DE2051479A1 - Process for polymerization and here for suitable monomeric emulsion stabilizers - Google Patents

Description

PA 29 ks

tDHE KEHHIALL COMPAHY 225 Franklin Street, Boston Mass., V.St.A.

Polymerization processes and monomeric emulsion stabilizers suitable therefor

Polymeric latexes derived from ethylenically unsaturated monomers are widely used in a variety of applications used for purposes, for example as an adhesive mass and as a binder for non-woven ifticher or wiri-fiber fleeces. The usual polymeric latexes are made by emulsion polymerization; H. by polymerization of monomers Materials while kept dispersed in an aqueous medium by a surfactant will. The surfactant can be anionic, for example a soap or liatric lauryl sulfate. on the other hand it can be nonionic, for example an ethylene oxide derivative or a polyhydroxy compound, or it can be cationic, for example an alkyl aromonium halide. The cationic agents are preferably used together with a nonionic agent in a better behavior used. The polymerization of the monomeric materials is also often in the presence of a water-soluble protective colloids or stabilizers

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guided. The use of a surfactant or a stabilizer results in the presence of water-sensitive constituents in the final product polymer latex. If the latex may need to be used, it is wet strength and durability against the influence of water are desired, for example as a coating for paper or during manufacture of non-woven cloths or non-woven fabrics and certain pressure-sensitive adhesive tapes, is the Presence of water-sensitive components in the polymeric mass undesirable.

The invention results in a new class of monomeric emulsion stabilizers, the quaternary Nitrogen atom covalently bound with an ethylenically unsaturated component and with a lipophilic group and ionically bound to an anionic group, which also act as a stabilizer for emulsion polymerization the ethylenically unsaturated monomers and serve as monomeric reaction participants in the polymerization, so that the salt becomes an integral part of the polymer, which is thereby stabilized by itself, without surface-active agents having to be used and which is free of water-sensitive components.

The invention results in a polymerization process in which ethylenically unsaturated monomers are combined copolymerized with a monomeric emulsion stabilizer of the formula

in which s

V an ethylenically unsaturated best of the following

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Classes:

a) Acid ester groups or acid amide groups of maleic acid, fumaric acid, citraconic acid or itaconic acid according to the formulas HO-CO-GH-GH-COO-, HO-CO-GH-CH-COM-, HO - «- CO-CH» C (GH, ) ~ COO-, HO-CO-CH-C (CH ₃ ) -CONH-, HO-CO-CH ₀ -C-COO- and HO-CO-Ch ₀ -CH-CONH-;

c ^GH 2

b) Acrylic ester groups or acrylamide groups of the formulas CH ₂ -CEn-COO- and CH ₂ -GE ^ -GONH-, where E ^ represents a hydrogen atom or a methyl group,

c) allyl groups, OH ₂ -CHJ-OH ₂ -, methallyl, CH ₂ -O (CEL) -CH ₂ -, vinyloxy, CH ₂ -CH-O-, allyloxy, CH ₂ -CH-CH ₂ -O-, Methallyloxy, CH ₂ -C (CH ₅ ) -CH ₂ -O-, vinyl acetoxy, GH ₂ -CH-O-CO-CH ₂ -, allylacetoxy, CH ₂ -CH-CH ₂ -O-CO-CH ₂ -; or methallylacetoxy groups, CH ₂ »C (0H ₃ ) -CH ₂ -O-CO-CH ₂ -,

where in the above formula the Eest A is absent if V is an allyl, methallyl, vinylacetoxy, allylacetoxy or Methallylacetoxygruppe, while otherwise A is a divalent Eest from the classes

a) Ethylene, -CH ₂ -CH ₂ -, propylene, -CH ₂ -CH ₂ -CH ₂ -, hydroxypropylene, -CH ₂ -CHOH-GH ₂ -, acetoxypropylene, -GH ₂ -CH-CH ₂ -,

0-COOH, 5

and isopropylene, -CH ₂ -GH (GH,), with ethylene, propylene, isopropylene and hydroxypropylene groups being preferred,

b) -O-CH ₂ -CHE ^ (0-CH ₂ -CHE ^) _n -, where η represents the numbers 0, 1, 2, 3 or 4 and E ^ represents a hydrogen atom or a methyl group.

S, a lipophilic Eest which contains an aliphatic ^ hydrocarbon chain with V to 28 carbon atoms, chains with 9 to 18 carbon atoms being particularly preferred, this hydrocarbon group being covalently bonded to the nitrogen atom either directly or through one of the following intermediate bonds, in which L represents a hydrocarbon group: a benzyl group, an ester group such as -CH ₂ -CHp-O-CO-L, a poly-

alkylene oxide group, for example CHR ^) ₁₁ -OL, where R ^, a water to ff atom or a methyl group and η is a number from 0 to 4, an alkylacetoxy or alkylacetamido group, such as -CH ₂ -CO-OL and -OH ₂ -OO-NHL, an _{alkylalkylene ether group such as -CH 2} -OL, an alkylamide group such as -CH ₂ -CH (CH ^) - HH-CO-L, a hydroxysuccinyloxy group Rq-O-CO-CH (L) -CH ₂ -COOH, a hydroxysuccinylamino group Rg-KH-CO-CH (L) -CH ₂ -COOH, where Ro indicates a divalent radical, preferably ethylene, propylene, isopropylene, 2-hydroxypropylene, acetoxypropylene, or -0-CH ₂ -CHRQ ( O-CH ₂ -CHRn) _n , where R _{n 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 attached to the Carboxyl group adjacent carbon atom is bonded, wherein the aliphatic hydrocarbon chain L can be linear or branched, saturated or unsaturated, R ^ preferred either an alkyl group with 1 to 7 carbon atoms or a benzyl group and R ₂ either an alkyl group with 1 to 7 carbon atoms or a benzyl group or one of the following groups Rc-O-CO-CH ₂ - and Rc-NH-CO-CH ₂ -, where R ₁ - indicates a water atom or an alkyl group with 1 to 4 carbon atoms, and preferably the radicals R _- . and R _{2 are} lower alkyl groups, in particular methyl groups,

where N, R. and R ₂ together also form a (part of a heterocyclic tertiary amine of the formulas

-N

can form and

X is one of the simple acid residues F ", Cl" ", Br", I ", CH, S07

^{1111 (1} CH - (~ Ö \ - SO · »" »of ^{which C1} ~» ^Br ~ "u ¹¹ * ³ · ^CH x ^S0 4 ~ before-3 \ / ^ ^

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are added, or on the other hand X is an alkyl sulfate, wherein the alkyl portion contains 7 to 28 carbon atoms Alkylbenzenesulfonate wherein the alkyl moiety is 7 to 12 carbon contains atoms, a phenoxy or alkylphenoxyalkylene or polyalkyleneoxyalkylene sulfate of the formula

where R "denotes a water atom or an alkyl group having 1" to 12 carbon atoms, R " ¹ denotes a hydrogen atom or a methyl group and η denotes zero or an integer, a dialkyl sulfosuccinate in which the alkyl group contains 1 to 24 carbon atoms, or an alkyl phosphate in which the alkyl group contains 1 to 18 carbon atoms, where R then: represents a lipophilic radical with a hydrocarbon chain of 8 to 28 carbon atoms.

Such complicated acid parts X are favorably produced by first adding a suitable monomer a simple portion X, for example a halide, is prepared and then the monomer with a suitable one Alkali or ammonium salt is reacted as follows is explained.

The monomeric emulsion stabilizers according to the above Formula can by reacting a corresponding ethylenically unsaturated alkylene halide with a tertiary amine containing a lipophilic group, or with a suitable ring compound containing the nitrogen atom contains in the ring, or by reacting a halogenated en compound which has activated halogen, with an ethylenically unsaturated compound which is a tertiary Amine group contains, are produced.

Illustrative production methods are the reactions between allyl chloride and dimethyldodecylamine or dimethylhexa-

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decylamin, between allyl bromide and N-coconut morpholine which the nitrogen atom in the morpholine ring covalently Mixture of saturated alkyl groups with an average of 12 carbon atoms bonded between dimethylallylamine and dodecyl chloroacetate and between maleic anhydride and the reaction product of dimethylamine ethanol and Lauryl bromide.

example 1

Production and use of Vinyloxyäthyl-dimethyl- ^ tridecyloxycarbonylmethylammoniumchlorids.

28.8 g of dimethylaminoethyl vinyl ether were dissolved in 98 g of acrylonitrile solved. After cooling the solution to 15 ° C., 69-3 g of tridecyl chloroacetate were added with stirring. Stirring was continued at 25 ° O for 72 hours. Analysis showed a 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 ° 0, whereupon the polymerization was initiated and maintained using HoO ^ and a reducing agent as in Example 10 below. No bagulate was formed in the polymer emulsion obtained and the yield was 92 % of theory.

Example 2

Production and use of Methacryloyloxyäthyldimethyl-dodecyloxycarbonylmethylammoniumchlorids.

15.9 g of dimethylaminoethyl methacrylate and 26.6 g of dodecyl chloroacetate were in 4-5 g of ethyl acetate at room temperature

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stirred. After stirring for a short time, formed the white, crystalline, solid quaternary ammonium compound that has been separated.

3.0 g of this quaternary compound were dissolved in 350 g of water and a mixture of 10 g of ethyl acrylate and 75 »6 g of 2-ethylhexyl acrylate was added with stirring. The pH of the emulsion obtained was 6.0. It was cooled to 18 ° G and the polymerization was initiated and maintained as in Example 10. The polymer yield was about 90 %.

Example 3

Production and use of allyloxycarbonylmethyldimethyl-hexadecylammonium chloride.

6 Allyl chloroacetate were added to 26.9 g of dimethylhexadecylamine in 40 g of dimethylformamide with stirring. Initially two layers formed, but continued stirring for 16 hours at 25 ° C. gave a clear, light yellow homogeneous solution. Ea was left to stand for 6 days and the solvent was then removed under vacuum at 40 ° G. The solid obtained was washed with ethyl ether and dried. The product was somewhat greasy 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 emulsified using 3% by weight of the above monomeric emulsifier based on the weight of vinyl acetate and butyl acrylate dissolved in 280 g of water. The polymerization was initiated and maintained using HgOg and the reducing agent. The polymer yield was 83 %,

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Example 4

Production and use of allyl dodecylmorpholinium bromide.

91 »3 β N-eocosmorpholine and 45 g of allyl bromide were stirred in 506 g of water at 25 ° for 24 hours. The clear, colorless solution contained 96 % of the theoretical yield of the quaternized ammonium salt.

5 g of the above 50% strength aqueous solution were 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 was added with stirring. The emulsion obtained was polymerized using 0.3 S tert-butylperoxymaleic acid and 4.1 g of a ferrous ammonium stilfate-ascorbic acid reducing solution. The yield of the polymer was 96 % of theory.

Example 5

Production and use of 3 ~ (4-hydroxymaleoyl) aminopropyl-dimethyl-tridecyloxycarbonylmethylammonium chloride.

This quaternary connection was established in two stages. 20.4 g of diethylaminopropylamine 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 chlorine content was found in the quaternized salt. The solution was cooled and 19.6 grams of comminuted maleic anhydride was added, cooling to keep the exothermic reaction below 22 ° 0. The analysis showed chloride ions in an amount of 100 % of theory.

6 g of the above solution was dissolved in 280 g of water and a mixture of 80 g of ethyl acrylate, 10 g of butyl acrylate and 7 β acrylonitrile added with drilling. The received Eaulsion with a pH of 4.0 to 4.5 was made

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cooled and the polymerization initiated and maintained by the HpOp reducing agent system described in Example 10. Less than 1 % ebagulate was formed and the yield of the polymer was 92 %

Example 6

Production and use of vinyloxyethyl-dimethylp-dodecylbenzylammonium chloride.

11.5 g of dimethylaminoethyl vinyl ether and 29.5 g of p-dodecylbenzyl chloride were in 41 g of acrylonitrile at 25 ° 0 stirred 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 of butyl acrylate and 24 g of acrylonitrile was added with stirring. The emulsion obtained was polymerized using a total of 35 g of BE 3% strength EUOp and 11 g of the reducing agent solution according to Example 10. No bagulate was formed and the polymer yield was 91% of theory.

Example ?

Production and use of 3-methacryloyloxy-2-hydroxypropyl-dimethyl-octadecylmethylammonium sulfate.

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

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2.25 g of the preparative 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 HpOp reducing agent system. Less than 1 g of eoagulate was formed and the polymer yield was 96 % of theory.

Example 8

Production and use of allyl hexadecyl dimethylammonium fluoride.

AHyl-hexadecyl-dimethylammonium chloride was obtained from IJm-P Settlement of allyl chloride and dimethylhexadecylamine produced. 17.8 g of the chloride in a 23.5% aqueous solution Solution were made with a stoichiometric excess AgF treated in aqueous solution until the analysis of the filtrate shows only traces of chloride ions showed. The excess of silver ions was removed by careful addition of NaCl, whereby 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 allylhexadecyldimethylammoöiuafluorids 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% total aqueous HgOg 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 heat development was 10 ° G 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 end of the polymerization. No coagulate was formed and the polymer yield was 95%

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Example 9

Manufacture of allyl-hexadecyl-dimethylainmoniumdodidB

16.8 g of AUyl ^ odid were dissolved in 44.6 g of ethyl acetate and 27.8 g of dimethylhexadecylamine slowly with stirring at room temperature admitted. 15 minutes after the addition of the amine had ended, the viscosity of the solution increased and crystallization increased took place. After 24 hours the crystals were filtered off, washed with ethyl acetate and dried. That colorless, crystalline product contained 88% of the theoretical amount of iodide ions.

Production of monomeric emulsion stabilizers, which derive from alkyl or alkeny succinic anhydride

As stated above, the lipophilic group E, be covalently bonded to the nitrogen atom via a hydroxy succinyloxy or hydroxysttccinylaaino group. Different favorable processes are available for the preparation of such monomers, for example

1. Implementation of an alkyl or alkenyl succinic anhydride with a tertiary amino alcohol or amine, whereby an intermediate product is obtained, which subsequently is reacted with a monomer containing an active halogen atom and a monomeric emulsion stabilizer yields, wherein Σ is halide. Alternatively, a tertiary aminoamine can first be quaternized by a suitable ethylenically unsaturated halide, whereupon the reaction with the alkyl or alkenyl succinic anhydride he follows.

2. Quaternization of a vinyl monomer that has a tertiary Aine group contains, through a haloalcohol or amine, followed by reaction with the alkyl or alkenyl succinic anhydride he follows.

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3 · Conversion of an alkyl or alkenyl succinic anhydride with a tertiary amino alcohol or amine containing vinyl groups, followed by quaternization in the usual way Way done.

All of the compounds of the formula above can be prepared by the above methods, except those in which B ,. and Ro together form part of a morpholine or Form piperidine ring.

The following examples illustrate the preparation of monomeric Eoaul si ons stabilizers in which the lipophilic group P IU 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 added. The clear solution obtained was kept at 25 ° C. for 25 hours; after this period the solution was crystallized. 21.2 grams of octenyl berastinic anhydride were then added to the crystallized mixture and the resulting mixture heated to 50 ° C during ^ Heated for 5 hours and obtain a homogeneous solution. The solvent was removed in vacuo leaving a dark, orange-brown viscous liquid was obtained. The potentiometric titration for carboxyl ions showed that the allyldimethyl-octenylhydroxysuccinyloxyäthylammoniumchlorid 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 with a thermometer, Stirrer, nitrogen inlet and dropping funnel was fitted. To an amount of 4.5 g of the monomeric emulsions described in the previous paragraph Stabilizer, dissolved in 425 g of water, was

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The monomer was added as a mixture. The pH of the emulsion obtained was 4.0 to 4.5. After cooling to 20 ° C. using an ice bath, 15 ml of 3% HpOo in water were added to the emulsion and 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. 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 ° O 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 HoOo and reducing agent. The yield of the polymer was 95 % of theory and no eoagulate was formed.

Example 11

7.7 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 was left to stand at room temperature for 24 hours. A solution of 26.7 g of r-dodecenylsuccinic anhydride in 26.7 S acetonitrile was then added and the mixture was kept at 50 ° G 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 diaethylaminoethanol were slowly added at 17 ° C a solution of 88.3 g of allyl chloride in 500 g of acrylic acid enitrile added, after 90 minutes an exotherm became

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Heat development of 26 ° 0 observed. The solution was then cooled to 35.degree. C., at which temperature crystallization took place, which resulted in an exothermic evolution of heat of 10.degree. Tetrapropenyl succinic anhydride, which is an alkenyl succinic anhydride having an average of 12 carbon atoms and a carbon-carbon double bond, was added to the crystallized mixture in an amount of 310 g of BU; 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-dimethyl-tetrapropenylhydroxysuooinyloxyethylammonium chloride ψ had been obtained.

Example 13

A solution of 29.5 g of n-Ietradodeoenylsuccinic 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 was added heated from 55 ° 0 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 k the allyl-dimethyl-n-tetradodecenylhydroxysuccinyloxyethylammonium chloride had been obtained _e

Example 14

Following the procedure of Example 13, 35.6 g of isoootadeoenylsuccinic anhydride were added to the reaction product of dimethylaminoethanol and allyl chloride in aoetonitrile. After 5 hours at 55 ° C., the solvent was removed in vacuo and a viscous, orange-colored Get liquid. Analysis of the carboxyl ion content confirmed that the allyl-dimethyl-ieoootadecenylhydroxysuooinyloxyethyl ammonium chloride had been obtained.

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A mixture of 120 g of ethyl acrylate, 15 g of butyl aerylate and 15 g of aoryl acid nitrile in 425 g of water was emulsified using 4.5 g of allyl-diaethyl-isooctadecenylhydroxysucoinyloxyethylaimnonium chloride. The emaleion, which had a pH of 4 _f 5 "to 5> 0, was cooled slightly below room temperature. 15 ml of a 3 # HgOg 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

8.9 g of dimethylaminoethanol were converted into 9 »06 g of methallyl chloride 6 g of acetonitrile were added in 44j. The mixture was left to stand for 24 hours at room temperature and a clear, get homogeneous solution. After adding 26.6 g of tetrapropenylsuccinic anhydride an exothermic reaction occurred. The solvent was removed in vacuo and a viscous, liquid product obtained. The analysis of the carboxyl ion content confirmed that the methallyl-dimethyltetrapropenylhydroxysuecinyloxyethylammonium chloride had been received.

Example 16

6.02 g of yinyl chloroacetate were added to the reaction product of 4.5 g of dimethylaminoethanol and 17.8 g of isooctadodecenylsuccinic anhydride added in 27 g of dimethylformamide. The reaction mixture was left at room temperature for 24 hours left to stand and a homogeneous solution obtained. The analysis for chloride ions showed that the vinylacetoxy-dimethyl-is ooctad e c enylhydroxysuc cinyloxyäthylammoniumohlorid had been received.

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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 a vinylacetoxy-dimethyl-iBoootadeeenylhydroxysuecinyloxyäthylainmoniuinohlorid solution (68 wt. # In dimethylformamide) emulsified. The emulsion obtained with a pH from 4.5 was cooled to 18 ° C. The polymerization was initiated by adding 15 »1 of 3% HgOg in water ι whereupon the dropwise addition of 2.2 ml of the reducing agent solution given in the preceding examples took place. A total of 8 ml of the reducing agent solution was used for the polymerization. It was no coagulate formed and the yield of the polymer was 94% of theory,

Example 17

20.4 g of dimethylaminopropylamine were converted into 15.3 g of allyl chloride, dissolved in 35.7 g of acetonitrile, added. 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 were obtained slowly added to the reaction solution with stirring, after removal of the Solvent, the product was obtained, which 96 # the theoretical carboxyl ion content of allyl-dimethyltetrapropenylhydroxysuccinylaminopropylammonium chloride fc had.

Example 18

15.7 g of dimethylaminoethyl methaorylate were added with stirring at room temperature to a solution of 12.5 g of 2-bromoethanol added in 28.2 g of acetonitrile. There was a minor occurrence exothermic reaction. The reaction solution was left to stand for 4 days. Then 26.6 g of tetrapropeny / succinic anhydride were added added to the solution. A slightly exothermic reaction occurred. The reaction mixture was left to stand at room temperature for 24 hours, whereupon the

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Analysis for carboxyl! on en showed that the Methaoryloyloxyäthyl-dimethyl-tetrapropenylhydroxysuccinyloxyäthylammoniumbromid had been received.

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 resulting emulsion with a pH of 4.5 was cooled to 17 ° C. and the polymerization was _{initiated by adding 10 ml of a 3 # H 2} O ₂ solution and then 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

Following the procedure of Example 18, 11.5 g of dimethylaminoethyl vinyl ether were obtained at room temperature A solution of 12.5 g of 2-bromoethanol in 24.3 g of acetonitrile was added. The reaction was slightly exothermic. The reaction mixture was allowed to stand at room temperature for 4 days and a clear, homogeneous solution was obtained. To this solution was added 26.8 g of tetrapropenyl succinic anhydride admitted. This reaction mixture was allowed to stand at room temperature for 48 hours, followed by analysis on carboxyl ions showed that the Vinyloxyäthyl-dimethyltetrapropenylhydroxysuocinyloxyäthylammoniumbromid had been received.

Example 20

6.73 g of allyl chloroacetate was added to the reaction product from 4.5 g of dimethylaminoethanol and 17.8 g of isooctadodecenylsuccinic anhydride added in 27 g of dimethylformamide. The analysis for chloride ions showed that the allylaeetoxy-

ORIGiNAL INSPECTED

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d ime thy 1- i sooctadec enylhydroxysue ο inyloxyäthylammoniu »- chloride had been obtained.

Example 21

A solution of 26.6 g of tetrapropenylsuccinic anhydride in 25 g of dimethylformamide was slowly added with stirring at 25 ° C. to a solution of 13.1 g of hydroxyethylmorpholine in 20 g of dimethylformamide. The reaction was exothermic and a pale orange-brown, homogeneous solution was obtained which showed 93% of the theoretical carboxylone content. 10.9 g of allyl bromide were added to the solution tk and the resulting mixture was allowed to stand for 6 days at room temperature. The analysis of the bromide ion content showed that the allyl-tetrapropenyl-hydroxysuccinyloxyethylmorpholinium bromide had been obtained.

Example 22

A solution of 26.6 g of tetrapropenylsuccinic anhydride in 25 g of dimethylformamide was slowly added with stirring at 25 ° C. to a solution of 8.9 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 Ψ. An equimolar amount of 2-bromoethanol was added to this solution at 25 ° C with stirring.The reaction was slightly exothermic whereupon 82 jC of the theoretical bromide ion content was determined. 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 for carboxyl ions indicated that the 2- (4-hydroxymaleoyl) -oxyethyldimethyldodecenyl-hydroxysucoinyloxyethylammonium bromide had been obtained.

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Production of monomeric emulsion stabilizers, in which X represents a complex anion

As indicated above, the radical X of the anionisohen Proportion of the products according to the invention τοη more complex Be nature. Such stabilizers are made by first a monomeric emulsion stabilizer, in which X is a halide, according to the methods given above The halide is then treated with an alkali or ammonium alkyl sulfate, an alkali or ammonium alkyl benzene sulfonate, an ammonium phenoxy (or alkylphenoxy) alkylene (or Polyalkyleneoxyalkylene -) - sulfate, an alkali or ammonium dialkyl sulfosuccinate or an alkali or ammonium alkyl phosphate, "for example with sodium heptyl sulfate, sodium otacosyl 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 manufacture and use of monomeric emulsion stabilizers ait complex groups X is explained in the following examples:

Example 25

Allyl-hexadecyl-dimethylammonium chloride was made by reaction made of allyl chloride with dirnethylhexadeoylamine, 15.1 g of an aqueous solution of allyl hexadeoyldimethylammonium chloride, which contained 23.5 Grew. # of the chloride and 2.88 g of dodeoyl sodium sulfate were in 50 g of water treated for 48 hours at room temperature and obtained the allyl hexadecyldimethylammonium dodecyl sulfate.

22.5 g of this monomeric emulsion stabilizer solution in 275 g of water were placed in a 4-neck resin kettle which was supplied with Thermometer, stirrer, nitrogen inlet and drip device

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was equipped. 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. The polymerization started after 0.8 ml of the reducing agent solution had been added, which was indicated by an exothermic heat build-up of about 28 ° C. in 10 minutes. A total of 10 ml of the reducing agent _{solution and 15 ml of HgO 2} were added until the polymerization was complete, 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 «

Example 24

Allyl-dimethyl-dodecenylhydroxysuccinyloxyethylammonium chloride was prepared by reacting allyl chloride with dimethylaminoethanol in acetonitrile and then reacting with dodecenylsuccinic anhydride in acetonitrile. 43.2 g of this compound were shaken with 32.2 g \ sodium dodecylbenzenesulfonate in 300 ml of acetonitrile for 24 hours at 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

A mixture of 280 g of ethyl acrylate, 35 g of aoryl acid nitrile and 35 g of butyl acrylate in 843 g of water was made using 157 g of an aqueous solution containing 10.5 g of des Allyl-dimethyl-dodeoenylhydroxysuccinyloxyethylammonium chloride contained, emulsified · The pH of the initial

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Emulsion was about 4.5. It was cooled to 16 ° C. and 35 ml of a 3 # strength solution of clay H ₂ O ₂ in water were added, whereupon the reducing agent solution given in the preceding examples was added dropwise. The polymerization began after the addition of 15 ml of the reducing agent solution.

The proportion by weight of the monomeric emulsion stabilizer used to stabilize the polymerization of other ethylenically unsaturated monomers 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 major monomer, resulting in allgeminen $ 0.5> of the emulsion stabilizer, a satisfactory polymerization. In the case of 2-ethylhexyl aerylate, the amount of stabilizer should be increased to $ 3 to $ 5.

Ethylenically unsaturated monomers which are used for copolymerization with the monomeric emulsion stabilizers according to the Suitable invention include vinyl acetate, vinyl chloride, acrylonitrile and acrylic monomers corresponding to the formula

CH ₂ = C - ₇ ,

where Rg is a hydrogen atom or a methyl group and R _{7 is} a saturated alkyl radical having 1 to 14 carbon atoms. It is known that the softness of the polymer and the difficulty of initiating polymerization increase with an increase in the number of carbon atoms in the ester group. If the acrylic monomer more than 8 carbon atoms in the Estergruppe, it is advantageous to vermisohen it with at least 20 $> a Acrylesters containing less than 4 carbon atoms in the Estergruppe to the polymerization initiate and increase the stability of the dispersion. Esters in which the ester group

109819/2055

205U79

- 22 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, and in order to obtain special properties, such as toughness, rigidity or crosslinking reactivity of the polymer, a smaller proportion, usually less than 20 mol%, of the main monomer by a further ethylenically unsaturated monomer, such as vinyl ester, for example vinyl laurate or vinyl stearate, vinyl ether, for example vinyl methyl ether, vinyl ethyl ether or vinyl butyl ether, diunsaturated monomers, for example diethylene glycol ψ diacrylate, ethyl glycolic acid, acrylic or methacrylic acid, acrylamide or acrylamide, diallyl. Methacrylamide, hydroxyethyl acrylate or methacrylate, hydroxypropyl aylate or methacrylate or styrene are replaced o

In the above examples is the use of the emulsion stabilizers described in the case of partial processing, but their application is also in the same way for a continuous polymerization is quite possible.

109819/2055

Claims (1)

205H79 - 23 patent claims 1. A method for polymerization, characterized in that that with ethylenically unsaturated monomers a monomeric emulsion stabilizer of the formula c © is polymerized, where V is one of the following ethylenically unsaturated Leftovers: a) Acid ester groups or acid amide groups according to the formulas HO-CO-CH = OH-COO-, HOJ-CO-CH = CH-CONH-, HO-CO-CH = C (CH ₅ ) -COO-, HO-CO-CH = C (CH ₅ ) -CONH-, HO-CO-CH ₀ -C-COO-, or HO-CO-CH ₀ -C-CONH-, ^ It ^C Il CH ₂ CH ₂ b) Acrylic ester groups or aorylamide groups corresponding to the formulas CH ₂ = CR ₄ -COO- and CH ₂ = CR.-CONH-, in which R. represents a hydrogen atom or a methyl group, c) allyl, methallyl, vinyloxy, allyloxy, methallyloxy, Vinylacetoxy, allylacetoxy or methallyla c e t oxy groups, A, which is missing if V is an allyl, methallyl, vinyl acetoxy, allylacetoxy or methallylacetoxy group and otherwise an ethylene, propylene, hydroxypropylene, aoetoxypropylene, isopropylene group or -0-CH ₂ -CHR _{4 group} - (O-CH ₂ -CHRa) _n "", in which R. represents a hydrogen atom or a methyl group and η represents the numbers 0, 1, 2, 3 or 4, indicates the quaternary nitrogen group N ⁺ R- R ₂ R ₅ a ) aliphatic tertiary amines, in which R _{1 is} an alkyl or beneyl group having 1 to 7 carbon atoms and R _{2 is} either an alkyl or benisyl group having 1 to 7 carbon atoms or one of the groups 1098 1 9/2055 205H79 RO-CO-CH ₂ - or E ₅ -HH-CO-CH-, in which Rc denotes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, b) groups in which H, E ₁ and E ₂ together form part of a heterocyclic tertiary amine of the formulas or forms, Ε, a propophilic Best with an aliphatic hydrocarbon chain of 7 to 28 carbon atoms, and X ~ one of the best (a) F ~ ", Cl"",Br"",I", CB ₅ SOT, C ₂ H ₅ SO ₄ "", CH ^ Y ^ - ^S0 3 ~ or (b) an alkyl sulfate, wherein the alkyl moiety contains 7 to 28 carbon atoms, an alkylbenzene sulfonate, wherein the alkyl moiety Contains 7 to 12 carbon atoms, a phenoxy (or alkylphenoxy) alkylene (or polyalkyleneoxyalkylene) sulfate of the formula E "-C ₆ H ₄ O- (CH ₂ -CHE" ¹ -O) _n -CH ₂ -CHH " ¹ SO ₄ ", where B "represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, B ^n> a hydrogen atom or a methyl group and η represents the number Full or an integer, a dialkylsulfosuccinate group in which the alkyl groups contain 1 to 24 carbon atoms, or an alkyl phosphate group in which the alkyl group has 1 to 18 carbon atoms, where, if X ~ has the meaning (b), R, a lipophilic best with a hydrocarbon chain of Means 8 to 28 carbon atoms. 1, η q κ 1Π / 7055 2. The method according to claim 1, characterized in gekennseich.net, that 0.1 Ws 1Q.0% by weight of the monomeric emulsion stabilizer with 99.9 "to 90.0 wt. 56 of the ethylenically unsaturated Monomers are copolymerized. 3. The method according to claim 1 or 2, characterized in that that the monomeric emulsion stabilizer used is a compound in which X is "a group F", 01 ", Br" or I * "" means · 4. The method according to claim 3, characterized in that the monomeric emulsion stabilizer used is a compound in which V is an allyl, methallyl, vinyl ethoxy, allyl ethoxy or methallylacetoxy group and the quaternary nitrogen nitrogen group N ⁺ R ,. Ep R3 (a) aliphatic tertiary amines, in which R .. and R2 Represent alkyl groups having 1 to 4 carbon atoms, or (b) Groups in which N, R ₁ and Rp are part of a heterocyclic tertiary amine of the formulas ) or form,
mean. Process according to claim 3 _f, characterized in that the monomeric emulsion stabilizer used is a compound in which V is an acryloyloxy, methacryloyloxy, vinyloxy or 4-hydroxymaleoyl group and the quaternary nitrogen group NR ₁ Rp R ™ a) aliphatic tertiary amines, in which R ₁ and Rp represent alkyl groups with 1 to 4 carbon atoms, b) Groups in which N, R ₁ and R ₂ together form the part of one ORIGINAL INSPECTED 1 π a β η / 2 ο 55 - 26 heterooyolous tertiary amines of the formulas or -H "form, mean. 6. Monomeric emulsion stabilizer eur stabilization the polymerization of ethylenically unsaturated monomers in a copolymerization reaction of the formula »7 R ₁ -N ⁺ X ", > l
R ₂ R ₃ wherein V is one of the following ethylenically unsaturated Leftovers: a) Acid ester groups or acid amide groups according to the formulas HO-CO-CHaCH-COO-, HO-CO-Ch = CH-CONH-, HO-CO-CH = C (CH ₅ ) -COO-, HO-CO-CH = C (CH ₅ ) -CONH-, HO-CO-CH ₀ -C-COO-, or HO-CO-CH ₀ -C-CONH-, CH ₉ CH ₉ la) aoryl ester groups or acrylamide groups accordingly the formulas CH ₂ = CR ₄ -COO- and CH ₂ = CH ₄ -CONH-, where R. is a hydrogen atom or a methyl group, c) allyl, methallyl, vinyloxy, allyloxy, methallyloxy, Vinylaoetoxy, allylaoetoxy or methallylaoetoxy groups, A, which is missing if V is an allyl, methallyl, vinyl acetoxy, allylacetoxy or methallylacetoxy group j and otherwise an ethylene, propylene, hydroxypropylene, acetoxypropylene, isopropylene group or group -0-CH ₂ -CHR ₄ - (O-CH ₂ -CHR.) _N -, where R. is a H) 9 B 1 9/2 0 5 5 205U79 Hydrogen atom or a methyl group and η represent the numbers 0, 1, 2, 3 or 4-, the quaternary nitrogen group H ⁺ R ^ E ₂ E, a) aliplia-fcisclie -tertiary AadLne, in front of R ^ an alkyl or bensyl group with 1 to 7 carbon atoms and E ₂ either an alkyl or benzyl group with 1 to 7 carbon atoms or one of the groups RO-CO-CH ₂ - or R _{5 represents} -MH-CO-CH-, where Rc denotes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, b) Groups in which Ϊ, R * and R ₂ together form a rope of a heterocyclic tertiary amine of the formula or form, R, represents a lipophilic radical with an aliphatic hydrocarbon chain of 7 to 28 carbon atoms,
and X "one of the radicals (a) F", Cl "*, Br", I ", (HUSO,", C ₂ H ₅ SO ₄ "", GE ^ \ ^ y ~ SO ₃ or (b) an alkyl sulfate, wherein the alkyl portion contains 7 to 28 carbon atoms, an alkylbenzenesulfonate in which the alkyl moiety contains 7 to 12 carbon atoms, a phenoxy (or Alkylphenoxy} alkylene (or polyalkyleneoxyalkylene) sulfate the Pormel R "-C ₆ H ₄ O-CCH ₂ -CHR" ■ -0) _n -CH ₂ -CHR ^MI SO ₄ ", where R "is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ^{nt is} a hydrogen atom or a methyl group and η is the number zero or one 1 fj 9 y 1 9, / 2 0 5 5 represent whole Zalil, a dialkyl sulfosucoinate group, wherein 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, a lipophilic radical with a hydrocarbon chain of Means 8 to 28 carbon atoms. 7 connection according to claim 6, characterized that X means "a group]? ~, oil", Br "or I" · 8. A compound according to claim 7, characterized in that that V is an allyl, methallyl, vinylaoetoxy, allyl-faoetoxy, or methallylacetoxy group and the quaternary nitrogen group N ⁺ R ₁ Rg R ₅ a) aliphatic tertiary amines, in which R ₁ and R _{2 represent} alkyl groups having 1 to 4 carbon atoms, or b) groups in which N, R ₁ and R _{2 form} part of a heterocyclic tertiary amine of the formulas or -N IN form, mean 9 Allyl-dimethyl-tetrapropenylhydroxysucoinylaminopropylammonium chloride 10, Allylaoetoxy-dimethyl-isooctadeoenylhydroxysuooinyloxyäthylammoniumohlorid · 11 · Allyl-tetrapropenylhydroxysuooinyloxyäthylmorpholiniumbroaid. 109819/2055 205U79 12. Vinyloxyäthyl-dimethyl-trideoyloxyoarbonylmethylammoniumchlorid, 13. A compound according to claim 7, characterized in that V is an acryloyloxy, methaeryloyloxy, vinyloxy or 4-hydroxymaleoyl group and the quaternary nitrogen group N ⁺ R ₁ R ₂ R, a) aliphatic tertiary amines, in which R and R _{2 represent} alkyl groups with 1 to 4 carbon atoms, or b) Groups in which N, R- and R ₂ together form part of a heterocyclic tertiary amine of the formulas or -If, 0 form, mean. 14 · Methacryloylethyl-dimethyl-tetrapropenylhydroxysuc oinyloxyethylammonium bromide. 15. Vinyloxyethyl-dimethyl-tetrapropenylhydroxysuccinyloxyethylammonium bromine d 16. 2- (4-Hydroxy-maleoyl) -oxyethyldimethyldodecenylhydroxysuo c inyloxyethylammonium bromide 17. Vinyloxyethyl-dimethyl-p-dodecylbenjsylammonium chloride. 18. A compound according to claim 6, characterized in that X "" denotes one of the groups (b). 19 · Organic polymer, consisting of a smaller one Proportion of groups which are derived from a compound corresponding to the formula according to claim 6, and a larger proportion of groups that differ from minor 109819/2055 at least one further äthylenisoh-unsaturated monomers derive. 2oo polymer according Anspruoh _t 19 characterized in that the further äthyleniBch-unsaturated monomers of a Aoryleäure- or methacrylates having from 1 his 14 carbon atoms in the alkyl moiety of the Estergruppe consists " 109819/2055