7 g of acrylonitrile were added with stirring. The emulsion obtained, with a pH of 4.0 to 4.5, was cooled and the polymerization was initiated and maintained _{by the H 2 O 2 reducing agent system described in Example 10.} Less than 1% coagulum was formed and the yield of the polymer was 92%.

Example 6

Manufacture and use of the

Vinyloxyethyl-dimethyl-p-dodecylbenzyl-

ammonium chloride

11.5 g of dimethylaminoethyl vinyl ether and 29.5 g p-Dodecylbenzyl chloride were added to 41 g of acrylonitrile stirred at 25 ° C for 24 hours. The chloride found in the analysis was completely quaternized.

2.5 g of the above solution was dissolved in 700 g of water. A mixture of 200 g of ethyl acrylate, 25 g Butyl acrylate and 24 g of acrylonitrile were added with stirring. The emulsion obtained was under Use a total of 35 g of 3% H2O2 and 11 g of the reducing agent solution according to the example 10 polymerized. No coagulum was formed and the polymer yield was 91% of theory.

Example 7

Manufacture and use of the

S-methylacryloyloxy ^ -hydroxypropyl-dimethyl-

octadecylmethylammonium sulfate

Equimolar amounts of N-methyl-N-octadecylamine and glycidyl methacrylate were reacted together in methanol to methacryloyloxyhydroxypropylmethyloctadecylamine. 14.3 g of the amine obtained were in Dissolved 20 g of dimethylformamide and slowly added 4.2 g of dimethyl sulfate with stirring. It was 10 days at Left to stand at 25 ° C and then 9 g of crystalline material isolated, washed with ether and dried. The sulfate band of the crystalline product was identified in the infrared spectrum

2 ^ 5 g of the above stabilizer were dissolved in 290 g of water. 75 g of ethyl acrylate were added with stirring. The polymerization was initiated and maintained with the usual HiOz reducing agent system . Less than 1 g of coagulate was formed and the polymer yield was 96% of theory.

Example 8

Manufacture and use of the
Allyl hexadecyl dimethylammonium fluoride

Allyl-hexadecyl-dimethylammonium chloride was produced by reacting allyl chloride and dimethylhexadecylamine. 17.8 g of the chloride in one 23.5% aqueous solution were with a stoichiometric excess of AgF in aqueous Solution treated until analysis of the filtrate shows only traces of chloride ions present showed. The excess of silver ions was removed by careful addition of NaCl, the AgCl was filtered off.

64 g of ethyl acrylate, 8 g of butyl acrylate and 8 g of acrylonitrile were emulsified by slow addition with stirring to 2.4 g (3% by weight) of the allylhexadecyldimethylammonium fluoride in 120 g of water. The pH of the emulsion was about 6.0. The emulsion was cooled to 20 ° C. and 10 g of 3% strength aqueous H ₂ O _{2 were} added, whereupon the reducing agent solution according to Example 10 was added dropwise until the polymerization was initiated after addition of 5 g of the reducing agent. The exothermic development of heat was 10 ^° C. in 13 minutes. A total of 14 g of the reducing agent and 13 g of aqueous H ₂ O ₂ were used until the polymerization was complete. No coagulum was formed and the polymer yield was 95%.

Example 9

Manufacture of the
Allyl-hexadecyl-dimethylammonium iodide

16.8 g of allyl iodide were dissolved in 44.6 g of ethyl acetate and 27.8 g of dimethylhexadecylamine were slowly added with stirring at room temperature. 15 minutes after the addition of the amine had ended, the viscosity of the solution rose and crystallization took place. After 24 The crystals were filtered off for hours, washed with ethyl acetate and dried. The colorless, crystalline Product contained 88% of the theoretical amount of iodide ions.

Production of monomers

Emulsion stabilizers that differ from alkyl

or derive alkenyl succinic anhydride

As indicated above, the lipophilic group R3 can be covalently attached to the nitrogen atom via a Hydroxysuccinyloxy or hydroxysuccinylamino group be bound. Various inexpensive procedures are available for the production of such monomers, for example

1. Reaction of an alkyl or alkenylsuccinic anhydride with a tertiary amino alcohol or amine, an intermediate product is obtained, which is then reacted with a monomer containing an active halogen atom, 6G and a monomeric emulsion stabilizer, wherein X is halide.Alternatively, a tertiary Aminoamine are first quaternized by a suitable ethylenically unsaturated halide, whereupon the reaction with the alkyl or alkenyl succinic anhydride takes place

2. Quaternization of a vinyl monomer, the one contains tertiary amine group, by a halogen

alcohol or amine, whereupon the reaction with the alkyl or alkenyl succinic anhydride takes place. 3. Reaction of an alkyl or alkenylsuccinic anhydride with a tertiary amino alcohol or amine containing vinyl groups, whereupon quaternization takes place in the usual manner.
All of the compounds of the formula above can be prepared by the above methods, with the exception of those in which Ri and R ₂ together form part of a morpholine or piperidine ring.

The following examples illustrate the preparation of monomeric emulsion stabilizers, in which the lipophilic Group R3 to a nitrogen atom via a hydroxysuccinyloxy or hydroxysuccinylamino group is bonded

Example 10

7.7 g of allyl chloride were gradually added at 25 ^° C. to a solution of 8.9 g of dimethylaminoethanol in 16.6 g of acetonitrile. The clear solution obtained was kept at 25 ° C. for 25 hours; after this period the solution had crystallized. 21.2 g octenyl succinic anhydride were then added to the mixture crystallized and the resulting mixture heated at 50 ⁰ C for 5 hours and obtain a homogeneous solution. The solvent was removed in vacuo to give a dark, orange-brown viscous liquid. The potentiometric titration for carboxyuons showed that the allyldimethyl-octenylhydroxysuccinyloxyethylammonium chloride had been obtained.

120 g of ethyl acrylate, 15 g of butyl acrylate and 15 g of acrylonitrile were placed in a 4-neck resin kettle equipped with a thermometer, stirrer, nitrogen inlet and dropping funnel. To an amount of 4.5 g of the monomeric emulsion stabilizer described in the preceding paragraph, dissolved in 425 g of water, the monomer mixture was added under nitrogen. The pH of the emulsion obtained was 4.0 to 4.5. After cooling to 20 ⁰ C using an ice bath, 15 ml of 3% H2O2 in water were added to the emulsion and added dropwise a reducing agent solution consisting of 0.02 g of iron (II) ammonium sulfate and 0.4 g ascorbic acid in 10 ml of water is added . The polymerization began after 2.5 ml of the reducing agent solution had been added, which was indicated by an exothermic heat build-up of about 29 ° C. in 10 minutes. A total of 9 ml of the reducing agent solution was added until the end of the polymerization was indicated by the cessation of the exothermic evolution of heat upon further addition of a small amount of H2O2 and reducing agent. The yield of the polymer was 95% of theory and no coagulate was formed

Example 11

7J g of allyl chloride were slowly added with stirring to a solution of 8.9 g of dimethylaminoethanol in 16.6 g of acetonitrile. The reaction solution crystallized after it had been left to stand at room temperature for 24 hours. A solution of 26.7 g of n-dodecenylsuccinic anhydride in 26.7 g of acetonitrile was then added and the mixture was kept at 50 ° C. for 5 hours and a clear, homogeneous solution was obtained. The solvent was removed in vacuo and a viscous, orange liquid was obtained. The potentiometric titration for carboxyl ions showed that the allyl-dimethyl-n-dodecenylhydroxysuccinyloxyethylammonium chloride had been obtained.

Example 12

102 g of dimethylaminoethanol were slowly added at 17 ° C. to a solution of 88.3 g of allyl chloride in 500 g of acrylonitrile. After 90 minutes, an exothermic evolution of heat of 26 ° C. was observed. The solution was then cooled to 35 ° C, was carried out at this temperature for crystallization, which gave an exotherm of 1O ⁰ C. Tetrapropenylsuccinic anhydride, which is an alkenylsuccinic anhydride with an average of 12 carbon atoms and one carbon-carbon double bond, was added to the crystallized mixture in an amount of 310 g: after 45 minutes a clear, homogeneous solution was obtained. This solution was left to stand for 48 hours. By analyzing the chloride ions, it was found that the allyl-dimethyltetrapropenylhydroxysuccinyloxyethylammonium chloride had been obtained.

Example 13

A solution of 29.5 g of n-tetradodecenylsuccinic anhydride in 29.5 g of acetonitrile was added to the reaction product of 8.9 g of dimethylaminoethanol and 7.7 g of allyl chloride in 16.6 g of acetonitrile, as described in Example 10, and the resulting mixture heated from 55 ⁰ C for 4 hours. Removal of the solvent in vacuo gave 42.6 g of a fatty, pale white solid. The analysis of the carboxyl ions showed that the allyl-dimethyln-tetradodecenylhydroxysuccinyloxyethylammoniumchlorid had been obtained.

Example 14

In accordance with the procedure according to Example 13, 35.6 g of isooctadecenylsuccinic anhydride were added added to the reaction product of dimethylaminoethanol and allyl chloride in acetonitrile. After 5 hours at 55 ° C., the solvent was removed in vacuo and a viscous, orange-colored liquid was obtained. The analysis of the carboxyl ion content confirmed that the allyl-dimethyl-isooctadecenylhydroxysuccinyloxyethylammonium chloride had been received.

A mixture of 120 g of ethyl acrylate, 5 g of butyl acrylate and 15 g of acrylonitrile in 425 g of water was emulsified using 4.5 g of allyl dimethyl isooctadecenylhydroxysuccinyloxyethylammonium chloride. The emulsion, which had a pH of 4.5 to 5.0 , was cooled slightly below room temperature. 15 ml of a 3% H2O ₂ solution were then added and then the reducing agent solution given in the preceding examples was added dropwise. A total of 7 ml of the reducing agent solution was used in the polymerization; no coagulum was formed and the yield of the polymer was 93% of theory.

Example 15

83 g of dimethylaminoethanol were added to 9.06 g of methallyl chloride in 44.6 g of acetonitrile. The mixture was left to stand for 24 hours at room temperature and a clear, homogeneous solution was obtained Addition of 26.6 g of tetrapropenylsuccinic anhydride resulted in an exothermic reaction. The solvent was removed in vacuo and a viscous, liquid one

ί3

Product received. The analysis of the carboxyl ion content confirmed that the methallyl-dimethyltetrapropenylhydroxysuccinyloxyethylammonium chloride had been received.

Example 16

6.02 g of vinyl chloroacetate were added to the reaction product of 4.5 g of dimethylaminoethanol and 17.8 g Isooctadodecenylsuccinic anhydride in 27 g of dimethylformamide was added. The reaction mixture was left to stand at room temperature for 24 hours and a homogeneous solution was obtained. The analysis on Chloride ions resulted in the Vinylacetoxy-dimethylisooctadecenylhydroxysuccinyloxyäthylammoniumchlorid had been received.

A mixture of 120 g of ethyl acrylate, 15 g of butyl acrylate and 15 g of acrylonitrile was mixed with 425 g of water and 6.6 g of a vinylacetoxy-dimethyl-isooctadecenylhydroxysuccinyloxyethylammonium chloride solution (68

% By weight in dimethylformamide) emulsified. The emulsion obtained with a pH of 4.5 was cooled ^{to 18 ° C.} The polymerization was initiated by adding 15 ml of 3% H2O2 in water, followed by the dropwise addition of 2.2 ml of the reducing agent solution given in the preceding examples, a total of 8 ml of the reducing agent solution was used for the polymerization. No coagulum was formed and the yield of the polymer was 94% of theory.

Example 17

20.4 g of dimethylaminopropylamine were added to 15.3 g of allyl chloride dissolved in 35.7 g of acetonitrile. the The reaction was carried out at the temperature of the ice bath. After 24 hours at room temperature 53.2 g of tetrapropenyl succinic anhydride was slowly added to the reaction solution with stirring. After removal of the solvent, the product was obtained, which is 96% of the theoretical Carboxyl ion content of allyl-dimethyltetrapropenylhydroxysuccinylaminopropylammonium chloride Has

Example 18

15.7 g of dimethylaminoethyl methacrylate were added to a solution of 12.5 g with stirring at room temperature 2-bromoethanol in 28.2 g of acetonitrile was added. A slight exothermic reaction occurred. The reaction solution was left to stand for 4 days. Then, 26.6 g of tetrapropenyl succinic anhydride was added to the Solution added. A slightly exothermic reaction occurred. The reaction mixture was at Left to stand room temperature for 24 hours, whereupon the analysis of carboxyl ions showed that the methacryloyloxyethyl-dimethyl-tetrapropenylhydroxysuccinyloxy- ethylammonium bromide had been obtained.

100 g of ethyl acrylate and 290 g of water were added to 4.5 g of the above monomeric emulsion stabilizer solution (66% by weight in acetonitrile). The emulsion obtained with a pH of 4.5 was cooled to 17 ° C. and the polymerization was carried out by addition of 10 ml of a 3% H ₂ O ₂ -LoSUHg and then of 2 ml of the reducing agent solution according to the preceding examples. A total of 3 ml of the reducing agent solution was used in the polymerization. No coagulate was formed and the yield of the polymer was 95% of theory.

Example 19

According to the procedure of Example 18, 11.5 g of dimethylaminoethyl vinyl ether were added at room -> added temperature to a solution of 12.5 g of 2-bromoethanol in 24.3 g of acetonitrile. The implementation was slightly exothermic. The reaction mixture was left to stand at room temperature for 4 days and a clear, homogeneous solution was obtained. to

in this solution was 26.8 g of tetrapropenyl succinic anhydride admitted. Ciieses reaction mixture was left to stand at room temperature for 48 hours, whereupon the analysis for carboxyl ions showed that the Vinyloxyäthyl-dimethyltetrapropenylhydroxysuccij nyloxyäthylammoniumbromid had been obtained.

Example 20

6.73 g of allyl chloroacetate were added to the reaction product of 4.5 g of dimethylaminoethanol and 17.8 g Isooctadodecenylsuccinic anhydride in 27 g of dimethylformamide was added. Analysis for chloride ions showed that the Allylacetoxydirnethyl-isooctadecenylhydroxysuccinyloxyäthylammoniumchlorid had been received.

Example I 21

A solution of 26.6 g of tetra propenyl succinic anhydride in 25 g of dimethylformamide was slow with stirring at 25 ° C to a solution of 13.1 g of hydroxyethylmorpholine in 20 g of dimethylformamide added. The reaction was exothermic and a pale orange-brown, homogeneous solution was obtained, which showed 93% of the theoretical carboxyl ion content. 10.9 g of allyl bromide was added to the solution and the resulting mixture was allowed to stand at room temperature for 6 days. Analysis of the bromide ion content showed that the allyl-tetrapropenyl-hydroxysuccinyloxyäthylmorpholiniumbromid had been received.

Example 22

A solution of 26.6 g of tetra-propenysuccinic anhydride in 25 g of dimethylformamide was slowly added with stirring at 25 ° C. to a solution of 83 g of dimethylaminoethanol in 10 g of dimethylformamide. The reaction was exothermic and after 24 hours gave a clear, homogeneous solution which showed 100% of the theoretical carboxyl ion content. An equimolar amount of 2-bromoethanol was added to this solution at 25 ° C. with stirring. The reaction was slightly exothermic. The reaction mixture was allowed to stand for 5 days at 25 ° C and then treated 3 '/ 2 hours at 45 to 50 ⁰ C, after which 82% of the theoretical bromide ion were detected. An equimolar amount of maleic anhydride was added to this solution; the addition was carried out with stirring at room temperature. After 24 hours at room temperature, the analysis of carboxyl ions indicated that 2- (4-hydroxymaleoyl) -oxyethyldimethyldodecenyl-hydroxysuccynyloxyethylammonium bromide had been obtained.

Production of monomers

Emulsion stabilizers, where X is a complex

Represents anion

As indicated above, the radical X can des anionic portion of the products according to the invention. be of a complex nature. Such stabilizers are produced by initially using a monomeric

Emulsion stabilizer, in which X is a halide, is prepared according to the methods given above. The Halogesid is then with an alkali or Ammonium alkyl sulfate, an alkali or ammonium alkyl benzene sulfonate, an ammonium phenoxy (or -alkylphenoxy) -2lkylene- (or polyalkyleneoxyalkylene-) sulfate, an alkali or ammonium dialkyl sulfosucdnate or an alkali or ammonium alkyl phosphate implemented, for example with

Sodium heptyl sulfate,

Sodium octacosyl sulfate

Sodium isooctyl sulfate,

Sodium oleyl sulfate,

Sodium dodecylbenzenesulfonate,

Di-tetradecyl sodium sulfosuccinate,

Dimethyl sodium sulfosuccinate,

Sodium dimethyl phosphate,

Sodium octadecyl phosphate or

Sodium di-2-ethylhexyl phosphate.
The production and use of monomeric emulsion stabilizers with complex groups X is explained in the following examples:

Example 23

AUyl-hexadecyl-dimethylammonium chloride was by reacting allyl chloride with dimethylhexadecylamine prepared 15.1 g of an aqueous solution of Allyl-hexadecyldimethylammonium chloride, the 23.5 % By weight of the chloride contained, and 2.88 g of dodecyl sodium sulfate were added to 50 g of water for 48 hours Treated room temperature and the allyl hexadecyldimethylammomumdodecyl sulfate obtain.

22.5 g of this monomeric emulsion stabilizer solution in 275 g of water were placed in a 4-neck resin kettle equipped with a thermometer, stirrer, nitrogen inlet and dropping device. 75 g of vinyl acetate were added to this solution under nitrogen, whereupon the pH of the emulsion obtained was 4.5. It was cooled to 19 ° C. and 10 ml of 3% H ₂ O ₂ in water were added to the emulsion, whereupon a reducing agent solution of 0.02 g of ferrous ammonium sulfate and 0.4 g of ascorbic acid in 10 ml of water was added dropwise was added. The polymerization started after 0.8 ml of the reducing agent solution had been added, which was indicated by an exothermic evolution of heat of about 28 ° C. in 10 minutes. A total of 10 ml of the reducing agent solution and 15 ml of H ₂ O ₂ were added until the end of the polymerization, which was indicated by the absence of exothermic heat generation when small amounts of H ₂ O ₂ and reducing agent solution were further added. The yield of the polymer was 89% of theory and no coagulate was formed

2 e i s ρ i e I 24

Allyl-dimethyl-dodecenylhydroxysuccinyloxyethylammonium chloride was by reacting allyl chloride with dimethylaminoethanol in acetonitrile and subsequent reaction with dodecenylsuccinic anhydride in acetonitrile. 43.2 g of this Compound were treated with 32.2 g of sodium dodecylbenzenesulfonate in 300 ml of acetonitrile for 24 hours Shaken room temperature. The resulting precipitate was filtered off, washed with acetonitrile and dried. After the acetonitrile had been removed, 64.5 g of allyl dimethyl dodecenylhydroxysuccinyloxyethylammonium dodecylbenzenesulfonate were obtained obtain.

A mixture of 280 g of ethyl acrylate, 35 g of acrylonitrile and 35 g of butyl acrylate in 843 g of water was emulsified using 157 g of an aqueous solution containing 10.5 g of allyl-dimethyl-dodecenylhydroxysuccinyloxyethyl-> ammonium chloride. The pH of the initial Emulsion was about 4.5. It was cooled to 16 ° C and 35 ml of a 3% solution of H ₂ O ^ in water were added, whereupon the reduction given in the previous examples

H) medium solution was added. The polymerization began after the addition of 15 ml of the reducing agent solution.

The percentage by weight of the monomeric emulsion stabilizer used to stabilize the

ΐϊ Polymerization of other ethylenically unsaturated Monomers used depends on the nature of the latter. In general, 0.1 to 10 wt .-% of the stabilizer, preferably 1 to 5%, is used when ethyl acrylate is the main monomer

2i> , generally 0.5% of the emulsion stabilizer gives a satisfactory polymerization. in the

In the case of 2-ethylhexyl acrylate, the amount of stabilizer should be increased to 3 to 5%.

Ethylenically unsaturated monomers that are used for copo-

2i lymerisation π it the monomeric emulsion stabilizers Suitable according to the invention include vinyl acetate, vinyl chloride, acrylonitrile and acrylic monomers according to the formula

CH ₂ = C-COOR ₇

wherein Rt, a hydrogen atom or a methyl group and R? denote a saturated alkyl radical having 1 to 14 carbon atoms. As is well known, she takes Softness of the polymer and the difficulty of initiating polymerization with an increase in the Number of carbon atoms in the ester group increases. When the acrylic monomer has more than 8 carbon atoms contains in the ester group, it is advantageous to mix it with at least 20% of an acrylic ester which contains less than 4 carbon atoms in the ester group to initiate the polymerization and the Increase the stability of the dispersion. Esters in which the ester group contains 1 to 4 carbon atoms, are therefore preferred.

Mixtures of more than one ethylenically unsaturated monomer of the formula above can be used as Emulsion stabilizers are used, and to achieve special properties, such as toughness, or rigidity To maintain crosslinking reactivity of the polymer, a minor proportion, usually less than 20 mol%, of the main monomer by another ethylenically unsaturated monomer, such as Vinyl esters, for example vinyl laurate or vinyl stearate, vinyl ethers, for example vinyl methyl ether, vinyl ethyl ether or vinyl butyl ether, diunsaturated monomers, for example diethylene glycol diacrylate, ethylene glycol diitaconate, Diallyl phthalate or divinylbenzene, acrylic acid or methacrylic acid, acrylamide, methacrylamide, Hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate or styrene replaced will.

In the examples above is the application

b5 of the emulsion stabilizers with batch processing described, but their use is equally good for continuous polymerization possible.

130 266/22

Claims (3)

Patent claims: 1. Process for the emulsion polymerization of an ethylenically unsaturated monomer in the presence an emulsion stabilizer, characterized in that as an emulsion stabilizer in an amount of 0.1 to 10.0% by weight of an ethylenically unsaturated quaternary ammonium compound, which is copolymerized to form part of the polymers, represented by the following formula V
A. R ₁ -N ⁺ X- is used, in which V is one of the following ethylenically unsaturated radicals:
a) acid ester groups or acid amide groups according to the formulas HO-CO-CH = CH-COO- HO - CO - CH = CH - CONH -
HO-CO-CH = C (CHj) -COO-HO-CO-CH = C (CHj) -CONH- ^j "HO - CO - CH ₂ -C-COO- CH ₂ or ^r> HO-CO-CH ₂ -C-CONH- 40 CH ₂ b) Acrylic ester groups or acrylamide groups according to the formulas CH ₂ = CR ₄ -COO- and
CH ₂ = CR ₄ -CONH-, wherein R _{4 represents} a hydrogen atom or a methyl group, c) allyl, methallyl, vinyloxy, allyloxy, methallyloxy, vinylacetoxy, allylacetoxy or methallylacetoxy groups, A, which is missing if V is an allyl, methallyl, vinylacetoxy, allylacetoxy or methallylacetoxy group represents, and otherwise an ethylene, propylene, hydroxypropylene, acetoxypropylene, isopropylene group or grouping -0-CH ₂ -CHR ₄ - (O-CH ₂ -CHR ₄ ) ,, -, where R «is a hydrogen atom or a methyl group and π is the numbers O, 1, 2, 3 or 4, indicates the quaternary nitrogen group N ⁺ Rt R ₂ R ₃ bo a) aliphatic tertiary amines, where Ri is an alkyl or benzyl group 1 to 7 coal Substance atoms and R ₂ either an alkyl or benzyl group with 1 to 7 carbon atoms or one of the groups R ₅ -O-CO-CH ₂ - or
R ₅ -NH-CO-CH- represents wherein R5 is a hydrogen atom or indicates an alkyl group having 1 to 4 carbon atoms, or Groups in which N, Ri and R ₂ together form part of a heterocyclic tertiary amine of the formulas or —N +
- N form, R3 is a lipophilic radical, which is an aliphatic hydrocarbon chain with 7 to Contains 28 carbon atoms, this hydrocarbon chain L covalently attached to the Nitrogen atom attached either directly or through one of the following intermediate bonds is: a benzyl group, an ester group, a polyalkylene oxide group, an alkylacetoxy group or an alkylacetamido group, an alkylalkylene ether group, an alkylamide group, a hydroxysuccinyloxy group R ₈ -O-CO-CH (L) -CH ₂ -COOH,
a hydroxysuccinylamino group R ₈ -NH-CO-CH (L) -CH ₂ -COOh,
wherein Rs indicates a divalent radical, or -0-CH ₂ -CHR ₉ (O-CH ₂ -CHR ₉ ) ,,, wherein R _{9 is} a hydrogen atom or a methyl group and η is the numbers 0.1, 2, 3 or 4, or an isomer of the above hydroxysuccinyloxy or hydroxysuccinylamino groups, in which the hydrocarbon group L is bonded to the carbon atom adjacent to the carboxyl group, the aliphatic hydrocarbon chain L is linear or branched, saturated or unsaturated, and X- represents one of the radicals (a) F-, CI-, Br-, I-, CH3SO ₄ -, C ₂ H ₅ SO ₄ -, CHj- or (b) an alkyl sulfate in which the alkyl moiety contains 7 to 28 carbon atoms, an alkylbenzenesulfonate, wherein the alkyl moiety contains 7 to 12 carbon atoms, a phenoxy (or alkylphenoxy) alkylene (or polyalkyleneoxyalkylene j sulfate the formula R "-C ₆ H ₄ O- (CH ₂ -CHR"'- O) _n -CH ₂ - CHR "' SO ₄ -, where R "represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R '" represents a hydrogen atom or a methyl group and η represents the number zero or an integer, a dialkyl sulfosuccinate group in which the alkyl groups have 1 to 24 carbon atoms atoms, or an alkyl phosphate group in which the alkyl group has 1 to 18 carbon atoms has mean, where, if X- has the meaning (b), R3 has a lipophilic radical with represents a hydrocarbon chain of 8 to 28 carbon atoms 2. The method according to claim 1, characterized in that that a compound is used as a monomeric emulsion stabilizer in which X- F-, Cl-, Br-orl- means 3. The method according to claim 2, characterized in that the monomeric emulsion stabilizer used is a compound in which V is an allyl, methallyl, vinyl acetoxy, allylacetoxy or methallylacetoxy group and the quaternary nitrogen group is N + Ri R ₂ R3 (a) aliphatic tertiary amines, in which Ri and R _{2 represent} alkyl groups having 1 to 4 carbon atoms, or (b) Groups in which N, Ri and R _{2 are} part of a heterocyclic tertiary amine of the formulas