Heat-sensitization of anionic and non-ionic aqueous polymer dispersions

© Start of patent term: 15.NOV EH BER 1974 Longest possible duration:

© Issued on: 10th of September 1975

Oy Inventor:

© dependence:

© Pamphlets considered to delineate the prior art:

No. 324702

It is known that polymer dispersions can be coagulated by the addition of sensitizers under heating. These may be natural or synthetic latices and also secondary dispersions may be heat-sensitized. When using the heat-sensitized polymer dispersions, migration of the polymer particles during drying is reduced or prevented, after coagulation 5 a particularly easy separation of the aqueous phase allows. Sensitizing agents are used in the processes of German Pat. 869861 and German Laid-Open Patent Application No. 1569119 polyvinylalkylether, in the process of German Auslegeschrift 1066734 water-soluble polyacetals, in the process of British Patent No. 1,206,036, German Patent No.1243394 and German Offenlegungsschrift 2005974 oxalkylated polysiloxanes and in the process of German Laid-Open Patent 1619049 , 10 1619050 and 1948301 cationic substances. However, the known sensitizers do not satisfy in many respects: cationic substances as sensitizers, in particular in the sensitization of anionic latices, generally lead to a strong reduction of the stability at room temperature and thus to poor storage properties, as well as to an increase in the sensitivity to shear forces, such as often during processing, eg during padding occur.

In order to increase the stability of the sensitized latexes, in the case of the use of oxalkylated polysiloxanes as sensitizers, it is generally necessary in addition to add emulsifiers during storage. If polyvinyl alkyl ethers are used as sensitizers, the properties of the coagulum are often adversely affected, for example, they can become tacky. When using polyether thioethers and polyacetals as sensitizers, low solids polymer dispersions (<30%) can only be incompletely coagulated.

It has now been found that anionic and nonionic aqueous polymer dispersions can be advantageously heat-sensitized by the addition of inverse-solubility polyalkylene oxides by adding inverse solubility alkoxylated amines to the polymer dispersions and reducing the ppp of the mixture to less than 6, as far as this is not below 6 anyway.

The new process is suitable for heat sensitization of virtually all natural and synthetic, primary and secondary polymer dispersions. Natural rubber latex should be mentioned as an example of a natural polymer dispersion. As a secondary dispersion come, for example those of polyisobutylene or polyethylene and of synthetic polyamides, such as polycaprolactam and polyhexamethylene adipamide, which may be prepared in a conventional manner using the usual anionic and nonionic emulsifying and dispersing aids.

Suitable synthetic anionic and nonionic aqueous primary dispersions of polymers may, for example of mono and diolefins, especially ethylene and butadiene, of monovinylaromatic compounds, such as especially styrene, vinyltoluenes, ct-methylstyrene or o-chlorostyrene, vinyl and / or vinylidene halides, especially vinyl chloride and vinylidene chloride, monoolefinically unsaturated carboxylic acid esters, which are usually 3 to 20, in particular 4 to 14 carbon atoms, such as vinyl esters of saturated straight-chain or branched aliphatic carboxylic acids, for example Vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl pivalate, vinyl laurate and vinyl stearate, acrylic acid and methacrylic acid alkyl esters, such as methyl acrylate and methacrylate, ethyl acrylate, n-butyl acrylate and methacrylate, tert-butyl acrylate, n-hexyl acrylate and methacrylate, 2-ethylhexyl acrylate and methacrylate, n-decyl acrylate and n-dodecyl acrylate and dialkyl esters, ct, 0-mo40 noolefinically unsaturated dicarboxylic acids, such as dimethyl maleate, fumarate and itaconate, diethyl ester, di-n-butyl ester and di-n-hexyl ester, and vinyl ethers such as vinyl methyl ether, vinyl ethyl ether,

Vinyl-n-butyl ether and vinyl sec-butyl ether.

The aqueous polymer dispersions of the type mentioned may contain one or more such monomers in copolymerized form. Of particular interest are, for example the customary aqueous dispersions of 45 ethyl / vinyl acetate copolymers, of butadiene / styrene and / or acrylonitrile copolymers, of acrylic ester copolymers, of acrylic ester / styrene copolymers, of vinyl chloride / acrylic ester copolymers, of vinylidene chloride / acrylic ester / copolymers , vinyl chloride / vinylidene chloride copolymers and vinylidene chloride / acrylonitrile gopolymates.

The polymer dispersions of this type can also in amounts, which are usually between 3 and 20% of Poly50 merisatgewichts, nitriles a, ß-olefinically unsaturated carboxylic acids, such as acrylonitrile and also in amounts of usually 0.5 to 10, especially from 0 , 5 to 5 wt .-% of olefinically unsaturated monomers having reactive groups, which are often water-soluble, eg a, ß-unsaturated, usually 3 to 5 carbon atoms containing mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid and their optionally on the nitrogen atoms by Methy lolgruppen or usually 1 to 4 G-Ato55 me containing alkoxymethyl groups substituted amides, such as in particular acrylamide, methacrylamide, N-methylacrylamide, maleic acid amide and maleimide, hydroxyalkyl acrylates and methacrylates such as glycol monoacrylate and monomethacrylate, Butanediol-l, 4-monoacrylate and methacrylate, monoalkyl esters of α, δ-olefinically unsaturated dicarboxylic acids of the type mentioned, such as maleic acid mono and mono-n-butyl esters, heterocyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylimidazole, Mono60 mers with several isolated double bonds, such as divinylbenzene, methylenebisacrylamide and diallyl phthalate,

No.324702 and also vinyl sulfonic acid and their esters and alkali metal salts, in copolymerized form.

The polymer dispersions may be prepared using the usual anionic and / or nonionic emulsifiers and optionally conventional protective colloids. Examples of suitable emulsifying and dispersing aids are alkyl sulfates, such as lauryl sulfate, alkali metal salts of fatty acids, such as sodium stearate and potassium oleate, alkyl sulfonates, oxyethylated alkylphenols having alkyl groups containing from 8 to 12 carbon atoms, which have from 5 to 30, in particular from 10 to 25, ethylene oxide residues and their sulfurization products and oxalkylated, in particular oxyethylated, fatty alcohols, fatty amines and fatty acids, and also, if appropriate, in small amounts polyvinyl alcohol, partially hydrolyzed vinyl acetate polymers, carboxymethylcellulose and hydroxyethyl ellulos e.

The content of emulsifiers in the polymer dispersions is generally between 0 and 5, preferably between 0.1 and 2,% by weight, based on the amount of polymer, and the dispersions can often contain both anionic and nonionic emulsifiers. In this case, the polymer dispersions having average particle diameters of more than 0.2 μ usually contain 0.1 to 1 wt .-% emulsifiers, polymer dispersions having average particle diameters below 0.2 μ, usually 1 to 4, especially 1 to 2 wt .-% , based on the polymers, of emulsifiers.

In the new process, the alkoxylated amines with inverse solubility in water are added to the polymer dispersions of the type mentioned. The solubility of the alkoxylated amines used as sensitizers should thus be greater at low temperature, eg at room temperature, in water than at elevated temperature, for example at 50 or 90 ° C. The alkoxylated amines can be derived from monovalent or polyvalent amines, which generally have 1 to 10, preferably 1 to 3, amino groups. Of particular interest are amines with 2 amino groups.

The amino groups of the alkoxylated amines may be primary, secondary or tertiary. The alkoxylated amines are preferably derived from straight-chain or branched aliphatic amines, in particular from polyhydric straight-chain aliphatic amines, such as ethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, and tetraethylenepentamine, and also from ethanolamine, diethanolamine and triethanolamine, with ethylenediamine being of particular interest.

The alkoxy radicals of the alkoxylated amines can be derived in particular from ethylene oxide and / or propylene oxide. If the alkoxylated amines are derived from ethylene oxide and propylene oxide, then ethylene oxide and propylene oxide can be randomly attached or usually as blocks in themselves. The alkoxylated amines should preferably contain propylene oxide or ethylene oxide and propylene oxide when derived from alkylamines containing a total of up to 4 C atoms in the molecule. If the alkoxylated amines of alkylamines are derived with more than 4, in particular more than 8, carbon atoms in the molecule, they may contain alone ethylene oxide, propylene oxide alone or else ethylene oxide and additionally propylene oxide.

If the alkoxylated amines contain ethylene oxide and propylene oxide, it has proven to be advantageous that they contain the more propylene oxide attached the more amino groups the amine used as starting material has. The molar ratio of ethylene oxide to propylene oxide in such alkoxylated amines is often between 1:10 and 1: 1 and the average molecular weight of the alkoxylated amines is generally between about 200 and 15,000, preferably between 800 and 6,000 (measured by determining the hydroxyl number after the acetic anhydride -Method). The average molecular weight of propoxylated amines containing only propylene oxide is generally between 600 and 1400.

The alkoxylated amines generally have a cloud point of between about 10 and 70 ° C in 1% aqueous solution. As alkoxylated amines of particular interest are those derived from ethylenediamine by addition of propylene oxide or of ethylene oxide and propylene oxide in a molar ratio of 1: 1 to 1: 5, wherein the Äthylenoxydreste and propylene oxide may be arranged randomly or as blocks.

It is surprising that alkoxylated amines of the type mentioned are suitable as heat sensitizers for polymer dispersions, since, for example, copolymers of propylene oxide and ethylene oxide with inverse solubility of the comparable amounts cause no or only slight heat sensitization with incomplete coagulation.

In the new process, the oxalkylated amines of the type mentioned can polymer dispersions, which generally have a polymer content of 5 to 60, in particular from 20 to 50% by weight, at room temperature in amounts, usually between 1 and 20 Wt .-%, based on the polymers, are, preferably in amounts of 2 to 10 wt .-%, are added. The amount of oxalkylated amines which is at least required in the case of the various dispersions and which is in each case desired for the purpose of heat sensitization can easily be determined by preliminary experiments.

For the purpose of heat sensitization, the pH of a mixture can then be adjusted below 6 or, if appropriate, even after possible storage, when starting from polymer dispersions having a pH of 6 or more. For example, dilute mineral acids, such as hydrochloric acid, sulfuric acid or phosphoric acid, and also organic acids, such as acetic acid, can be used. Preferably, the pH should be set to below 4, in particular to 1 to 3 and at pH values ​​between 4 and 6, it has proved to be advantageous, the mixture also still electrolytes, such as sodium chloride or magnesium4

No.324702 chloride, in amounts of about 1 to 3 wt .-%, based on the amount of polymer, add. Assuming polymer dispersions having a pH below 6, in particular from 1 to 3, and adds the alkoxylated amines with inverse solubility to these, so the acidification is unnecessary; In this case, sometimes the addition of electrolytes or a further lowering of the pH, eg from pH 5 to pH 2, may be advantageous to enhance the heat sensitization. In some cases it may also be expedient to simultaneously add the alkoxylated amines and dilute acids to polymer dispersions having a p.sub.1 value of 6 and more.

The new method for heat sensitization of polymer dispersions is characterized in particular by the fact that the coagulation takes place particularly quickly and completely when heated. In addition, the sensitized polymer dispersions at room temperature, especially at a pH above 4 are extremely stable in storage and show no disturbing increase in viscosity. Finally, products obtained from the polymer dispersions heat-sensitized by this process by coagulation of the polymers and further processing are particularly prone to electrical charges. In addition, the process-sensitized polymer dispersions are sufficiently stable to shear during processing.

The polymer dispersions which are heat-sensitized by the novel process are of particular interest as binders for nonwoven fabrics for the production of coatings and coatings, hollow bodies, for example of glass or plastics, and z, for example on paper, fabrics, and for the production of foams. The process is generally suitable for heat coagulation of polymer dispersions.

The parts given in the following examples are parts by weight.

For example: To a prepared in a conventional manner 20% aqueous dispersion of a copolymer of 60 parts of butadiene, 38 parts of styrene and 2 parts of itaconic acid containing 0.6 parts of sodium lauryl sulfate as an emulsifier, are added to 100 parts of 1 part of a custom-made statistical polyaddition product of 48 moles of propylene oxide and 20 moles of ethylene oxide per mole of ethylenediamine (Sensitizer A). 10% aqueous hydrochloric acid is added until pH 2 is reached, giving a heat-sensitized polymer dispersion which completely coagulates at 38.4 ° C. in a few seconds.

Example 2: To 100 parts of a 20% aqueous dispersion of a copolymer of 84 parts of vinylidene chloride, 10 parts of methyl acrylate and 5 parts of itaconic acid containing 1.5 parts of the sodium salt of a C₁₂- to C₁₆Alkylarylsulfonats, are added 2 parts of the sensitizer A and the pH of the mixture by addition of 5% aqueous sulfuric acid to 1.8, to give a polymer dispersion which is completely coagulated at 73.2 ° C within a few seconds , The dispersion is suitable for example for hollow body coating.

Example 3: To 10 parts of a 20% aqueous dispersion of a copolymer of 50 parts of methyl methacrylate, 20 parts of methyl acrylate, 20 parts of ethyl acrylate and 10 parts of methacrylic acid containing 0.8 part of the sodium salt of a C₁₂- to G₁₆Alkyl sulfonate and 0.2 part of the sodium salt of a usually sulfonated condensation product of p-octylphenol and 20 moles of ethylene oxide as emulsifier, are added 1 part of the sensitizer A and the pH by adding 10% aqueous maleic acid to 1, 9th This gives a heat-sensitized polymer latex which practically completely coagulates at 26 ° C. within a few seconds.

Example 4: To 100 parts of a 20% (40%) aqueous dispersion of a copolymer of 50 parts of n-butyl acrylate, 48 parts of styrene and 2 parts of methacrylic acid containing 1.5 parts of the sodium salt of a C_lg- to C_lgAlkyl sulfonate as emulsifier, are added 1.6 parts (3.2 parts) of the sensitizer A and the pn value by addition of dilute aqueous hydrochloric acid to 2 (1,9). A polymer dispersion is obtained which coagulates virtually completely at 45 ° C. (37.5 ° C.) within a few seconds. The sensitized dispersion is suitable as a binder for fiber webs,

Example 5: To 100 parts of a conventionally prepared 20% aqueous dispersion of a copolymer of 80 parts of methyl methacrylate, 10 parts of methyl acrylate and 10 parts of methacrylic acid containing 1.8 parts of a C₁₂- to C_lsAlkylaryl sulfonate as emulsifier, 2 parts of sensitizer A are added, and the pn value is adjusted to 2 by the addition of dilute sulfuric acid. A sensitized polymer dispersion is obtained which coagulates virtually completely at 38.3 ° C within a few seconds.

Example 6: To 100 parts of a conventionally prepared 20% aqueous dispersion of a copolymer of 47 parts of n-butyl acrylate, 51 parts of vinyl acetate and 2 parts of acrylic acid containing 2% based on the polymer lauryl sulfate as an emulsifier, are added to 1.6 Parts of the sensitizer A and sets the pn to 2. A sensitized polymer dispersion is obtained which coagulates almost completely at 45 ° C within a few seconds. The sensitized dispersion is suitable for the production of coatings, textile coatings and binders for leather fiber webs.

Example 7: To 100 parts each of a conventionally prepared 20% aqueous dispersion of a copolymer of 90 parts of n-butyl acrylate, 6 parts of acrylonitrile, 2 parts of acrylamide and 2 parts

Methacrylic acid, the 0.5 wt .-%, based on the polymer, of the obtained in the usual manner Anlageungs5

Nr.324702

Contains 1 part of the sensitizer A or 0.7 parts of the reaction product prepared in the usual manner of 79 mol of propylene oxide and 18 moles of ethylene oxide per mole of triethylenetetramine (sensitizer B) or 25 mol of ethylene oxide per mole of pn-nonylphenyl. 1 part of the reaction product prepared in the usual manner of 77 moles of propylene oxide and 16 moles of ethylene oxide per mole of diethylenetriamine (sensitizer C), or 0.7 parts of the customarily prepared reaction product of 67 mol of propylene oxide and 37 moles of ethylene oxide with 1 mole of dipropylene triamine (sensitizer D) or 1.4 parts of the reaction product prepared in the usual manner of 82 moles of propylene oxide and 22 moles of ethylene oxide per mole of tetraethylene pentamine ( Sensitizing agent E) and by addition of dilute hydrochloric acid to p_H 2. In addition, to the batch containing Sensitizer B, 0.2 part of ammonium chloride is added, to the mixtures containing Sensitizers C, D and E, respectively, 0.4 part of ammonium chloride. Each gives a sensitized polymer dispersion which practically completely coagulates at 45.1 or 53 or 35.8 or 50.9 or 40.2 ° C within a few seconds. The sensitized dispersion is suitable for example for the production of adhesive coatings.

Example 8: To 100 parts of a mixture of equal parts of each of ZCPfoig & n aqueous dispersions of (a) a copolymer of 45 parts of n-butyl acrylate, 53 parts of styrene and 2 parts of itaconic acid and (b) 62 parts of butadiene, 35 parts of styrene and 3 parts of fumaric acid containing 1.5 and 0.7 wt .-%, based on the amount of the polymers, sodium lauryl sulfate as an emulsifier, are added 1 part of the sensitizer A. The p.sub.2 value is then adjusted to 2, giving a sensitized polymer dispersion which practically completely coagulates at 41.5.degree. C. within a few seconds.

Example 9: To each 100 parts of a conventionally prepared 20% aqueous dispersion of a copolymer of 90 parts of n-butyl acrylate, 6 parts of acrylonitrile, 2 parts of acrylamide and 2 parts of methacrylic acid containing 0.5 based on the polymer, sodium dodecylsulphonate as an emulsifier in each case 5%, based on the amount of polymer in the dispersion, sensitizer A and 3% (based on the amount of the polymer in the polymer dispersion) maleic acid and 0.1 or 0.6 or 1.1% sodium dodecylsulfonate. This gives heat-sensitized dispersions whose coagulation temperature

54.5 and 51.2 and 56.4 ° C and have the pjj value of 2 to 2.5.

The average particle size of the polymer dispersion is 162 μm. Sensitizer A is a reaction product of triethanolamine with 20.2 moles of propylene oxide, whose 1% aqueous solution has a cloud point of 41 ° C.

Example 10: To 100 parts of the 20% aqueous dispersion indicated in Example 1 are added in each case 5%, based on the polymer of the dispersion, sensitizer B and in each case 2%, based on the polymer of the dispersion, maleic acid and 0.2 or 1.5 wt .-%, based on the Po lymerisatanteil the dispersion, sodium dodecylsulfonate. This gives sensitized dispersions whose coagulation temperature is 39.6 and 42.6 ° G, respectively.

Sensitizing agent B is a propoxylated amine prepared in the usual way from ethylenediamine by reaction with 14.2 moles of propylene oxide, whose 1% aqueous solution has a cloud point of 53 ° C.

B Ice pe 11: To 100 parts of an aqueous dispersion, as indicated in Example 1, are each 2 wt .-%, based on the polymer of the dispersion, maleic acid and 5 to 4 wt .-%, based on the Polymerization proportion of the dispersion, sensitizer C. Heat-sensitized polymer dispersions are obtained whose coagulation temperatures are 43 and 47.5 ° C. Their pH is 2.5 and 2.2, respectively.

Sensitizer C is a conventionally prepared reaction product of ethylenediamine and 12 moles of propylene oxide, whose 1% aqueous solution has a cloud point of 65 ° C.

Example 12: To 100 parts of a conventionally prepared 20% aqueous dispersion of a copolymer of 69 parts of butadiene, 30 parts of acrylonitrile and 1 part of N-methylolmethacrylamide

Containing 1.5 parts of sodium lauryl sulfate as an emulsifier, are added 5 wt .-%, based on the amount of polymer, of sensitizer C and 2 parts of maleic acid. This gives a heat-sensitized polymer dispersion whose pjj value is 3.6 and whose coagulation temperature is 42.5 ° C. The sensitized dispersion is suitable for binding needle-punched fiber webs, which are used, for example, as starting material for the production of leather substitutes.

Example 13: To 100 parts of a customarily prepared 20% strength aqueous dispersion of a copolymer of 50 parts of n-butyl acrylate, 48 parts of styrene and 2 parts of acrylic acid which contains 1.5 parts of alkylarylsulfonate as emulsifier are added 5% by weight. , based on the amount of polymer, the sensitizer A and 2 parts of maleic acid. This gives a heat-sensitized dispersion whose pn value is 4 and whose coagulation temperature is 49.6 ° C.

Example 14: To 100 parts of a conventionally prepared 20% aqueous dispersion of a

Copolymer of 47 parts of n-butyl acrylate, 51 parts of vinyl acetate and 2 parts of acrylic acid, 2%, based on the polymer, addition product of the sodium salt of the sulfuric acid monoester of HD-Ocenol

Sp. 60/65 (mixture of saturated and unsaturated fatty alcohols) with 25 moles of ethylene oxide as emulsifier, are added 5 wt .-%, based on the amount of polymer of the dispersion, sensitizer C and 1 part

Nr.324702

Oxalic acid. This gives a heat-sensitized polymer dispersion whose pfj value is 3 and whose coagulation temperature is 37.4 ° C.

Example 15: To a conventionally prepared 30% aqueous dispersion of a copolymer of 96 parts of n'-Buty lacry lat and 3 parts of N-methylolmethacrylamide and 1 part of divinylbenzene, the 1 part of the sodium salt of a C₁₄-C_l8Contains alkyl sulfonate as emulsifier and ph4.3, is added at room temperature to 100 parts of 1 part of a polyadduct prepared in the usual way from 25 moles of propylene oxide and 5 moles of ethylene oxide per mole of ethylenediamine. The heat-sensitized mixture has pH 4.5 and completely coagulates when heated to 63 ° C in a few seconds.

Example 16: To a conventionally prepared 35% aqueous dispersion of a copolymer of 87 parts of n-butyl acrylate, 10 parts of acrylonitrile, 2 parts of N-butoxymethylmethacrylamide, and 1 part of acrylic acid containing 0.8 part of the sodium salt of a C₁₂-C_uContains alkylarylsulfonate and 0.5 parts of sodium pyrophosphate and pg 4, are added 0.7 parts of a polyaddition product of 25 moles of propylene oxide and 6 moles of ethylene oxide per mole of ethylenediamine. The resulting mixture has pn 4.3 and completely coagulates when heated to 52 ° C within a few seconds. The dispersion is suitable as a binder for nonwoven fabrics.

Example 17: To 100 parts of a 30% aqueous dispersion of a conventionally prepared copolymer of 50 parts of styrene and 50 parts of n-butyl acrylate containing 0.8 part of the sodium salt of lauryl sulfonate and 0.3 part of a C₁₂-C₁₆-Fettsäureamido-Nn-propylbetaingemisches

CH,

I (C_12rl4CONH (CH₂)₃-N-CH_ZCOO®) contains as emulsifiers and pH 2.6, is added at room temperature 1.2 parts of a polyaddition product of 20 moles of propylene oxide and 5 moles of ethylene oxide per mole of ethylenediamine.

The resulting mixture has p ^ 3 and coagulates rapidly and completely when heated to 68 ° C. The mixture can be easily foamed and is suitable in foamed form for foam impregnation of nonwoven fabrics, wherein the subsequent heating to at least 68 ° C coagulation to solidify the nonwoven fabric occurs virtually without migration of the binder polymer.

Bis 18: To 100 parts of a 20% aqueous dispersion of a copolymer prepared in conventional manner from 97 parts of n-butyl acrylate, 2 parts of N-methylolmethacrylamide and 1 part of methacrylic acid, the 0, 6 parts of the Oxäthylierungsproduktes of a C_8th-C₁₂ Contains alkylphenol with 10 moles of ethylene oxide as an emulsifier and pn 2, are added 1 part of the polyaddition product of 20 moles of propylene oxide and 5 moles of ethylene oxide per mole of ethylenediamine. The heat-sensitive mixture has pp [2,2 and coagulates rapidly and completely when heated to 46 ° C. The sensitized dispersion is useful, for example, as a binder for nonwoven fibers of natural and / or synthetic fibers.

Example 19: To 100 parts of a conventionally prepared 20% aqueous dispersion of a copolymer of 60 parts of butadiene, 38 parts of styrene and 2 parts of itaconic acid containing 0.6 parts of sodium laurylsulfonate as an emulsifier and pn has 1.8, are added to 100 parts of 1 Part of a randomly prepared polyaddition product of 48 moles of propylene oxide and 20 moles of ethylene oxide per mole of ethylenediamine, The resulting mixture has pn 2 and completely coagulates when heated to 38.4 ° C in a few minutes.

Example 20: To a prepared in a conventional manner 30% aqueous polystyrene dispersion containing 1 part of the sodium salt of lauryl sulfonate as an emulsifier, are added to 100 parts of dispersion 0.9 parts of a polyadduct prepared in the usual way of 25 moles of propylene oxide and 5 moles of ethylene oxide per mole of ethylenediamine, hereinafter referred to as Sensibilisierungsmitteil. This heat-sensitive dispersion mixture has a p value of 2.5 and coagulates rapidly and completely when heated to 35 ° C.

Example 21: To a conventionally prepared aqueous dispersion of a copolymer of 67 parts of styrene, 30 parts of methyl acrylate and 3 parts of acrylic acid containing 2 parts of a sodium salt of the sulfated Oxyäthylierungsproduktes a C_l2-C_l8-Alkanol with 5 moles of ethylene oxide as emulsifier, are added to 100 parts of dispersion:

a) at a solids content of the dispersion of 20%

1. 0.6 part of sensitizer I. This mixture has a p.sub.1 of 1.8 and completely coagulates when heated to 50.degree. C. in a few seconds.

Second 0.8 parts of Sensitizer I. This mixture has a pjj of 2 and completely coagulates when heated to 40 ° C in a few seconds.

No. 324702

b) at a solids content of 30% of the dispersion

1. 1.2 parts of sensitizer I. This mixture has a pjj of 2 and completely coagulates when heated to 34 ° C in a few seconds.

Second 1.5 parts of the sensitizer I. This mixture has a pj-j value of 2 and completely coagulates when heated to 30 ° C in a few seconds.

Example 22: To a 20% commercial natural rubber dispersion, which was mixed with 5 wt .-% (based on the solids content) of the sodium salt of lauryl sulfonate to be sufficiently stable, are given at a ρπ value of 1.8 1 part Sensitiser I to 100 parts of natural latex. When heated to 38 ° C, the latex completely coagulates. The natural latex, which is only post-stabilized with laurylsulfonate, does not change on warming.

Example 23: To a conventionally prepared secondary dispersion of polyethylene, the

<td>20 parts</td><td>polyethylene</td>

<td>4 parts</td><td>the Oxäthylierungsproduktes of 1 mole of n-nonylphenol and</td>

<td>10 mol</td><td>ethylene oxide</td>

<td>Part 1</td><td>Sodium salt of the sulfated Oxäthylierungsproduktes 1 mole of n-nonylphenyol with 25 moles of ethylene oxide</td>

contains and has a ρπ value of 2, are added to 100 parts of dispersion 0, 5 parts of the sensitizer

I. This heat-sensitive secondary dispersion coagulates rapidly and completely when heated to a temperature of 62 ° C. The sensitized dispersion is suitable, for example, for the coating of fabrics and knitted fabrics.

Example 24: To a commercially available secondary dispersion of polyisobutylene, molecular weight, according to Überreiter, Macromolecular Chemistry, Vol. 8 [1952], pp. 21 to 28, from 100,000 to 200,000, which contains a protective colloid based on a vinylpyrrolidone polymer and 1% sodium lauryl sulfonate as emulsifier ( based on the solids content) and has a pH of 1.2 at a solids content of 20%, are added to 100 parts of dispersion, 0.6 parts of the Sensitizing I. This heat-sensitized secondary dispersion completely coagulates when heated to 42 ° C.

EXAMPLE 25 1.5 parts of Sensitiser I are added to a polyvinyl chloride dispersion prepared in the customary manner and containing 2. 5% of the solid content of sodium lauryl sulfate as emulsifier per 100 parts of dispersion. The heat-sensitive polymer dispersion has a solids content of 30% pH of 1.8 and coagulates completely when heated to a temperature of 44 ° C in a few seconds.

Example 26: To a conventionally prepared 30% aqueous polyvinyl chloride dispersion containing 2.5% sodium lauryl sulfate (based on the solids content) as an emulsifier, are added to 100 parts

1.5 parts of the polyaddition product of 21 moles of propylene oxide per mole of triethanolamine. The heat-sensitive mixture has a pn value of 1.8 and coagulates when heated to 44.7 ° C in a few seconds.

Example 27: To a prepared in a conventional manner 30% aqueous dispersion of a copolymer of 98 parts of vinyl acetate and 2 parts of acrylic acid, based on the solids 1.2 parts of the condensation product of p-octylphenol and 20 moles of ethylene oxide and 1.2 parts of the sodium salt of a usually contains sulfonated condensation product of p-octylphenol and 20 moles of ethylene oxide as an emulsifier, Are added to 100 parts of dispersion, 1.8 parts of a prepared in the usual way polyaddition product of 25 moles of propylene oxide and 5 moles of ethylene oxide per mole of ethylenediamine. This heat-sensitive dispersion mixture has a ppj of 1.8 and coagulates rapidly and completely when heated to 72 ° C.