DE1469834A1 - Aqueous polymer dispersion - Google Patents

Description

Aqueous polymer dispersions It is known that polymers of most diverse kind to be dispersed in water. You can either manufacture from Run out of polymers, if necessary after dissolution in an organic Solvents to be dispersed; but it is also possible to go straight through Emulsion polymerisation to produce plastic dispersions. In any case, the The dispersion obtained contain emulsifiers for stabilization.

A large number of emulsifiers are known. However, only a few of them can be used in polymer dispersions. For example, plastic dispersions are known which contain alkali metal salts of longer-chain alkane sulfonic acid treatments as emulsifiers. Such dispersions have a number of disadvantages: they tend to foam strongly and, moreover, have unsatisfactory storage and heat stability. It is also known compounds of the general formula where R is an unbranched alkyl chain with about 8 to 18 carbon atoms, Ri. N and R3 are hydrogen or a short alkyl chain and Me is a metal cation, to be used as an emulsifier in Em-Sßionspolymerisation. It has been found, however, that such emulsifiers have an inadequate emulsifying effect compared to some polymers. In addition, polymer dispersions which contain these substances also have an undesirably high foaming power.

It has now been found that aqueous polymer dispersions containing one to two alkyl radicals with at least 6 carbon atoms onium salts of β-alkoxyalkanesulfonic acids do not have the abovementioned disadvantages. The onium salts can be derived from all basic substances which are capable of being converted into the onium form by peralkylation. It can therefore be, for example, oxonium, hydrazonium, ammonium, sulfonium and phosphonium salts. The last three salt classes mentioned are preferred. Of these, those salts have a particular technical meaning, those of the general formula correspond. In this formula, Y is a radical of the formula tg -S, -P-R8 or -N-R9, R1 is an alkyl radical with 1 to 20 carbon atoms, R2, R3 and R4 are hydrogen atoms or alkyl radicals with 1 to 4 carbon atoms, R5 is an alkyl radical with 1 to 20 carbon atoms, R6, R7 and R8 aliphatic radicals with 1 to 4 carbon atoms, aromatic or cycloaliphatic radicals with up to 7 carbon atoms and Rg an alkyl radical with 1 to 4 carbon atoms or part of a heterocyclic radical formed together with N and R7, 5 - or 6-membered ring; this ring, consisting of the interconnected parts Ns b and R7, can also contain a double bond between N and Rq, but the radical R6 is omitted. At least one of the radicals R1 and R5 must contain at least 6 carbon atoms.

Because of their ready availability, those salts are the above especially preferred formula shown, which contain B-alkoxy-sthansulfonskurereste, in which the radicals R2, R3 and R4 are hydrogen atoms. As examples of acid residues of this type are the anions of methyl, ethyl, propyl, isopropyl, isoamyl, n-octyl, isooctyl, isononyl, d-decyl, isodecyl, n-dodecyl, the branched Tridecyl and n-Octadecyloxäthansulfonsäuren.

As ammonium, sulfonium and phosphonium cations that interact with the acid anions are connected, for example: tetramethylammonium, methyl-tributylammonium, Ethyltributylammonium, Trimethylstearylammonium, Trimethylphenylammonium, Dimethyldiphenylammonium, Dimethylethyl-phenylammonium, methylenebis-phenyltrimethylammonium, dimethyl-hydroxyethyl- (3-methyl- < phenyl) ammonium, trimethylcyclohexylammonium, tripropylcyclohexyl @ ammonium, N-methylpyridinium, N-ethylpyridinium, N-n-decylpyridinium, N, N-dimethylpiperidinium, N, N-dimethylpyrrolidinium, N-ethyl-N-dodecyl-pyrrolidinium, trimethylsulfonium, Triethyl sulfonium, dimethyl tert-butyl sulfonium, dimethyl dodecyl sulfonium, dimethyl phenyl sulfonium, Dimethyl- (4-methylphenyl) -sulfonium, methyl-diphenyl-sulfonium, methyltriphenylphosphonium, n-octyl triphenylphosphonium, dodecyl triphenylphosphonium, Tetraethylphosphoniumj. Octad @ cyl-triäthylphosphonium, Tetrabutylphosphonlum.

The anions and cations of the type mentioned can be used in any desired manner be combined to form salts, provided that in at least one of the two types of ions an alkyl radical with at least 6 carbon atoms is included.

The production of the onium salts described above can be carried out per se known methods. For example, they can be produced by neutralization of B-alkoxyalkanesulfonic acids with onium hydroxides9, in particular ammonium, sulfonium and Phosphonium hydroxides, the B-alkoxyalkanesulfonic acids such. B. from B-haloalkanesulfonic acids and alkali metal alcoholates of aliphatic alcohols and the onium hydroxides e.g. B. by converting ammonia, aliphatic or aromatic amines, thioethers or phosphines with known alkylating agents such as alkyl iodides or alkyl sulfates, and subsequent release of the hydroxides from the resulting salts with silver oxide or the like. are available.

A particularly advantageous process for the preparation of the onium salts of B-alkoxyethanesulfonic cures consists in the fact that B-alkoxyethanesulfonic acid alkyl esters are used with tertiary amines or phosphines or with thioethers, optionally with addition an inert solvent. The reaction is at temperatures of about 50 to 120 ° C finished in one to several hours and immediately provides the desired High purity salts.

For the production of the onium salts of B-alkoxyalkanesulfonic acids no protection is sought in the context of the present application.

The polymer dispersions according to the invention contain the above defined onium salts of B "AlkoxyalkanesulfonsKuren as dispersants, namely they preferably contain amounts of 0.1 to 10% by weight, preferably 1 to 5% by weight, one or more of these salts, based on the anhydrous polymer.

The dispersions according to the invention can be used as polymers Polymers made from ethylenically unsaturated polymerizable compounds Contain substances. The amount of polymers in the dispersions depends on the intended use. The dispersions according to the invention generally contain 40 to 6C% by weight of polymers, but they can, if necessary, substantially less, for example 5% by weight or even more, polymer up to approximately 65% by weight contain.

As ethylenically unsaturated polymerizable compounds come for example vinyl. and vinylidene compounds in consideration of such compounds here, for example, acrylic acid and acrylic acid compounds, such as acrylonitrile, Acrylic acid esters of aliphatic alcohols containing 1 to about 18 carbon atoms have calculated, as well as methacrylic acid and the corresponding methacrylic acid compounds. Α-chloroacrylic acid is also suitable as a monomeric compound. More monomers Compounds are styrene, which is in the vinyl group or on the core by halogen or Alkyl, for example by chlorine or methyl, can be substituted, or vinylnaphthalene, Vinyl ketones, such as vinyl methyl ketone or vinyl lactamea such as vinyl caprolactam or vinyl pyrrolidone, or vinyl esters such as vinyl. acetate and vinyl propionate and also vinyl and vinylidene halides, such as vinyl chloride and vinylidene chloride Also serve, like Bl adien, Isoprene or chloroprene can be used. The monomers mentioned can alone or also as a mixture with one another or with other monomers not yet mentioned Compounds, for example with ethylene, vinyl ethers, maleic acid, itaconic acid, fumaric acid or their esters and nitriles have been polymerized, or with allyl compounds, optionally in the presence of small amounts of water-soluble unsaturated Ethylene derivatives, such as vinyl sulfonic acids or acrylic acid amide.

The polymer dispersions according to the invention can per se known processes are produced. So it is possible, for example, first the abovementioned homopolymers or copolymers by block, solution or bead polymerisation to produce in the usual catfish and then, if necessary, the finished polymers after dissolution in an organic solvent, with the addition of the onium salts of To disperse B-alkoxyalkanesulfonic acids in water (so-called secondary dispersions). In many cases, however, it is more advantageous to use the polymer dispersions according to the invention directly prepared by using the monomers or monomer mixtures the onium salts of B-alkoxyalkanesulfonic acids emulsified in water and then after the customary processes of emulsion polymerization (so-called primary dispersions).

Both primary and secondary dispersions of the invention Art zzl ¢ can be distinguished by exceptional shelf life and by very gringes Foaming power.

The polymer dispersions according to the invention can also mentioned contain other additional components, the nature of which depends on which one Intended use the dispersions are intended. As additional components be for example protective colloids, such as gelatin, polyvinylpyrrolidone or polyvinyl ether, Plasticizers, pigments, dyes, and textile treatment agents such as curable aminoplastics or hydrophobic agent called. The new polymer dispersions are suitable excellent for many purposes, for example for leather finishing, textile coating and paper finishing.

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The parts and percentages given in the examples are weight units.

Example 1 100 parts of a 40% strength benzene solution of a Hete @ ropolymerisats from 54 parts of butyl acrylate and 46 parts of vinyl acetate in a Starmix kneading machine at speed 1 with 0.8 parts of decyloxäthansulfonsaurem Trimethylphenylammonium, dissolved in 3 parts of water, added and at speed level 2 homogenized. Then 30 parts of water are slowly added so that there is a concentration of the polymer of 30% is achieved, whereupon the dispersion obtained is still Stir for 20 minutes at speed 2 and 15 minutes at speed 3. The dispersion is stable for several months.

Example 2 An acidic polymer dispersion which, based on the Total mixture, 40% of a copolymer of 94 parts of ethyl acrylate and 6 parts Acrylskure, and, based on the copolymer, Contains 2% n-decyloxäthansulfonsaures trimethylphenylammonium as an emulsifier Stable at 80 ° C for 500 to 600 hours. Only after this time do the first begin Deposits to occur.

A dispersion that, with otherwise the same composition, instead of the Above emulsifier, 2% methylox-thanesulfonic acid trimethylstearylammonium is stable for over 700 hours under the same conditions.

A dispersion of a known type counteracts the otherwise identical composition instead of the emulsifiers mentioned, 2% sodium alkylsulfonate with alkyl residues of Containing 12 to 18 carbon atoms is only 200 under the same conditions Stable for up to 250 hours. The three dispersions were immediate in the usual way by emulsion polymerization from the monomers with the addition of the emulsifiers mentioned has been manufactured. As a polymerization. catalyst was hydrogen peroxide in an amount of 0.4%, calculated on the weight of the monomers, was used. The polymerization temperature was 90 ° C.

Example 3 An aqueous dispersion contains 50% of a copolymer from 57 parts of butyl acrylate and 42.8 parts of vinyl acetate and used as a dispersant 2.4%, based on the copolymer, of n-decyloxäthansulfonsaures trimethylphenylammonium. The dispersion is made by emulsion polymerization at 80 to 85 ° C with 0.4% potassium persulfate, calculated on the weight of the monomers.

The dispersion is filled 100 mm high into a tube with a fritted base and introduces air through the floor, so after 5 minutes a quantity of foam develops, which has a height of 200 to 230 mm.

Claims (2)

A dispersion of known type produced in the same catfish, the with otherwise the same composition as a dispersant instead of n-decyloxäthansulfonsauren Trimethylphenylammonium 2, 4 alkylsulfonic acid sodium with alkyl radicals from 12 to Contains 18 carbon atoms, forms under the test conditions given above a foam layer of about 450 mm height, claims 1. characterized by a content of one to two alkyl radicals with at least 6 Onium salts of ß-alkoxyalkanesulfonic acids containing carbon atoms. 2. Aqueous polymer dispersions characterized by a content of salts of the general formula in which Y is a radical of the formula -S, -P-R8 or -N-R9, R1 is an alkyl radical having 1 to 20 carbon atoms, R2, R3 and R4 are hydrogen atoms or alkyl radicals having 1 to 4 carbon atoms, R5 is an alkyl radical having 1 to 20 carbon atoms, R6, R7 and R8 ali. Phatic radicals with 1 to 4 carbon atoms, aromatic or cycloaliphatic radicals with up to 7 carbon atoms, and Rg is an alkyl radical with 1 to 4 carbon atoms or a heterocyclic, 5- or 6-membered ring formed together with N and R7, which also instead of R6 can carry a double bond between N and b, where at least one of the radicals R1 and R5 contains at least 6 carbon atoms.