DE1570809A1 - Process for the production of alkali-soluble resins - Google Patents

Description

SC »Johnson & Son, Inc, Racine, Wisconsin, V ₀ St ₀ A ₀

Process for the preparation of alkali-soluble resins

The present invention relates to alkali-soluble resins. More particularly, it relates to low-molecular-weight alkali-soluble ones Resins, resin solutions (cuts), and processes for their production and cleaning ο

The alkali-soluble resins of the present invention are general Low molecular weight substances with a high acid number, dissolved in alkalis, especially as emulsifiers, leveling agents and film formers are suitable »In detail, these alkali-soluble resins have an average molecular weight of about 700 to 5000 and an acid number of about 140 to 300 and contain at least two monomers, for example a carboxyl group-containing monomer and a carboxyl group-free monomer. Probably affects the distribution of this. Monomers in the resin molecule reduce the effectiveness of the resin solution as an emulsifier

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and / or as a leveling agent. Therefore, only those monomer pairs, d "h _e carboxyl group-containing monomer and monomer free from carboxyl groups, which have a smaller relative reactivity ratio than 1.0 at 80 °, can be used to prepare the resins of the invention.

In the present invention, a resin is considered to be alkali-soluble if it contains no less than about 0.0025 equivalents of carboxyl groups per g of resin and is practically completely dissolved if at least about 80 to 90 % of these carboxyl groups by an aqueous alkaline solution of substances such as borax , Amines, ammonium hydroxide, sodium hydroxide and or «or potassium hydroxide have been neutralized.

In the invention, an aqueous alkaline solution is referred to as resin dissolution (resin cut), which is produced by dissolving of a resin according to the invention is obtained by means of an aqueous base such as ammonium hydroxide.

The resins of the present invention can be described as alkali-soluble substances which

(a) an acid number of about 140-300,

(b) an average molecular weight of about 700-5000,

(c) at least two monomers with a reactivity ratio at 80 ⁰ V of less than about 1.0 including at least one carboxyl group-free,

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polymerizable, ethylenically unsaturated monomers (hereinafter referred to as carboxyl group-free monomer) and at least one carboxyl group-containing, polymerizable, ethylenically unsaturated monomer (hereinafter referred to as carboxyl group-containing monomer)
and

(d) a molar ratio of carboxyl group-free polymerizable, ethylenically unsaturated monomer to carboxyl group-containing polymerizable, ethylenically unsaturated monomer from about 3: 1 to Have 1: 1.

According to the invention, the carboxyl group-free monomer of the resin is preferably a monomer such as ötyrol, vinyltoluene and / or a mixture of both compounds of the structural formula

Ar - CH = CH ₂ (I),

, wherein Ar is an aryl and or, or alkaryl radical, e.g. one Phenyl ~ and or «or tolyl group» This structural formula - is hereinafter referred to as formula I ".

• According to the invention, the one containing carboxyl groups Monomer of the resin preferably a monomer such as acrylic acid, methacrylic acid and / or a mixture thereof, and can by the structural formula

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- ■ 4 "*

R.
CH ₂ m C - COOH (II)

represented v / ground, in which R is hydrogen or a methyl radical. can be. This formula is hereinafter referred to as Formtl II designated·

Pie alkali-soluble resins are made by solution polymerization which consists in that one

(1) the monomers of formula I and II in the presence of a chain transfer medium such as a chain transfer medium Solvent polymerized,

(2) uses a chain transfer medium that dissolves a substantial amount of the monomers and hardness, and

(3) the monomers, part of the chain transfer medium and a polymerization initiator to the Remainder of the chain transfer medium, which is under reaction conditions, with sufficient Speed indicates that there is an excess of waste Monomers in the chain transfer medium is avoided during the polymerization.

The above-mentioned resin dissolution can be described as a practically clear solution which is according to the invention contains low molecular weight alkali-soluble resin and an aqueous base · The resin dissolution has

(a) is a pH greater than about 7;,

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(b) is capable of reducing the surface tension of the water by at least about 20 dynes / cm at 25 ^° C. in a concentration of about 20% by weight and has

(c) a color on the 1953 Gardner's color scale below about 4 and is

(d) a leveling agent »

The smoothing properties of these substances can be seen when you add them to coating compounds, which then can be applied to a support «Under these conditions it was found that the resins promote the formation of promote uniform, cohesive, well-converging films which usually have a high gloss «. A leveling agent according to the invention is a resin solution, that when added to a coating compound

(1) causes the mass to flow evenly when it is applied to a base and

(2) after the coating composition has dried, it forms part of the resulting film and thereby the formation of a smooth, coherent film that no longer shows any features of the application.

(a). Acid number

The acid number of the low molecular weight according to the invention Resins directly influences the solubility of these resins in aqueous-alkaline mixtures and the effect of these resins

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as emulsifiers and / or leveling agents. It has been found that the resin is not soluble in alkali if the acid number of certain resins according to the invention is substantially below about 140. For example, a styrene-acrylic acid resin with an acid number of 110 is not soluble in alkali in the sense given here. This means that a substantial amount of the resin will not be solubilized. Furthermore, if the acid number is considerably greater than about 300, ie about 350, certain resin resolutions are no longer satisfactory as leveling agents, emulsifiers and / or film formers in certain water-resistant coating compositions, since they give the films formed too great a water sensitivity. According to a preferred embodiment of the invention, the resins have an acid number of about 180-250. Resins according to the invention having an acid number of about 190-230 are particularly preferred.

The acid number of the resins of the invention, the current or measured V / ert in contrast to the theoretical value and can be determined by placing the resin in a solution of 66 wt _e - dissolved ^ ethanol and 34 wt .- ^ benzene and the mixture with 0 , 1 η aqueous NaOH is titrated against phenolphthalein. This general procedure is in "Practical Course of Polymer Chemistry" by S »Η. Pinner, Pergamon Press, New York, (1961) p. 113.

It has been observed that the acid number of certain methacrylic acid-containing resins of the present invention is lighter can be determined when the resin is dissolved in acetone and the

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Solution with 0.1 η aqueous NaOH against phenolphthalein over is titrated beyond the transition point. That titrated Resin-acetone mixture is then about 1 hour at room temperature left to stand and then back-titrated with 0.1 η HGl against phenophthalein. The solvent must be used for comparison titrated under the same conditions and the acid number obtained corrected by the blank value. It it has been found that the reproducibility is better when the titrations are carried out at room temperature The terms acid number and acid value are used here in the same sense «

(b) Average molecular weight

As mentioned above, the average molecular weight of the resins according to the invention can be between about 700 and 5000. According to a preferred embodiment, the average molecular weight is between approximately 1000 and 4000. Particularly molecular weights of about 1200-3600 are preferred. All molecular weights given here are mean molecular weights, those with a vapor pressure osmometer model 301A of the Mechrolab, Mountain View, California. Kit with the designation molecular weight always means mean molecular weights.

The molecular weight of the alkali-soluble resins of the present invention is essential in that it is outside of the Resin resolutions in the middle range from about 700 to 5000 no longer satisfactory as a smoothing agent or emulsifier

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gators are.

If certain resin solutions according to the invention are used as emulsifiers for the production of emulsion polymers, such as polymethyl methacrylate, can be used by free radical emulsion polymerization as described in "Fundamental Principles of Polymerization "by G.F. D'Alelio, J * Wiley & Sons, New York, (1952), pp. 201 ff., It was also found that the molecular weight of the resin in the Resin dissolution should be about 1000 to about 2000, preferably about 1000 to 1500. For example, it was found: If such resin dissolutions are used as emulsifiers, the emulsion polymers obtained are stable and contain practically no coagulate, while when using a resin according to the invention with a larger molecular weight, E.g., significantly above 2000, is used as an emulsifying agent, the emulsion polymer obtained has a lower resistance and an undesirable content of coagulate. Although only certain resin resolutions as Emulsifiers in certain emulsion polymerizations Of course, other alkali-soluble resins of the present invention having molecular weights up to. about 5000 successful for resin dissolutions for emulsification different coating compounds can be used.

It has been observed that certain resin solutions according to the invention are particularly effective as smoothing agents containing film formers in various metals

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metallic coating compositions are "If _ζ β Β β specific resin resolutions according to the invention, in which the resin has a molecular weight of about 2100 to about 3600, are added to these coating compositions, they bring about an unexpected improvement of the smoothing and film-forming properties of these coating compositions" If they Coating compositions are added which contain a larger amount of an emulsion polymer, cause certain resin solutions according to the invention, namely those which contain resins with a molecular weight of about 1000 3500, a surprising improvement in the gloss, the smoothness and the water resistance of the films produced from these compositions

(c) Relative rate of reaction ratios

The relative ratio of the reaction rates (cf. Journ ", Polymer Science, 54" 411-455 (1961)) of the monomers of formula I and II influences the composition of the resin. If z «> B _o the relative reaction rate ratio of the monomers is less than about 1.0, preferably less than about 0.45 _y at 80 ^° C. and if the polymerization is carried out in solution as described below, resins with a satisfactory composition are obtained This means that the monomers of the formula I and II in the resin achieve an approximately random distribution compared to a resin in which these monomers are not randomly distributed, i.e. in the repeating units of one monomer with repeating units of the other

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Monomers are connected. The cheapest distribution will be achieved when the resin consists alternately of carboxyl group-free and carboxyl group-containing monomers. When the relative reactivity ratio of the monomers reaches 0.0, the distribution of the monomers in the Polymer of the alternating distribution · If, on the other hand, the relative reactivity ratio of the monomers I and II is significantly greater than about 1.0, resins with unsatisfactory Distribution of the monomers arise. So ζ.Β, physical mixtures of two homopolymers would be unsatisfactory » A satisfactory distribution is achieved when resins, which form clear solutions as resin dissolutions, with a molecular weight of about 700-5000 and an acid number of about 140-300 under the selected polymerization conditions can be obtained.

(d) Molar ratio of the monomers of formula I to those of formula II

It has been found that the molar ratio of the carboxyl group-free monomer (Formula I) to the carboxyl group-containing monomer (Formula II) in the resin affects the balance of the hydrophilic and hydrophobic properties. The monomer containing carboxyl groups (formula ΐΊ ) gives the resin the necessary functional properties in order to achieve the acid number and alkali solubility described above. In the resin dissolution, the carboxyl groups of the carboxyl group-containing monomer form

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the centers of the hydrophilic properties and the carboxy group-free monomer (formula I) the hydrophobic properties, a balance between hydrophilic and hydrophobic properties being obtained which leads to a practically water-insoluble, alkali-soluble polymeric wetting agent (polysurfactant). The resins of the invention have a molar ratio of carboxyl group-free a. Monomer to carboxyl group-containing monomer from about 3: 1 to 1: 1, and then form useful polymeric surfactants in alkaline solution. However, if the molar ratio of the carboxyl group-free monomer to the carboxyl group-containing monomer is outside this range, a satisfactory balance between hydrophobic and hydrophilic properties will not be achieved. For example, if the molar ratio of carboxyl / Z / igruppe-free monomer to the carboxyl group-containing monomer is substantially greater than about 3: 1, the resin is at least partially insoluble in aqueous alkaline media and can therefore not be satisfactory as a polymeric surfactant in an oil-in-water -Emulsion work. It goes without saying that the aqueous alkaline compound which contains this resin would not be resin dissolution in the sense given here. On the other hand, if the molar ratio is substantially less than about 1: 1, the resin gradually loses its properties as an alkali-soluble polymeric surfactant because the balance between hydrophobic and hydrophilic properties has shifted too much to the hydrophilic side and

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the resin dissolution approaches the behavior of a water-soluble polycarboxylic acid.

According to the invention, a molar ratio of carboxyl group-free Monomers to monomers containing carboxyl groups from about 2: 1 to 1.2: 1 are preferred. Of course The acid number of the resin also depends on the ratio of the carboxyl group-free monomer to that containing carboxyl groups From monomers.

Solution polymerization

The resins according to the invention are obtained by addition polymerization in solution because the monomers are ethylenic are unsaturated. The method of polymerization, including chain transfer medium, addition method and Solubilization of monomer and resin is described below.

As resins of the invention have a relatively low molecular weight, ie, _e has an average molecular weight of about 700 to 5,000 can be assumed that the terminal groups of the resin molecule constitute a substantial portion of the molecule and contribute according to the properties of the resin. In this regard, the influence of the chain transfer reaction medium used in the polymerization has proven to be essential. This means that resins according to the invention which are produced by the same process but in different reaction media

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have different properties as emulsifiers, leveling agents and the like solvents are connected via a chain transfer mechanism radicals which are capable of initiating the polymerization of "a significant concentration of these radicals solvent therefore, the terminal groups of the resin molecules _β It was observed that

(1) when using a chain transfer reaction medium, Z ₀ Bc a chain transfer solvent which is a good solvent for the monomers to be polymerized and the resulting resin, and

(2) when using a chain transfer reaction medium that has an appropriate chain transfer constant (suitable solvents are described below),

useful alkali-soluble resins of the invention are obtained which have a suitable molecular weight and are practical contain no undesirable by-products, furthermore, the resins obtained under these conditions have advantageous Properties that are at least partly due to the property " unit of the chain-transferring solvent end groups are ο

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Chain transfer constants are given in detail in the NRL Report 519Q entitled ⁿ Telomerization ^M dated November 19, 1958 from the US Naval Research Laboratory, Washington, DO. 25a, 25b, 25c and 25d. Examples of preferred chain transfer solvents are: methyl isobutyl ketone (about 6.0), toluene (about 0.4), xylene / p-cymene mixtures (about 0.5), 3-heptanone (about 6.0), isoamyl acetate (about 6.0), methyl isobutyl carbinol (about 1.0), butyl cellosolve (about 1.0), cyclohexanone (about <8.0), and mixtures thereof. All chain transfer constants above apply to radicals from styrene and have the value χ 10 at about 80 ^° C. given in brackets.

It is essential that the resins of the invention can be obtained by solution polymerization. The solvation capacity the chain-transferring reaction medium is therefore decisive, because only then the most favorable polymerization and monomer distribution can be achieved when monomers and resin are substantially soluble in the medium. The extent of the polymerization, and to some extent also that Monomer distributions in the resin are thus solvent-dependent The molecular weight of the resin obtained can thus also influence the solution polymerization process. For example, a resin with a molecular weight significantly greater than 5000 would give the reaction medium a greater viscosity to lend.

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If a chain transfer solvent, such as xylene or toluene, is used to make a particular invention Styrene-acrylic acid resin was used observed that the resin was only partially soluble in the solvent. The resin precipitated out during manufacture and was partially soluble in aqueous ammonia «, It is believed that fractionation was caused by precipitation during the Reaction took place, with the resin with the greatest acid content precipitating. The undesired monomer distribution shows due to the low alkali solubility. ■

The usual polymerization processes in bulk, in emulsion, in batch solution and / or as droplets are generally not suitable for the production of the low molecular weight resins according to the invention. At least it has proved to be s? ehv.jerig inventions according to this process To prepare resins that have a useful monomer distribution - have (see example 26). "ine good functional I *! onon: e:> avert eilung is to be noted from the fact that the received Resins Form clear resin solutions in aqueous alkali.

Polymerization initiators, such as benzoyl peroxide and azo-bis-isobutyric acid nitrile, can be used to feed the Polymerization can be used. The concentration of the Initiator helps regulate the molecular weight of the alkali see it at. In general, the higher the initiator concentration is, in general, the lower the molecular weight of the alkali-soluble resin. It was found

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that the resins of the invention are made can by adding about 0.5 to e; about 6.0 mol $ initiator, based on the total content of monomers, used under the polymerization conditions specified here.

That _e, when the addition rate of the starting solution is regulated so as found a more accurate control of the composition of the resin by the portionwise addition of monomer, polymerization initiator, and scored kettenübertragendem solvent to the polymerization mixture, in that a - is not only by the above-described processes of solution If an excess of unreacted monomers is avoided in the reaction medium, a substantial improvement in the monomer distribution is achieved (cf. Examples 20a, 20b and 20c).

Resin cut

V / ie mentioned above, the resin dissolution is pH ert a practically clear solution having a above about 7 »In a substantially lying below about 7 pH ^v, _ζ β Β β about 5, the resin resolution is not a homogeneous solution more; contains resin which has been made soluble in alkali, ie, at a pH value significantly lower than 7, the resins according to the invention therefore precipitate out of the solution. The pH of a resin solution of 20% by weight solids is preferably between about 7.6 and 11.0. Venn the alkali-soluble resin at 20 percent by _e - $ solids in excess of concentrated ammonium hydroxide (28 * .- Ge y £ ΝΗ · ζ) is dissolved, a resin dissolution of

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Maintained pH around 12.

Of course most commercial aqueous bases can be used for producing the resin resolution ", S, o can z ₀ B" aqueous solutions of ammonium 'hydroxide, sodium hydroxide, potassium hydroxide, borax and water-soluble organic amines, such _Ä B _o alkylamines, used, " Examples für.geeignete amines are methylamine, ithylamin, dimethylamine, diethylamine, isobutylamine, propylamine, isopropylamine and other low molecular weight alkylamines, etc ₀ and mixtures thereof., preferably, the alkaline solution of a major amount by weight of a basic substance, the ζ a volatile cation, _β Β · NIL ·, contains. When a resin resolution that contains a volatile alkaline substance, or as an emulsifying agent and 'or leveling agent is used in a coating composition, the volatile cation, d "h _o HH ₄ ^+, while the ^ transformation in the volatile gas NH- * ignore"

The stoichiometric amount of the base, z _o B, NH ₄ OH, which is required to neutralize all the carboxyl groups of the resin, leads to a resin dissolution with an approximate pH value of 8 the carboxyl groups of the resin are neutralized to practically 100 fo.

The effect of these resins on surface tension of water is an acronym for its usefulness as a surfactants «At a concentration of about 20 Grew "- $ £ powder substance set these resin dissolving elements the upper

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f laughing ens oltage of V / ater at least about 20 dynes / cm at 25 ⁰ C lower. Resolutions particularly preferred inventive resins the surface tension of the water at 25 ⁰ G by about 25 to 30 dynes / cm down. Thus, these substances are effective polymeric surface active agents in various aqueous base solutions.

The color of the resin dissolution is especially important when the dissolution is used for certain coating compositions where the finished film should be light in color · Colors on the 1953 Gardner color scale greater than about are undesirable and are often caused by by-products and or or resin degradation caused. If the color is for the Purpose of the resin dissolution is not essential, resin dissolutions with a color numbers much higher than 4 on the 1953 Gardner color scale can be used.

It is essential that the resins of the invention practically no longer contain any reaction solvent. For example, if there are significant amounts of reaction solvent in the Resin are contained, no homogeneous resin dissolutions can be obtained, it rather becomes a milky resin dissolution educated. Such solvent residues are in the resin dissolution undesirable when these are used as emulsifiers or leveling agents in various aqueous-alkaline mixtures for certain mixtures Mixtures is used. For example, minute amounts of such a solvent add to a resin solution the product often has an undesirable odor.

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Heretofore, similar resins have been purified by heating in various ways such as concentrating, distilling, pulverizing and dissolving. Drying consists of exposing the concentrated resin to elevated temperatures. The volatile solvent is driven off by distilling in vacuo in various ways. This dry process is time consuming and has the further disadvantage that the resin is degraded by the prolonged heating at higher temperatures _e It has been found that the inventive en resins can be practically removed under a minimum of degradation of the solvent by subjecting the mixture of the reaction solvent and resin obtained in the polymerization to a high solids content, i.e., "h _e is about 80 to 90 5, concentrated. The concentrated mixture of reaction solvent and resin is then treated with an aqueous alkaline base, e.g. Ammonium hydroxide, dissolved. The mixture of reaction solvent, resin dissolution ■ <:,! aqueous base is then distilled, and an aseotropic? A mixture of water and reaction solvent is distilled off from the resin solution until the distillate is practically free of solvent. When the alkaline solution is a volatile cation> d _e h _e NH. ⁺ , a part of this cation can be converted into KH-, which evaporates and collects in the distillate. In this case, the ammonia water;} :. part of the distillate can be separated from the solvent and returned to the solvent-free resin solution, which is removed from the distillation zone

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■ is, or returned directly to the distillation zone will. The polymerization and azeotropic distillation (dissolution) can of course be carried out continuously will"

Terpolymer Quaterpolymers

In addition to the abovementioned monomers of the formulas I and

t
II, the resin can contain at least one further monomer, such as N-vinylpyrrolidone, diethylaminoethyl methacrylate, 2- * ethyl-5-vinylpyridine, acrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methylhexyl acrylate, 2-ethylhexyl acrylate , Propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, fumaric acid esters such as diethyl and dimethyl fumarate, and itaconic acid esters such as dimethyl itaconate, and mixtures of these monomers.

If the resins according to the invention contain one or more of the additional monomers mentioned, the ratio of the monomers of formula I to those of formula II can of course deviate from the value given above, ie from about 3: 1 to 1: 1. JM to keep the acid number of the resin obtained (which now contains at least one further monomer) between about 140 and 300, the ratio of the monomers of formula I and formula II must of course be different from that of a resin that only contains monomers of formulas I and II contains. For example, a styrene-acrylic acid

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resin with a molar ratio of styrene to acrylic acid of about 1: 1 an acid number of about 298 (see example 24, • Table III), while a styrene-acrylic acid-butyl acrylate resin with an acid number of about 285 has a molar ratio of styrene to acrylic acid of about 0.18: 1 (cf. «, Example. 16, Table I).

If resins of the invention contain one or more of the additional monomers shown, the relative reactivity ratio of monomers of formula I and II unchanged "However, there remains caused by the presence of a third monomer, z" B · ethyl acrylate, further relative reactivity ratios _o In a resin, for example, · Which consists of styrene (29 mol $), ethyl acrylate (29 mol $) and acrylic acid (42 mol $), the reactivity ratio of the pairs of monomers is as follows; Ethyl acrylate: acrylic acid = 2.1: 0.37 styrene: acrylic acid = about 0.22: 0.35 ethyl acrylate: styrene = about 0.48: 0.80

(See the company publication "Glacial Methacrylic Acid Glacial Acrylic Acid "from Rohm & Haas Company SP-88)

The resin dissolutions of these substances, which contain at least one further monomer, are in this respect similar to the resin dissolutions, which only monomers of formula I and II contain, as they are practically clear solutions, the low molecular weight alkali-soluble (der- or quaterpolymers) according to the invention and an aqueous base contain * These resolutions are also the other copolymers according to the invention

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Risate resolutions very similar, in terms of color, Leveling properties and the ability to reduce surface tension of the water. These resolutions but can have a pH below about 7. This means that at a pH value below 7, e.g. about 6.2, certain such resin dissolutions remain in solution and form virtually no precipitate. For example, a Resin dissolution, which is a terpolymer of 50 mol $ acrylic acid, 25 moles of styrene and 25 moles of ethyl acrylate and ammonium hydroxide contains, at pH 6.2 and ambient temperature one practically clear solution.

The following examples describe preferred implementation forms the invention. All quantities are by weight, unless otherwise stated.

example 1

A reaction flask equipped with a mechanical stirrer, thermometer, dropper, nitrogen inlet tube and reflux condenser was de-aired by passing nitrogen through it. 500 parts of methyl isobutyl ketone as reaction solvent were placed in the flask and heated to reflux at 116 ⁰ C under positive nitrogen pressure was maintained throughout the Ifasetzung. Methyl isobutyl ketone has a chain transfer constant of about 6.0 χ 10 at about 80 ^° C. i

A starting solution was made from 208 parts of styrene monomer, 76 parts of aoryleic acid monoeaer, 21.8 parts of benzoyl

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peroxide and 300 parts of methyl isobutyl ketone. The reactivity ratio is 0.25 for styrene and 0.45 for acrylic acid at 80 ^° C. (cf. "Copolymerization Parameters" by L. Young in Journal of Polymer Science, Vol. 54, 411-455 (October 1961)). The molar ratio of styrene to acrylic acid in the starting solution is about 2.0: 1.1. The amount of benzoyl peroxide is about 3.0 moles based on the total monomer content. The starting solution is added to the reaction flask, which contains the boiling methyl isobutyl ketone, over the course of 2 hours at a rate sufficient to avoid an excess of styrene and / or acrylic acid in the reaction flask. After the addition has ended, the mixture is refluxed for a further hour. A further 3.63 parts of benzoyl peroxide and 16.4 parts of methyl isobutyl ketone are then added and the mixture is refluxed for a further 2 hours in order to ensure complete conversion of the monomers. The polymer and the monomers were completely soluble in the solvent. The methyl isobutyl ketone is then distilled off from the reaction flask at normal pressure until about 91% by weight of the original amount of solvent has passed over. The remaining solvent is recovered by distilling the residue in vacuo. After cooling, 294.5 parts of resin are obtained from the flask. The resin had an acid number of about 182 and an average molecular weight of about 1820. When 250 parts of the resulting resin desalted to 42 parts of concentrated ammonium hydroxide and 970 parts

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Water will be a clear solution with the color 1.0 (on the Gardner color scale 1953), the pH value 8.1 and a content of non-volatile components of 20.7 wt .- # obtain.

Of course, an aqueous base other than ammonium hydroxide can also be used to dissolve the resin from Example 1, above, can be used, for example, sodium hydroxide, Potassium hydroxide, borax, organic amines and mixtures of these "substances can be used in place of ammonium hydroxide.

Example 2

The procedure of Example 1 is repeated, except that butylcellosolve, which has a chain transfer constant of about 1.0 χ 10 "^ at 80 ⁰ C, is used as the chain transfer reaction solvent in place of methyl isobutyl ketone. The starting solution consists of 208 parts of styrene, 88, 6 parts of acrylic acid (molar ratio of styrene: acrylic acid approximately 2.0: 1.2), 23.45 parts of benzoyl peroxide (3 »0 Mo 1-06, based on the total monomer content) and 320 parts of butyl cellosolve. The reaction flask contains 518 parts of butyl cellosolve at approx 150 ⁰ C. 1 hour after the addition of the starting solution is finished are further 3.91 parts benzoyl peroxide dissolved in 20 parts of butyl cellosolve was added to the reaction flask and the reaction mixture held for 2 hours at 150 ⁰ C. 329.5 parts resin obtained which has an acid number of about 143 and an average molecular weight of about 2060. The influence of the solvent,

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Butyl cellosolve, the properties of the resin should be "observed. So", Z ₀ B ₀ would have a theoretical acid number of about 200 compared to the observed acid number 143 ".

When 275 parts of the resin obtained are desalted with 40.2 parts of concentrated ammonium hydroxide and 1,060 parts 'Water are mixed, a clear solution of pH 8.3 and Gardner color 2.0 is obtained. The resin can used as a substitute for shellac in certain coating compounds will",

Example 3

The following example shows the preferred method for separating the reaction solvent from those of the present invention alkali-soluble resins ",

A 1500 liter, glass-lined output tank is filled with 11.3 kg of inventive styrene-acrylic acid resin ($ 100 solid), to which 11.3 kg of methyl isobutyl ketone have been added as an artificial impurity, 34.3 kg of water and 2.9 kg of 28 tiger NHiOH charged "the residual styrene monomer of the charge was 1.2 ^, to 100 ° / o hard substance-related. The NH * 0H and water in.dem mixture sufficient to all the resin in a 20 solution followed dissolve "The mixture is dissolved in the starting tank, and pumped at about the 16th floor in a distillation tower having 23 sieve bottom. The distillation column is provided at its lower end with a heater with water vapor below 1.4 kg / cm. A distillate of water, methyl iso-

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butyl ketone and ammonia are used from the starting solution distilled off at a reflux rate of 11.3 kg per hour. Water and methyl isobutyl ketone form an azeotropic mixture, so it is refluxed for as long as until the distillate contains practically no more methyl isobutyl ketone »The distillate is condensed. The methyl isobutyl ketone will be recovered. The water-ammonia layer of the distillate is removed and placed in the purified one Resin dissolution is recycled, which is then from the bottom of the distillation column is removed. The purified resin solution, which is stored in a 1125 liter tank, is used sent through a cooler. If the pH is less than about 7, a milky solution is obtained. Then it will be additional NH.OH added to bring the pH of the resin dissolution to about 9.4, so that a clear solution is obtained will.

The column is initially charged with about 45.3 kg v / water, which of course dilutes the starting solution. Therefore the pesticide content of the starting product is small. However, the pesticide content of the product received later increases as soon as the company has reached a state of equilibrium. The final product contains about 9.6% by weight of pesticides, ₎ has a pH of about 9.4, a viscosity of about 3.8 gentipoise at 25 ° C, a residual styrene content of about 0.06 #, per 100 io pest substance related, and a residual content of methyl isobutyl ketone of about $ 0.5 to $ 0.75> ·

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A similar procedure was carried out on a laboratory scale using a 3 liter flask fitted with a reflux condenser and a still. The flask was charged with 766.8 parts of deionized water and 33 »2 parts of 28, ΟΗ. Then 7 »O parts of 28 # NH ₄ OH were added * 200 parts of powdered styrene-acrylic acid resin, which contained 5-6 wt .-% methyl isobutyl ketone as an impurity, were added, the mixture being heated ^{to 70 ° C.} As the solution temperature 97 ⁰ C had reached an azeotropic Gemisch.von water and methyl isobutyl ketone began abzudeetillieren. About 12.9 parts of moist methyl isobutyl ketone were obtained. The resin solution obtained was a clear solution with about 20 wt. - <$> powder substance at a pH of about 8.7

Examples 4-17

Various ter- and quaternary polymers containing monomers of the formulas I and II were prepared according to the general procedure given in Example 1 \. The initial

• ·

solution and charge, the amount of initiator added afterwards, Yield, acid number and molecular weight of the resins are in the. Table I below.

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Table I.

Starting
solution
Weight
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Weight
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Added
initiator
Weight
share Example 4 Styrene _f 208 N-vinyl pyrrolidone 44.6 Acrylic acid 115.0 Benzoyl peroxide 29.03 4.84 Methyl isobutyl
ketone 367.6 735.3 20.0 Yield ^ 372.4 Acid number ^ 223 Molecular
weight 1250 Example 5 Styrene 177.0 Acrylic acid 65.1 Diethylaminoethyl
methacrylate 25.4 Vazo ^(d > 13.45 2.24 Methyl isobutyl
ketron 267.5 535.0 20.0 Yield ^ 256.2 Acid number ^ ^b ^ 161 molecular
weight -

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Starting
solution
Weight δ
ι hurry feed
Facial
share later
added
initiator
Face
share Example 6 Styrene 177.0 Acrylic acid 65.1 2-methyl-5-
vinyl pyridine 16.4 Benzoyl peroxide 19.88 3.31 Methyl isobutyl
ketone 258.5 517 20.0 Yield ^ 255.2 Acid number ^ 177 Molecular
weight 2220 • Example 7 Styrene 229.0 Acrylic acid nitrile 31.8 Acrylic acid 86.4 Benzoyl peroxide 29.0 4.82 Methyl isobutyl
ketone 376.0 460.0 20.0 CCl, (tetrachlor
⁴ ! .Carbon) 312.0 Ethyl "benzene 212.0 Yield ^ ^a ^ 362.3, Acid number ^^ 148 Molecular
weight 1622

009811/1399

Starting
solution
Weight
share feed
Weight
share Later too
set
initiator
Weight
share I. Example 8 Styrene 156.0 Methyl acrylate 37.2 Acrylic acid 68.6 Benzoyl peroxide 20.9 3.48 Methyl isobutyl
ketone 282.7 565.4 22.0 Yield ^ 258.3 Acid number ^ ^b ^ 184 Molecular
weight 2240 Example 9 Styrene 78.0 n-butyl acrylate 333.0 Acrylic acid 119.0 Benzoyl peroxide 36.3 6.05 Methyl isobutyl
ketone 377.0 552.0 20.0 Yield ^ 543.5 Acid number ^^ 160 Molecular
weight 2050 -

009811/1399

Starting
solution
Weight
share feed
Weight
share * 489.8 Later, too
set
initiator
Weight
share • • 3.18 Example 10 20.0 Styrene 156.0 Acrylic acid 68.7 2-ethylhexyl acrylate 80.0 Benzoyl peroxide 20.97 3.5 Methyl isobutyl
ketone 325.7 567.4 20.0 Yield ^ 293.1 Acid number ^ 153 - * Molecular
weight , 2070 Example 11 Styrene 156.0 Methyl methacrylate 26.3 Acrylic acid 62.6 Benzoyl perox _v d 19.10 M ethyl isobutyl
ketone 244.9 Yield ^ ^a ^ 247.2 Acid number ^ 174 • Molecular
weight 2120

00981 1/1399

- Example 12 Starting
solution
Weight
share feed
Weight
share Later too
set,
initiator
Weight
share - 5.97 Styrene 40.0 n-butyl methacrylate 156.0 Acrylic acid 37.4 Benzoyl peroxide ^f 62.6 M ethy11s ο butyl-
ketone 6.37 1.06 Yield ^ 223.4 256.0 512.0 20.0 Acid number ^ 172 Molecular
weight 2950 Example 13 Styrene Butyl acrylate 46.3 Ethyl acrylate 57.1 Acrylic acid 47.4 Benzoyl peroxide 115.3 Methyl isobutyl
ketone 35.82 Yield ^ 289.0 266.1 532.2 Acid number ( ^b ) 292 Molecular
weight 1450

00 98 11/1399

example

Styrene vinyl toluene acrylic acid methacrylic acid benzoyl peroxide

Methyl isobutyl ketone

Yield (acid number

Molecular weight

345.0 291

1350

feed 1570809 Starting
solution Weight
share Later too
set
initiator Weight
share ■ Weight
share 80.0 90.9 64.8 77.5 40.5 6.75

313.2

626.4

40.0

example

Styrene vinyl toluene butyl acrylate acrylic acid benzoyl peroxide

Methyl isobutyl ketone

yield Acid number

Molecular weight

309 279

1600 49.9 56.7 61.5 126.8 38.70

294.9

589.8

. 6.48 40.0

009Ö 11/1339

Starting
solution 1 570809 By weight
share feed Later too
set /
initiator Weight
share Weight
share Example 16 33.3 Styrene 143.5 Butyl acrylate 126.8 Acrylic acid

(Styrene / acrylic acid molar ratio about 0.18: 1)

Benzoyl peroxide 23.22 Methyl isobutyl
ketone 303.6 Yield ^ 324 Acid number ^ 285 Molecular
weight 1500 Example 17 Styrene 62.4 Butyl acrylate 76.9 Acrylic acid 108.0 Benzoyl peroxide 23.28 Methyl isobutyl
ketone 247.3 Yield ^ 256 • Acid number ( ^b ) 300 Molecular
weight 1750

607.2

3.87

30.0

3.86

494.6

For footnotes (a), (b), (c) and (d) see Table II,

009811/1399

Examples 18, 19a and 19b

In Examples 18, 19a and 19b, a vinyl toluene-aoryl acid resin was used and two styrene-methacrylic acid resins Prepared according to the general procedure Clay Example 1. The starting solution, the feed, the one added later Initiator, yield, acid number and molecular weight of the resins are given in Table II:

Table II

Initial solution

Weight parts

feed

Parts by weight

Later appointed initiator

Parts by weight

Example t8 236.2 Vinyl toluene 76.0 Acrylic acid 21.8 Benzoyl peroxide * 328.0 Methyl isobutyl
ketone Yield ^ 326.0 Acid number ^ 174 . Molecular
weight 2086

546.0

3.63
16.4

09 811/1399

BAD ORSGJNAL

Starting
solution
Weight
share 15 70809
Later zii ~
set
Charging initiator
Weight- weight- '
share parts Example 19a Styrene 208.0 Methacrylic acid 112 Benzoyl peroxide . 24.2 4.03 Butyl cellosolve , 344.2 565.2 ^ ° ^ 20.0 Yield ^ 333.4 Acid number '' 193 Molecular
weight 1700 Example 19b Styrene 208.0 Methacrylic acid 112 Benzoyl peroxide 24.2 4.04 Methyl isobutyl
ketone 344.0 370.0 20.0 Ethylbenzene 318.0 Yield ^ 331 Acid number ^ 229.5 Molecular
weight -

(a) parts by weight

(b) Current (measured) acid number, not theoretical acid number

(c) reaction temperature 160-2 ⁰ C

(d) Azo-bis-isobutyric acid nitrile from E.I, duPont de Nemours & Co., Wilmington, Delaware.

009811/1399

Examples 20a, 20b and 20c Example 20a

A resin made from 69 mol% styrene and 31 mol- ^ acrylic acid was prepared according to Example 1. The resin had an acid number of 174 and an approximate molecular weight of 1900 and was soluble in an aqueous solution containing the equivalent amount of ΝΗ, ΟΗ for the acid content of the resin

Two other resins were made, with certain being The conditions described in Example 1 were modified and the theoretical molar amount of acid in the resin was smaller than with the resin described above «,

Example 20b

A resin made from 80 mol $ styrene and 20 mol $ acrylic acid was prepared by the starting solution of the monomers within one hour (compared to 2 hours in Example 1) was added to the reaction flask containing the refluxing methyl isobutyl ketone Reaction product not evaporated and isolated as in Example 1, but precipitated with heptane. The resin obtained had an acid number of about 108 and a molecular weight of about 2240 and was only partially soluble in an aqueous Solution containing the amount equivalent to the acid content of the resin

0 09811/1399

Example 20ο

Another resin made from 71.5 mole # styrene and 28.5 Acrylic acid was prepared according to Example 20b, except that the starting solution was only about 1 mol $ instead of about 3 mols Benzoyl peroxide added · The resin obtained had an acid number of about 151 and a molecular weight of about 3100 and was only partially soluble in an aqueous solution which contained the amount of NH.OH equivalent to the acid content of the resin.

Example 21

An example of a butt sheet coating composition which contained a resin according to the invention as a leveling agent, emulsifier and film former contained the following components: 12.5 parts of a resin solution of a styrene-acrylic acid resin according to Example 1; 65 parts of polystyrene emulsion with 14 i 'solids content (Ubatol UL-2001 of the UBS Chemical Co., Cambridge, Mass.) J 10 parts Polyäthylenwachsemulsion AC Polyethylene 629 with 14% solids, prepared by the in AC polyethylenes, revised edition, Allied Chemical Co., Semet Solvay Division, New York; 1.0 part tributoxyethyl phosphate and 0.9 part Benzoflex P-600 (polyethylene glycol 600 - dibenzoate from Tennessee Products & Chemical Corporation, Nashville, Tenn.).

If similar resins are added to metal-containing, aqueous alkaline coating compositions, they improve the leveling properties and the film-forming properties of such compositions. ^:

009811/1399

Example 22

A styrene-acrylic acid resin according to Example 1 with an acid number of about 169, a molecular weight of about 2100 was dissolved in aqueous ammonia to give a 20.8% solution of about pH 9-0. 96 parts of this resolution _f O have been used as emulsifiers for an emulsion · The other ingredients were 80 parts of methyl methacrylate, 0.9 parts of (NH,) ₂ S ₂ O _Q and 224.0 parts of deionized water ·

An example of the form of implementation described above now follows. The resin dissolution and deionized water (less than 10 parts of deionized water are required to dissolve the initiator) were placed in a 1 liter nitrogen-filled flask fitted with a mechanical stirrer, thermometer, dropping funnel. Cooler and nitrogen inlet pipe was provided. A positive nitrogen pressure is maintained during the reaction. The mixture is ^{heated to about 50 °} C. with stirring, and the methyl methacrylate is added. The stirring is continued and the ^{temperature is raised to about 75 °} C. and the initiator solution is added. An exothermic reaction sets in. The Umse.tZungstemperatur is held for about 2 hours between about 75 ° and 85 ⁰ C and then the reaction mixture cooled · The fine emulsion obtained is then reacted with ammonium hydroxide to about pH 9 »O, and filtered off the small amount of coagulum ·

A similar process is used to make a polystyrene with a similar resin made in butyl cellosolve to produce emulsion. After filtering, the

009 811/13 9 9 ^BAD original

tene polystyrene emulsion has a pH of about 8.75 and _# is reacted with ammonium hydroxide to about pH 9.0. The optical density of the emulsion polymer at a dilution of 1: 100 is about 0.402. The optical density is measured with a spectrocolorimeter from Bausch and Lomb Optical Co., Rochester, New York. The wavelength of the light source is 500 mu. _f

Example 23

The influence of the molecular weight of the resin on the particle size of an emulsion polymer was observed, by using various resins of the present invention as emulsifying agents in the emulsion polymerization of methyl methacrylate The polymer was prepared by a similar procedure to Example 22. According to the invention Styrene-acrylic acid resins prepared by the procedure of Example 1 were used as emulsifiers » The following results were obtained:

Molecular weight of the
Styrene acrylic acid
resin Optical density ^{v & /}
the polymer
emulsion Coagulate
± n g 1370 0.093 0.0 2580 0.930 3730 0.550 3.6

(a) Procedure and colorimeter as in Example 22; the dilution but was 1:25

(b) A coarse particle size emulsion contained approximately 5 # of the monomer as eoagulate

⁶⁴⁰ 009811/1399

Example 24

A series of styrene-acrylic acid resins with a molar ratio of styrene to acrylic acid of about 1: 1 to 2.3: 1 were prepared according to Example 1. Each resin was dissolved with about the stoichiometric amount of aqueous ammonium hydroxide and the resin solution to about pH 8, "brought 0 the average molecular weight and the acid number of these resins and the surface tension of these resin solutions are shown in Table III indicated, the surface tension of the resin resolutions was content at 20 io solid and 25 ⁰ C measured, since the surface tension of water at 25 0 72.8 dyn / cm, the effect of the resins on the surface tension of the water is easy to see «.

Table III

Average Molecular Ratio. Styrene / acrylic weight acid

Surface tension of an acid followed by resin dissolution number at 25 0 indynes / cm

2350 1: 1 298 30.3 1820 125: 1 228 41.2 1810 2.3: 1 166 44.1 1620 1.5: 1 217 39.6 1800 2.3: 1 167 43.5 2040 1.5: 1 222 39.9 2340 2.3: 1 ' 169 45.2 1770 1.5: 1 221 40.7 1660 2.3: 1 158 41.8

0 09811/1399

Examples 25a, 25b, 25c and 25d

Four resins made from 62 mole styrene and 38 mole acrylic acid were prepared with different reaction solvents and different reaction temperatures IY compiled results
forth,

T a b e 1 1 e IV

Starting
solution feed Later too
set
initiator I. Weight—
share Weight
share Weight
share Example 25a Styrene 208.0 Acrylic acid 88.6 Benzoyl peroxide 23.45 3.91 ' Cyclohexanone 320.0 518.0 Yield - Acid number ^ 197 Molecular
weight 1000 Polymerization at about 155 ⁰ C Example 25b - Styrene 208.0 Acrylic acid 88.6 Benzoyl peroxide 23.45 3.91 Cyclohexanone 320.0 518.0 · .: .aO-, 0 Yield ^ 318.0
Acid number ^ 207 "'' '- ■■ · · Molecular weight 1000 Polymerization at about 115 ⁰ C ÖO 981 1/1399

Example 25c -43- 1 570809 * Styrene Starting
solution
Weight ε
ι hurry feed
Weight
share Later too
set
initiator
Weight
share Acrylic acid Benzoyl peroxide 208.0 X «uryl mercaptan ^v ' 88.6 Cyclohexanone 23 _? 45 * 3.91 Yield ^ 60.8 32.4 Acid number ^ 173.2 320.0 518.0 20.0 Molecular
weight 700 Polymerization at about Example 25d Styrene 115 ⁰ C Acrylic acid Benzoyl peroxide 208.0 M ethyl isobutyl
ketone 88.6 Yield ^ 296- 23.45 3.91 Acid Number ( ^h ) 208 296.6 593.2 20.0 Molecular
weight 1620

Polymerization "at about 115 ° C

(a) parts by weight

(b) Measured acid number

(c) chain transfer agent

00981 1/1399

• ORIGINAL BATHROOM

Example 26

The following example describes the preparation of a styrene-methacrylic acid resin by batch solution polymerization. The starting solution, charge, yield and acid number of the resin are given.

Initial solution feed Parts by weight Parts by weight Example 26, Styrene 104.0 · ■. Methacrylic acid 34.4 Carbon tetrachloride 77.0 Methyl isobutyl ketone 169.0 1000.0 Benzoyl peroxide 10.2 Yield ^ 92.0 Acid number 175 Molecular weight (a) parts by weight

The batch was heated to 90 ° C. under nitrogen. Then all of the starting solution was added. The mixture was then allowed to ^{react at 108 °} G for 3 hours. Most of the solvent was then distilled off and the resin was precipitated. The resin was washed with heptane and then dried in vacuo. 50 parts of the resin obtained were stirred for ₄ OH and 190 parts of deionized water at 5O ⁰ C for about 1 hour with 10.4 parts of concentrated NH. A milky-looking dispersion was obtained which could not be filtered until clear, even with filter aids.

• *

The invention is not limited to the described implementation.

0098 11/1399

limited forms. ^^

- patent claims -

Claims (6)

Dr, Expl. Ι3 470-45 "claims 1. A process for the preparation of an alkali-soluble resin with an acid number of about 140 "to 300 and an average molecular weight of about 700 to 5000, characterized in that (a) at least two monomers are polymerized in the presence of a chain transfer medium, which at 80 ° is a smaller one have relative reactivity ratio than about 1.0, where one monomer is a carboxyl group-free, polymerizable, ethylenically unsaturated monomer of the structural formula Ar-OH = OH ₂ , where Ar can be an aryl or alkaryl group, and the second monomer is a carboxyl group-containing polymerizable, ethylenically unsaturated monomer of the structural formula GH ₂ = G (I) -OOOH, where R is hydrogen or a methyl group, and where the molar ratio of carboxyl group-free, polymerizable ethylenically unsaturated monomer to carboxyl group-containing polymerizable ethylenically unsaturated monomer is between about 3: 1 and 1: 1, (b) a chain transfer term medium which solubilizes a substantial amount of the monomers and resin, and (e) adds monomers, chain transfer solvents and a polymerization initiator to the reaction medium at such a rate "that an excess of unreacted monomers in the reaction medium is avoided" 2 «" method according to claim 1, characterized in that that the chain transfer medium is a chain transferring lo- 009811/1399 solvent is. 3. The method according to claim 2, dadureh that the chain transfer solvent Toluene, a xylene / p ~ gymol ~ Gemisqh, 3-heptanone, acetate, methylisobutylearbinol, butyloellesolve, hexanone or a mixture of these solvents 4 · Method according to claim 1, thereby being carried out that a chain transfer agent is added to the chain transfer medium. 5. The method according to claim 4, characterized in that that the polymerization initiator is in a concentration of about 0.5 mol- # to 6.0 mol- $, based on the total monomer content related, is added, with the initiator bentoyl peroxide or azo-bis-isobutyric acid nitrile and d ^ © chains · ^ transfer agent lauryl mercaptan is 6. The method according to any one of the preceding claims, for the preparation of alkali-soluble resins which contain practically no reaction solvent and a minimum of Hargabbau · "products, characterized in that (a) the mixture of alkali-soluble resin and reaction solvent, which is obtained in a polymerization reaction , ^ U a considerable solid content, (b) the concentrated mixture of alkali-soluble resin and ReaJrHons- > solvent dissolves with an aqueous base and (o) an azeotropic mixture of water and reaction solvent from the dissolution (b) separated by distillation, big that the distillate contains practically no Reaktissnsösungsaitte ^ any more. 0098 11/1399