DE1127590B - Process for the production of stable polymer dispersions - Google Patents

Description

It is known to use aliphatic sulfonic acids with longer Hydrocarbon residues as emulsifiers in the production of polymer dispersions by free radicals Polymerization of monomeric, polymerizable, unsaturated compounds in aqueous Me- S dium to use. So one has z. B. the sulfochlorination products of paraffins in the alkali salts the corresponding sulfonic acids and these as emulsifiers in the emulsion polymerization used. One already has long-chain aliphatic alcohols by splitting off water converted into olefinic compounds and sulfone from these by addition of sulfuric acid acids produced, the alkali salts of which are used in the production of polymer dispersions will.

However, all of these compounds have the disadvantage that they contain more or less large proportions of unsaponifiables Contains by-products and neutral salts. These undesirable minor ingredients have an effect detrimental to the course of the polymerization reaction by reducing the rate of polymerization and adversely affect the degree of polymerization of the resulting polymers.

Influencing the polymerization is particularly unpleasant because it is technically practical is not possible to produce the abovementioned customary emulsifiers so that the content of the By-products is constant. In addition, the common emulsifiers usually consist of mixtures of various isomers that occur in varying proportions during the manufacture of the emulsifiers. For these reasons, the production batches of the customary emulsifiers behave in terms of polymerization often different, so that it is not always possible to use these emulsifiers to produce polymer dispersions to produce with consistent qualities.

The unsaponifiable secondary components of the common emulsifiers and the content of neutral salts affect not only the course of the polymerization reaction, but also the stability the resulting polymer dispersions and the quality of the secondary products produced therefrom are disadvantageous the end.

So call z. B. the neutral salts swelling phenomena on paint films produced from the polymer dispersions. The streaks and cloudiness that often occur on pressed or injection-molded parts or on rolled films made from spray-dried or roller-dried emulsion polymers are mostly due to manufacturing processes
of stable polymer dispersions

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Hans Fikentscher, Bad Dürkheim,

Dr. Herbert Willersinn, Dr. Ernst Penning

and Dr. Harry Distler, Ludwigshafen / Rhine,

have been named as inventors

the neutral salts or the unsaponifiable components in the emulsifiers used.

It has now been found that stable polymer dispersions can be produced which are excellent Characteristics of the derived products made from it distinguish themselves if one is ethylenically unsaturated polymerizable compounds polymerized in a conventional manner in an aqueous emulsion and water-soluble salts of / J- (AIkOXy) -ethane-sulfonic acid as emulsifiers and / or the /? - (Alkylmercapto) ethane sulfonic acid with at least 6 carbon atoms used in alkoxy or alkyl mercapto radicals.

The; S- (alkoxy) -ethane-sulfonic acid salts or the / 3- (alkylmercapto) -ethane-sulfonic acid salts have the formula

RO-CH ₂ -CH ₂ -SO ₃ Me
R - S - CH ₉ - CH ₂ - SO, Me

where R is a straight-chain or a branched aliphatic Hydrocarbon radical with at least 6 carbon atoms, but its carbon chain can also be interrupted by heteroatoms, preferably oxygen atoms, and Me is a monovalent one Means metal or an ammonium radical.

The /? - (alkoxy) -ethane-sulfonic acid salts, especially In contrast, they can be used well as emulsifiers in emulsion polymerization easily free of common emulsifiers

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by neutral salts and unsaponifiable by-products or methyl, can be substituted, or to produce vinyl. You can e.g. B. be obtained by. naphthalene, vinyl ketones, such as vinyl methyl ketone or Addition of corresponding alcohols or alcohol vinyl lactams, such as vinyl caprolactam or vinyl mixtures, such as octyl alcohol, branched decyl pyrrolidone, or vinyl esters such as vinyl acetate and vinyl alcohols, Dodecyl alcohol, tridecyl alcohol, pälmityl propioüat, and also vinyl and vinylidene halides, alcohol, stearyl alcohol or the oxyethylation such as vinyl chloride and vinylidene chloride. Also serve, products of alcohols on alkyl vinylsulfonates such as butadiene, isoprene or chloroprene can be and transferring the addition products with the turn. The monomers mentioned can equivalent amount of an alkali metal alcoholate in the alone or in a mixture with others, not yet Alkali salts. - 10 mentioned monomeric compounds, z. B. with ethy-

The j8- (alkylmercapto) ethanes, vinyl ethers, maleic acid, itaconic acid, fumaric sulfonic acids can be used accordingly Salts by addition of alkyl mercapic acid or its esters and nitriles, copolymers, e.g. from dodecycaptan or tridecyl- or also with allyl compounds, Gegemercaptan, to the double bond of the vinyl sulfone, if necessary in the presence of small amounts of acid methyl ester and implementation of the addition 15 water-soluble unsaturated ethylene derivatives, such as products with sodium methylate are obtained. The vinyl sulfonic acids or acrylic acid amide. Production of the emulsifiers is not part of the · As catalysts for emulsion polymerization Invention. are the usual water-soluble compounds

In addition to the advantage that the invention is used in the under the conditions of the polymerization emulsion polymerization The emulsification to be used will disintegrate into polymerization-dissolving radicals. It gates free of neutral salts and unsaponifiable substances. these are preferably per compounds, e.g. B. water parts are, offer the jff- (alkoxy) -ethane-sulfonic acid material superoxide, salts of persulfuric acid, peracetic salts or the / ^ (alkylmercapto) -ethane-sulfonic acid and other water-soluble derivatives of water salts even more significant advantages. In contrast to fabric superoxides. Also water-soluble labile azo compounds the common emulsifiers, which - as above 25 fertilize, which can disintegrate with formation of radicals, already mentioned - mostly more or less undefined - z. B. azo-diisobutyric acid diamide, and other water isomer mixtures represent, they are precisely defined soluble radical formers as well as light, in particular short compounds, so that when they are used there is no wavy light, can be used as catalysts Complications will be due to shifting of the isomeric.

Ratios when using different emulsifiers - 3 ° - The catalysts can also be charged as mixtures are to be feared. be used or with the addition of non-water

Another notable advantage of the catalysts soluble in accordance with the invention, e.g. B. of benzoyl peroxide to be used in emulsion polymerization or cumene hydroperoxide.

the emulsifiers lies in their favorable consistency. · The formation of radicals from the peroxidic catalysis while the usual emulsifiers often lubricators and thus the speed of the polymer, Represent cumbersome to handle masses, sation can in a known manner by Mitverwenlegen The new emulsifiers are accelerated as a dry, free-flowing mixture of activators. Suitable Crystal powders that are easy to weigh and handle- Compounds of this type are, for example, Redukhaben permit. tion agents, such as salts or derivatives of the sulphurous

Of course, the essence of eric acid, sugar or ascorbic acid, which in turn is exhausted, is exhausted The reason for this is not the use of single, specific compounds with small amounts of soluble heavy salts of /? - (alkoxyethane sulfonic acids or /? - (alkyl metal salts can be used. mercapto) ethane sulfonic acids, but it can As emulsifiers according to the invention

also mixtures of various such salts as emulsified water-soluble salts of ^ - (alkoxy / ethane surfontoren be used. The acids according to the invention and / or 5- (alkylmercapto) ethane sulfone can also be used Emulsifiers to be used are used together with acids. It is preferred to use the other known emulsifiers, e.g. with alkyl sodium salts, the alkoxy radical or the alkyl aromatic Sulphonic acids, ethoxylation products mercaptorest should have at least 6, but preferably 8 of alkylphenols, aliphatic carboxylic acids, containing up to 18 carbon atoms, Acid amides and the like can be used. Also the 50 emulsifiers are used in amounts of about 0.1 simultaneous use of protective colloids, such as up to 10 percent by weight, preferably 2 to 5 percent by weight gelatin, Polyvinylpyrrolidone or polyvinyl ether, percent based on the monomers, used. the in addition to the new emulsifiers is possible. optimal amount depends on the type of emul-

With the new emulsifiers mentioned, all gators and the monomers used, Ethylenically unsaturated polymerizable compounds 55 The polymerization can be carried out in the usual manner fertilize in an aqueous emulsion in known temperatures between about 5 and 120 ° C vorge-way be polymerized or copolymerized. be taken. The choice of polymerization ais Ethylenically unsaturated polymerizable temperature depends, among other things, on the species ties come z. B, vinyl and vinylidene compounds of the catalyst system used, and vice versa, fertilize in question. Such compounds are for example 60 Furthermore, the polymerization in the open wise acrylic acid and acrylic acid compounds, such as vessel under normal pressure or under pressure in one Acrylic acid nitrile, acrylic acid ester can be carried out by aliphatic autoclave. Generally depends Alcohols having 1 to about 18 carbon atoms depend on the vapor pressure of the monomers in the as well as methacrylic acid and the corresponding meth- selected polymerization temperatures, acrylic acid compounds. Oi-chloroacrylic acid is also 65. The polymer dispersions can be unchanged suitable as a monomeric compound. Further monomers can be used further, e.g. B. for the production of Compounds are styrene, which is in the vinyl group or paints. You can do this in well-known on the nucleus by halogen or alkyl, ζ. B. by chlorine way with plasticizers, pigments or dyes

Claims (1)

5 6 "Luftsauerstorf was removed from the boiler before, during or after the polymerization will. '6000 parts of vinyl chloride poured in, and the kettle The polymer dispersions can, however, also be sealed in a pressure-tight manner. This is then carried out in a known manner to give solid polymers on a polymerisation mixture which is heated to 50 ° C. with stirring. This can e.g. B. done by '5 and held at this temperature for a time of ¹ to failures (coagulation), washing of the emulsifier initially pressure of 8 atm to 5.5 atm falls. The rest and drying. But you can also dry the polymer contents of the kettle directly to room temperature, e.g. B. in a cools, relaxed and the formed polyvinyl chloride atomization dryer or on a drying roller. dispersion drained. In this case, the emulsifier remains in the poly- ίο A finely divided, white dispersion is obtained merisat. Due to their purity and their solids content of 21.4%. which are free from In this case, the inventions of coagulate and which are characterized by good compatibility have a good effect emulsifiers according to the invention are characterized by far less disruptive stability. out than the previously common emulsifiers, which are often The polymer dispersion is made with soda solution Cloudiness, discoloration and reduction of the 15 set neutral, and 0.1% ^of further soda cause thermal stability. (based on the solids content). At- The parts mentioned in the following examples are finally the dispersion in an atomizing Parts by weight. The K values were determined after the dryer was dewatered. A white polymer is obtained Fikentscher method in »Cellulose Chemistry«, powder with a K value of 69. When pressed 13 (1932), p. 58. 20 at 170 ° C one obtains completely clear platelets, Beisüiell ^e * ⁿ ^ character ^for the S ^ute compatibility of it contained emulsifier. 8 parts of the addition product of decyl alcohol Repeat the experiment and swap of methyl vinyl sulfonate, which then leads to the emulsifier used above by the same Sodium salt was saponified, and 2 parts of potassium per- 25 amount by weight of an ampho soap, then obtained sulfate are dissolved in 600 parts of deionized water. a polymer that only becomes cloudy when pressed, In this solution, heated to 80 ° C, is left within opaque platelets, 400 parts of methyl acrylate within 45 minutes. to run. Example 4 is then heated for a further 30 minutes to 80 ° C, then increases the temperature to 90 to 95 ° C 30 8 parts of the sodium salt of 2- (dodecylmercapto) - and thereby removes the unreacted acrylic ethane sulfonic acid and 2 parts of potassium persulfate acid esters in the course of one hour. It is dissolved in 600 parts of water at 30.degree. In this solution 100 parts of ethyl acrylate are placed over the heated dispersion with a weak nitrogen with stirring electricity conducted. After cooling down one becomes very emulsified. The dispersion is then heated to 80.degree finely divided dispersion of polyacrylic acid methyl ester 35 heated. After the onset of the reaction, the mixture is left obtain. The polymer content is 40% · The further 300 parts of ethyl acrylate in the course Dispersion is suitable for making coatings, add dropwise for half an hour and then heat on paper and text; it can also be used for a further 30 minutes at 80 ° C. By brief by saponifying with ammonia or alkali hydroxide heating to 90 to 95 ° C, the unreacted solutions Produce highly viscous aqueous solutions that sold 40 ethyl acrylate. You get a very are suitable as thickeners and binders. finely divided 40% dispersion of polyacrylic acid ethyl ester, which gives clear, soft films Example 2 on drying. Part of the film is made in cyclohexanone too dissolved in a 0.5% solution. With this solution In 500 parts of salt-free water, 2 parts of 45 and the K value of the polymer = 75 are measured. Potassium persulfate and 10 parts of its sodium salt A completely analogously prepared polyacrylic acid ethyl transferred addition product of tridecyl alcohol ester, but dissolved in vinylsulfonic acid methyl ester during its production as an emulsifier. The solution, instead of the sodium salt of 2- (dodecylmercapto), is heated to 75 to 80 ° C. In the course of a sodium salt of a C _I4 ethane-sulfonic acid alkyl-hour is added to a mixture of 200 parts of 50-sulfonic acid is used, however, has an acrylic acid-n-butyl ester and 300 parts of vinyl propionate. K value of 67. Further processing is carried out according to the ρ · · 1 ς in Example 1 carried out in the specified manner. After cooling, example 5 becomes a 50% ^e finely divided, very stable mixed poly- After the procedure given in Example 4 merisatdispersion obtained, which is suitable for preparation 55 again using the sodium salt of of adhesive films and tapes. 2- (Dodecylmercapto) -ethane-sulfonic acid as an emulsifier a 40% dispersion of a polyacrylic acid n-butyl example 3 esters made. The K value of the polymer is 71, while a sodium salt of a C ₁₄ alkyl sulfone In a stirred pressure vessel, 18,000 parts of 60 acid-water produced as an emulsifier, 150 parts of emulsifier, obtained by ad-n-butyl ester in cyclohexanone solution, have a K value of 64 from tridecyl alcohol to vinyl sulfonic acid. methyl ester and transferring the addition product
in the sodium salt, 6.0 parts of sodium tripolyphosphate, 12.0 parts sodium pyrophosphate, 20.6 parts water- 65 PATENT CLAIM: substance superoxide (33%) and 6.0 parts of potassium persulfate submitted. After a process for the production of stable poly- of nitrogen and subsequent evacuation of the merisate dispersions by polymerization of Ethylenically unsaturated polymerizable compound atoms in the alkoxy or alkyl mercapto radical fertilize in a conventional manner used in aqueous. Emulsion, characterized in that as Emulsifiers water-soluble salts of the ^ - (alkoxy) - Publications considered: ethane sulfonic acid and / or the /? - (alkyl mercapto) - 5 German Patent No. 634 037; Ethane sulfonic acid with at least 6 carbon- Swiss patent specification No. 307 331. © 209 559/533 4.62