DE2263921C2 - Heat sensitization of anionic and nonionic aqueous polymer dispersions - Google Patents

Description

example 1

For each 100 parts of a conventionally prepared 20% strength aqueous dispersion of a copolymer Risats of 90 parts of n-butyl acrylate, 6 parts of acrylonitrile, 2 Divider «acrylamide and 2 parts of methacrylic acid, the 0.5

3

Percentage by weight based on the polymer sodium and 2 parts maleic acid. A heat-sensitive dodecyl sulfonate is obtained the emulsifier contains a gelized dispersion, the pH of which is 4 and the because 5%, based on the amount of polymer, is at the coagulation temperature of 49.6 ° C Dispersion, sensitizer A and 3% (based on

on the amount of polymer in the polymer dispersion 5 B e i s ρ i e 1

sion) maleic acid and 0.1% or 0.6% or 1.1% Na-

trium dodecyl sulfonate. 100 parts of a heat-sensitized compound prepared in a conventional manner are obtained

Dispersions whose coaguladon temperatures are 54.5% strength aqueous dispersion of a copolymer or 51.2 or 56.4 ° C and the pH of 2 47 parts of n-butyl acrylate! at 51 parts of vinyl acetate,: nd to 23 have. 10 parts of acrylic acid, the 2%, based on the polymer

The average particle size of the polymer addition product of the sodium salt of the sulfur dispersion is 162 μm. Sensitizer A is an acid monoester of HD-Ocenol Sp 60/65 (mixture of a reaction product of triethanolamine with saturated and unsaturated fatty alcohols) with 25 moles of 20.2 moles of propylene oxide, the 1% aqueous solution of which contains ethylene oxide as an emulsifier and gives 5 levels of cloud point 41 ⁰ C has 15 percent by weight based on the amount of polymer

Dispersion, sensitizer C and 1 part oxaline

Example 2 acid. A heat-sensitized Polymerdi is obtained

spersion, whose pH value is 3 and whose coagula-

To 100 parts of the procedure given in Example 1 20% by weight tion temperature at 37.4 ° C, aqueous ^Dispers: on one gives 5% each, based on the Polymerisaisytei! of the dispersion, sensitizing agent B and 2% each based on the polymer content of the dispersion, maleic acid and 0.2 or 13 percent by weight based on the polymer content of the dispersion, sodium dodecyl sulfonate. Sensitized dispersions whose coagulation temperatures are 39.6 and 42.6 ° C. are obtained is

Sensitizer B is a conventional one from ethylenediamine by reaction with 14.2 mol propylene oxide produced propoxylated amine, the 1% aqueous solution of which has the cloud point 53 ° C

j Example 3

2 percent by weight, based on the polymer content of the dispersion, are added to 100 parts of an aqueous dispersion as indicated in Example 1. Maleic acid and 5 to 4 percent by weight based on the polymer content of the dispersion, sensitizing agent C. This gives heat-sensitized polymer dispersions whose coagulation temperatures are 43 and 473 ° C, respectively. Their pH value is 23 or 22-

Sensitizer C is a conventionally prepared one Reaction product of ethylenediamine and 12 moles of propylene oxide, its 1% aqueous solution has a cloud point of 65 "C.

Example 4 ι
To 100 parts one prepared in the usual way

20% strength aqueous dispersion of a copolymer of 69 parts of butadiene, 30 parts of acrylonitrile and 1 part N-methylol methacrylamide, containing 13 parts of sodium lauryl sulfate contains as an emulsifier 5 percent by weight, based on the amount of polymer, of sensitizing

Average C and 2 parts of maleic acid. You get one ί heat-sensitized polymer dispersion, the pH of which

"- value is 3.6 and its coagulation temperature at

423 ° C

j

| j example 5

To 100 parts one prepared in the usual way

η 20% strength aqueous dispersion of a copolymer

from 50 parts of n-butyl acrylate, 48 parts of styrene and 2 parts Acrylic acid, the 13 parts of alkylarylsulfonate as an emulsifier contains is 5 percent by weight, based on

the amount of polymer, of the sensitizing agent A

Claims (1)

Claim: Further development of the process for heat sensitization of anionic and nonionic aqueous polymer dispersions by adding polyalkylene oxide compounds with inverse solubility as a sensitizing agent, one of the polymer dispersions alkoxyüerte amines with inverse solubility added and the pH of the mixture under 6 is according to patent 22 26 269, characterized in that such alkoxylated Adds amines that have been produced exclusively by reaction with propylene oxide. The subject of patent 22 26 269 is a process for heat sensitizing anionic and nonionic aqueous polymer dispersions by adding polyalkylene oxide with inverse solubility as a sensitizing agent. which is characterized in that alkoxylated amines are added to the polymer dispersions with inverse solubility, which contain ethylene oxide and propylene oxide in a molar ratio of 1:10 to 1: 1 and molar weights have between 800 and 6000, adds and sets the pH of the mixture below 6. This method is used to heat sensitize virtually all natural and synthetic, primary and secondary Polymer dispersions suitable, for example for natural rubber latex, for polyisobutylene and polyethylene dispersions, for dispersions of synthetic polyamides such as polycaprolactam and polyhexamethylene adipamide, in the usual way using the usual anionic and nonionic emulsifying and Dispersing aids can be produced. Examples of suitable synthetic anionic and nonionic aqueous primary dispersions are z. B. those of polymers of mono- or diolefins, such as especially Ethylene and butadiene, of monovinylaromatic compounds, such as especially styrene, of vinyl and / or vinylidene halides, such as especially vinyl chloride, vinylidene chloride, of monoolefinically unsaturated Carboxylic acid esters, such as especially vinyl acetate and acrylic acid and / or methacrylic acid esters, have 1 to 8 carbon atoms containing alkanols and mixtures thereof. The polymer dispersions of the type mentioned can contain the usual anionic and nonionic emulsifiers and, if necessary, the usual protective colloids, z. B. alkyl sulfates such as auryl sulfate. Alkali salts of fatty acids, such as sodium stearate and potassium oleate, Alkyl sulfonates, oxethylated alkylphenols with 8 to 12 carbon atoms containing alkyl groups, 5 to 30, in particular 10 to 25 ethylene oxide residues, and their sulfonation products and alkoxylated, in particular oxethylated fatty alcohols, fatty amines and fatty acids and, if necessary, polyvinyl alcohol as protective colloids, partially saponified vinyl acetate polymers, carboxymethyl cellulose and hydroxyethyl cellulose. Alkoxylated amines having inverse solubility such, in this older method is used, the solubility of which is greater in water at room temperature than at elevated temperature, for example at 50 or 90 ⁰ C, and the aqueous generally dissolved in l% solution has a cloud point between about 10 and 70 ⁰ C. The alkoxylated amines, which are generally added to the polymer dispersions in the process of patent 22 26 269 in amounts between 1 and 20 percent by weight, preferably from 2 to 10 percent by weight, based on the polymers of the polymer dispersions, can be derived from monovalent or polyvalent amines, which generally have 1 to 10, preferably 1 to 3, amino groups, amines with 2 amino groups being of particular interest and the amino groups being primary, secondary or tertiary. The alkoxylated amines that are used in the older process contain ethylene oxide and propylene oxide added on. In a further development of the process for the heat sensitization of anionic and nonionic aqueous Polymer dispersions by adding alkoxylated amines with inverse solubility as sensitizers and adjusting the pH of the mixture to below 6, it has now been found that these are also alkoxylated Can use amines with an inverse solubility wedge that contain only propylene oxide attached. For this further development of the heat sensitization process Otherwise, the same points of view apply as for the patent process 22 26 269 apply, for example with regard to the polymer dispersions that are to be heat-sensitized, and the pH values that the mixtures should have. The propoxylated amines used in the new process are preferably derived from aliphatic amines, in particular from polyvalent aliphatic amines, such as ethylenediamine, diethylenetriamine, dipropylenetriamine, tripylenetetramine and tetraethylenepentamine, and also from ethyanolamine, diethanolamine and triethanolamine, of which the molecular weight is of particular interest propoxylated amines is generally between about 600 and 1400 and the cloud points of 1% aqueous solutions of the propoxylated amines from about 10 to 7O ⁰ C. The new process for the heat sensitization of polymer dispersions is distinguished from the State of the art is mainly characterized by the fact that the coagulation is particularly rapid and complete when heated In addition, the sensitized polymer dispersions are carried out at room temperature, in particular at a pH above 4, extremely stable in storage and show no disruptive increase in viscosity. Finally, products tend to be obtained from the polymer dispersions heat-sensitized by this process obtained by coagulation of the polymers and further processing, particularly little to see electrical Charges and heat-sensitized polymer dispersions according to the invention are in the process of being processed Sufficiently stable with respect to shear forces. The polymer dispersions heat-sensitized by the new process are of particular interest as binders demittel for fiber fleece, for the production of upper layers and coatings, ζ. B. on paper and fabrics, as well as for the production of foams. The procedure is generally suitable for heat coagulation of polymer dispersions. The parts given in the following examples are parts by weight.