DE2760406C2 - - Google Patents

Description

The invention relates to a water-soluble, by Air oxidation curable polymer and its use for coating a substrate. The polymer is derived from a hydroxyamide and an unsaturated one Oil fatty acid and contains carboxyl groups, Carboxylestergruppen and optionally radicals of other unsaturated monomers used for addition polymerization are capable. The polymers possess certain properties, such as content of carboxyl groups, Glass transition temperature of the cured film and a Molecular weight within a certain range.

In the past, similar polymers have been used for coatings and similar applications, such as putty sealants. In the US-PS 37 59 915 sealing compounds of this type are disclosed. The invention provides an improvement of the subject matter of US Pat. No. 3,590,016, in which coating compositions of this type are described. There, as well as according to the invention, the polymers contain an acrylic backbone with pendant carboxy units which, in the preferred embodiment, are labeled N- Hydroxylamides are implemented. In the US patent, the acid group of the hydroxyamide can be saturated or unsaturated and the polymers described in the examples are extremely brittle and have a high glass transition temperature (Tg) . The polymers of the US patent may be water-soluble or water-insoluble. The salts of the carboxyl group-containing polymers disclosed in the U.S. Patent can be neutralized with ammonia, certain amines or other bases, including those which are not suitable according to the invention, when a metal-containing, salt-like desiccant is used. These known polymers suffer from a number of problems, including gel formation, poor gloss on drying under high humidity conditions, slow blocking resistance development, and fugitive dispersions.

Water-soluble air-drying resins are known from FR-PS 20 01 310, which is obtained by reacting unsaturated oil fatty acids in the presence of boron compounds by heating to a condensation product containing at least 40% unsaponifiable, which separates unreacted oil fatty acids, the condensation product α, β- ethylenically unsaturated mono- or polycarboxylic acids, if appropriate in the presence of other vinyl or vinylidene compounds, and reacting the resulting reaction product by neutralization with ammonia or an organic base in water dispersible or soluble.

A water-soluble air-drying polymeric material has been found that has certain parameters and properties of the polymer that are critical to its use. For example, the finished coating must have a Tg below 65 ° C, preferably below 60 ° C. The calculated Tg of the prepolymer or backbone polymer should preferably be below 50 ° C prior to esterification, although it may be as high as 85 ° C if there is a greater content of amide units.

The invention is a in the claims defined in air oxidatively curable Polymer and its use for coating a Substrate.

The polymers used in the invention, the The units (a) contain one can by esterification a backbone or base polymer with produce a hydroxyamide.

The base polymer contains units of formula II

where X is the optional units represents, different from another Ethiopian derive unsaturated monomers, R⁸ = H is and R¹ and R⁵ have the already defined meaning.

The hydroxyamide, a fatty acid amide, has the formula III

where R², R³ and R⁴ have the meaning already indicated to have.

The Fettsäurehydroxyamid can be by esterification the carboxyl groups of the polymeric backbone through the Produce hydroxyamide. As publications for such Implementations may be mentioned: The Journal of the American Oil Chemist's Society, Vol. 46 (1969), pp. 355 to 364, where the use of diethanolamine to Preparation of fatty acid amide is described, however According to the invention, the monoethanolamine is preferred.  

Further references are DE-PS 19 40 471 and BE-PS 7 57 271 corresponding to the already mentioned US-PS 35 90 016, wherein the last two patents relate to hard coatings, such as paints. The US and BE patents are generally directed to polymers of the same type, although the products described therein have some drawbacks rendering them unusable for many applications. For example, all backbone polymers described therein are brittle or hard polymers. Examples of the examples of PS is the softest backbone polymer of a polymer of styrene and / or methyl methacrylate having a glass transition temperature (Tg) of 100 ° C or higher.

The fatty acid amide and consequently the radical R⁴ in the Formula I of claim 1 are derived from one or more drying Oils, such as linseed, tung, tall, safflower, conjugated safflor, isano, soybean, dehydrated Castor or citric oil.

A particularly preferred combination of unsaturated drying oil acids contains 50 to 90% of the Acids of dehydrated castor oil, safflower oil, conjugated Saffron oil or soy in mixture with 10 to 50% by weight of the acids of tung oil.  

There are also oils of synthetic origin into consideration, preferably a carbon chain of about 20 carbon atoms or less and such are unsaturated, that they are similar in air How to harden linseed oil. The preferred oils are those in which the main component is two or more olefinically unsaturated groups containing either conjugated or alternating and to which and dehydrated castor oil and which are predominantly Linoleic acid and / or linolenic acid included.

In a preferred embodiment R⁴ is derived from a blend of drying From 50 to 90% by weight of one or more of the oils dehydrated castor oil, safflower oil, conjugated Safflower or soybean oil and 10 to 50% by weight Tungöl included.

Formula II represents the part of Addition polymerization of prepared polymer backbone with free carboxyl groups and also carboxyl groups, by different alcohols in usual Have been esterified. The possibly existing Part -X- is derived from any well-known, polymerizable by addition Vinyl monomers, later defined become.

When R¹ and / or R⁵ are free carboxyl groups (-COOH) contain the hydroxamide with them  Ester groups give those of the Formula I are equivalent.

Examples of R¹ and R⁵ are:

Prior to esterification with the hydroxyamide is the base polymer a water-insoluble vinyl polymer containing the required proportion of carboxyl groups (-COOH) contains. The backbone polymers are known.

The proportion of monomers is in the backbone polymer at least 8 and not more than 15% by weight unsaturated carboxylic acid as units of formula II wherein R⁸ = -H; a special one preferred range is at 10 to 12%. For a good adhesion  It is very desirable that a significant proportion is present at free carboxyl groups and for Maximum flexibility is a minimum desired on functional groups of the drying oils.

The preferred base polymers are vinyl addition polymers which include as an essential component the α, β -unsaturated carboxylic acid, preferably acrylic acid or methacrylic acid. Other suitable copolymerizable acids are mentioned in US Pat. Nos. 3,098,760 and 3,261,796 and further examples are given later.

When a dry substance is present and the acid is in salt form with an amine, the amine is preferably a monoamine rather than a polyamine since the latter could react with the metal of the dry matter. Examples of copolymerizable ethylenically unsaturated monocarboxylic acids or polycarboxylic acids are sorbic acid, acryloxyacetic acid, acryloxypropionic acid, cinnamic acid, vinylfurancarboxylic acid, α- chlorosorbic acid, methacryloxypropionic acid, methacryloxyacetic acid, p-vinylbenzoic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, aconic acid, atropic acid, crotonic acid, itaconic acid or mixtures of such acids , Itaconic acid and the α, β- unsaturated monocarboxylic acids, especially methacrylic acid and acrylic acid, are preferred. Other copolymerizable acids include the alkyl half esters or partial esters of unsaturated polycarboxylic acids, such as itaconic acid, maleic acid and fumaric acid or the partial amides of these acids. Preferred half-esters are the lower alkyl (C₁-C₆) esters, such as acid methylitaconate, acid butyl itaconate, acid methyl fumarate, acid butyl fumarate, acid methyl maleate and acid butyl maleate. Such partial esters as well as the partial amides are considered according to the invention as "α, β- unsaturated monocarboxylic acids".

The term "vinyl monomer" closes Monomers with the following groups:

vinylidene CH₂ = C vinyl CH₂ = CH- and vinyls -CH = CH-,

it is irrelevant whether the individual monomers are homopolymerizable and it is only important that they give the optional units of the symbol X. Examples thereof are α, β- ethylenically unsaturated monocarboxamides, α, β- ethylenically unsaturated aldehydes, α, β- unsaturated dicarboxylic acid amides, α, β- ethylenically unsaturated nitriles, hydrocarbons, such as α- olefins, conjugated diolefins, vinylaryl compounds, vinyl alkyl ethers, vinyl halides, Vinylidene halides, vinyl sulfides, vinyl acyloxy compounds (esters of saturated carboxylic acids and ethylenically unsaturated alkanols), vinyl amines and their salts, vinyl acid amide monomers, vinyl compounds having heterocyclic nitrogen groups (HN <) and halo, hydroxyalkyl or aminoalkyl substituted derivatives of these compounds, whether or not is homo- or copolymers.

Examples of known vinyl polymers which can be used, and procedures too their preparation are described in "Polymer Processes" Schildknecht, Interscience, N.Y. (1956), p. 111 to 174. Mixtures of various Polymers can also be used.

Examples of suitable monomers which may be used to prepare the water-insoluble base polymer for use in the present invention in addition to the unsaturated acidic monomers and their esters with alkanols of 1 to 20 carbon atoms such as methanol, ethanol, butanol and pentadecanol are acrolein, methacrolein; Ethylene, propylene, isobutene, butadiene, isoprene, chloroprene; Styrene, vinyl toluene; Vinyl methyl ether, vinyl isobutyl ether, vinyl chloride, vinyl bromide, vinylidene chloride, vinyl sulfide, vinyl acetate, vinyl propionate, the vinyl pyridines; primary amino compounds such as β- aminoethyl vinyl ether, aminopentyl vinyl ether; secondary amino-containing compounds such as tert-butylaminoethyl methacrylate; tertiary amino compounds, such as dimethylaminoethyl methacrylate and the corresponding salts, such as the chlorides or hydroxides and ureido monomers, as described in US Pat. No. 3,356,627. Co- and graft copolymers as well as block or segment polymers are also suitable.

Another of the essential monomers except the acidic monomers, usually a larger one Makes up a proportion of the base polymer is a plasticizing Monomer of the following formula IV:

in the R = H or an alkyl radical having 1 to 4 carbon atoms and R¹¹ is a straight-chain or branched one chain-like radical of a primary or secondary alkanol, Alkoxyalkanols or Alkylthiaalkanols, with bis to 14 carbon atoms. Examples are Ethyl, propyl, n-butyl, 2-ethylhexyl, heptyl, hexyl, Octyl, propyl, 2-methylbutyl, 1-methylbutyl, butoxybutyl, 2-methylpentyl, methoxymethyl, ethoxymethyl,  Cyclohexyl, n-hexyl, isobutyl, ethylthiaethyl (ÄT-S-Ä), Methylthiaethyl (ME-S-ÄT), ethylthiapropyl (ÄT-S-PR), n-octyl,

Decyl and Dodecyl, wherein the radicals R¹¹ when the alkyl radical 2 bis 14 carbon atoms, preferably 3 to 12 carbon atoms contains, and R is preferably H or methyl. When R is alkyl and R¹¹ is alkyl, R¹¹ should be about 6 to about 14 carbon atoms and when R = H and R¹¹ is alkyl, should R 11 preferably contains from about 2 to about 12 carbon atoms, to act as a softening monomer.

Other ethylenically unsaturated copolymerizable vinyl monomers whose homopolymers have a much higher Tg are preferably used in combination with the aforementioned softening monomers, provided that they do not adversely affect the desired properties of the product, for example, undesirably increasing the overall Tg . These "hardening" monomers can be represented by the formula V:

in which R is as indicated above R²² is preferably alkyl and methyl is when R = H and an alkyl radical having 1 to about 25 carbon atoms or an alkyl radical having from 15 to about 20 carbon atoms is when R is methyl. Examples of these hard-hitting ester monomers or other hard-hitting ones Monomers are methyl acrylate, acrylamide, Acrylonitrile, isobutyl methacrylate, vinyl acetate, tetradecyl acrylate, Pentadecyl acrylate, methyl methacrylate, Ethyl methacrylate, tert-butyl acrylate, butyl methacrylate,  Styrene, pentadecyl methacrylate, vinyl toluene, methacrylamide and N-methylolacrylamide.

As is known, the extent and type of branching for a given number of carbon atoms in the alcohol moiety substantially affects the Tg , with the straight-chain products having a low Tg .

Since the Tg is obviously an important property of the backbone polymers, the choice and the proportion of monomers depends essentially on their influence on the Tg . The Tg is a common parameter for the hardness of a polymer and further discussion of this property and its measurement can be found in Flory, "Principles of Polymer Chemistry", (1953), pp. 56-57, Cornell University Press; "Polymer Handbook", Brandrup and Immergut, Sec. III, pp. 61-63, Interscience (1966). The Tg can be determined by measurements, but it can also be calculated, for example, Fox, Bull, Am. Physics Soc. 1,3 (1956) p. 123 or by using the "Rohm and Haas Acrylic Glass Temperature Analyzer" Publication no. CM-24 L / cb, Rohm and Haas Company, Philadelphia, p. 19105. Although the actual Tg is much lower than calculated due to the low molecular weights, the calculated Tg is an essential feature for the characterization of various polymers. Examples of the Tg of high molecular weight (<1 000 000) homopolymers and their inherent T g that allows such calculations are as follows:

Homopolymers of Tg n-octyl | -80 ° C n-decyl -60 ° C 2-ethylhexyl acrylate -70 ° C n-butyl acrylate -56 ° C octyl -20 ° C n-tetradecyl -9 ° C methyl acrylate 9 ° C n-tetradecyl 20 ° C tert-butyl acrylate 43 ° C methyl methacrylate 105 ° C acrylic acid 106 ° C

These and other monomers can be copolymerized together to obtain copolymers having the desired Tg .

The base polymer may preferably be prepared by solution polymerization of one or more of the ethylenically unsaturated acids with other unsaturated monomers. The other unsaturated monomers preferably include vinyl monomers, the esters of acrylic acid and / or methacrylic acid with benzyl alcohol, phenol or a saturated monohydric aliphatic alcohol, in particular an alkanol having 1 to 18 carbon atoms, such as cyclopentanol, cyclohexanol, methanol, ethanol, n-propanol, Isopropanol, n-butanol, methoxyethanol, ethoxyethanol, Methoxyäthoxyäthanol, Äthoxyäthoxyäthanol, isobutanol, sec-butanol, tert-butanol, any pentanols, hexanols, octanols, decanols, dodecanols hexadecanols and octadecanols, always the desired Tg of the acidic monomer not except Eight is left. Preferred vinyl monomers other than the acidic monomer are one or more esters of an α, β- unsaturated carboxylic acid or, if the contemplated vinyl monomers are used, an unsaturated nitrile, a vinyl halide, a vinylidene halide, an aromatic vinyl compound, a vinyl alcohol ester or an unsaturated hydrocarbon , in particular acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyl toluene, vinyl chloride or vinylidene chloride, these monomers serving to give units of the symbol X in formula II above. It is also possible to use mixtures of different base polymers.

The solvents used in the polymerization may be organic Solvent or mixtures thereof used such as benzene, toluene, xylene, solvent naphtha of aliphatic, aromatic or naphthenic Type, such as mineral spirits, ethers, esters, acetone or dioxane. Preferred solvents are commercially available monoalkyl (C₁ to C₄) ethers of ethylene glycol, diethylene glycol or Propylene glycol. Of course, other polymerization to be used. The amount of solvent may be at 0 to 80%, based on polymer solids, with a preferred range at 10 to 65% lies.  

It can be the usual desiccant used as the linoleates, naphthenates and Resinates of cobalt, zirconium, manganese, lead, cerium, chromium, Iron, nickel, uranium and zinc. Also salts of inorganic Acids are useful.

If a desiccant is used, its content may be 0.01 to 3% or higher based on the hydroxyamide of formula III. Good results are often achieved with combinations of desiccants, such as a combination of zinc naphthenate and cobalt naphthenate in quite small amounts. For example, a combination of 0.01 to 0.5% zinc naphthenate with 0.01 to 0.1% cobalt naphthenate is particularly effective. Co ⁺⁺ is suitable as cobalt acetate and can be used together with Mn ⁺⁺ , Zn ⁺⁺ , Zr ⁺⁺ or Pb ⁺⁺ .

A preferred polymer according to the invention contains for the components (b) to (e) the monomers:

• (b) one or more of the monomers ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, Isobutyl acrylate and isopropyl acrylate,
• (c) one or more of the monomers methyl methacrylate, Styrene, ethyl methacrylate, acrylonitrile, butyl methacrylate, Isobutyl methacrylate and vinyl toluene,  
• (d) one or more of the monomers acrylic acid, methacrylic acid, Maleic acid and itaconic acid, and
• (e) optionally one or more of the hydrophilic monomers Hydroxyethyl or hydroxypropyl (meth) acrylate.

The preferred average viscosity molecular weight is between 20,000 and 80,000, preferably 30,000 up to 50,000.

In a preferred polymer in the formula I n = 2, R³ is -H, -CH₃ or -CH₂CH₃ and R⁴ is the radical of one or more acids of drying oils from the above group.

A particular advantage of the products according to the invention is that they are directly on any Substrate can be used without the Need for a primer coat exists.

The substrates that come into consideration Include all types, including of silicate substrates, textiles of glass fibers, Asbestos cement products, cement, stone, stucco, Slate, sandstone, granite, ceramics and porcelain; fiber-reinforced plastic articles, like boats, boat hulls or other shaped bodies made with Glass fiber reinforced polyester or other plastics; Metals, such as aluminum, steel, iron and Bronze; Wood and other building materials; metal oxide layers, such as alumina and iron oxide; textiles made of cellulose, such as cotton, linen, artificial silk, cellulose ester, such as cellulose acetate, silk, wool, Polyamides, polyesters, such as polyethylene glycol terephthalate, Acrylonitrile polymers, vinylidene chloride polymers and other vinyl or acrylic ester polymers; movies, Skins, sheets and other molded articles of plastic, such as cellulose ethers or esters, including of hydroxyethyl cellulose, methyl cellulose, cellulose acetate,  Cellulose acetobutyrate, polyesters, such as polyethylene glycol terephthalate, Polyamides, polymers and copolymers of vinyl chloride or vinylidene chloride, polymers and copolymers of methyl methacrylate, aminoplast or phenoplast resins, organopolysiloxane resins or rubber.

Preferably, the dry coatings have a thickness of 0.0025 to 0.254 mm.

The polymers are especially useful as additives for latexes useful, as explained in Example 3. Suitable latexes are aqueous dispersions of addition polymers, which in general is easier Manufacture manner by direct emulsion polymerization. The most important of these dispersions for the production of aqueous-based paints are polymers including homopolymers and copolymers of

• (1) Vinyl esters of aliphatic acids of 1 to 18 Carbon atoms, in particular vinyl acetate,
• (2) acrylic esters and methacrylic esters of alcohols with 1 to 18 carbon atoms, in particular Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate and  
• (3) mono- and di-ethylenically unsaturated hydrocarbons, such as ethylene, isobutylene, styrene and aliphatic Serve, such as butadiene, isoprene and chlorobutadiene.

Poly (vinyl acetate) and copolymers of vinyl acetate are as film-forming components of aqueous Painting compounds known. Examples of comonomers of vinyl acetate are vinyl chloride, vinylidene chloride, styrene, Vinyltoluene, acrylonitrile, methacrylonitrile and a or more of the already mentioned acrylic and Methacrylic esters. Similarly, for aqueous Paints Copolymers of one or more of the mentioned acrylic ester and methacrylic ester with one or several of the following monomers are used: Vinyl acetate, vinyl chloride, vinylidene chloride, styrene, Vinyl toluene, acrylonitrile and methacrylonitrile. Also Homopolymers of ethylene, isobutylene and styrene and Copolymers of one or more of these hydrocarbons with one or more esters, nitriles or amines of acrylic or methacrylic acid or with vinyl esters, such as vinyl acetate, or with vinyl chloride or with vinylidene chloride can be used. The diene polymers are generally in aqueous Paints in the form of copolymers with one or more of the monomers styrene, vinyltoluene, Acrylonitrile, methacrylonitrile and the already mentioned Acrylic or methacrylic ester used. It is further usual, a small amount, such as 0.5 to 5% of an acidic Monomers in the emulsion polymerization of the mixture  of the monomers resulting from the copolymers of all these three types leads, added. Such acids are for example Acrylic, methacrylic, itaconic, aconite, Citraconic, crotonic, maleic and fumaric acid and the dimeric methacrylic acid.

One can these aqueous dispersions using of one or more emulsifiers of the anionic, cationic or non-ionic type. It can mixtures of two or more emulsifiers regardless of the type used with with the exception that it is generally not favorable, a cationic with an anionic emulsifier in significant quantities because they tend to to neutralize themselves. In addition, many are emulsifiers of the cationic type with the polymers according to the invention incompatible. The amount of emulsifier may be in the range of 0.1 to 5 wt.% or more fluctuate, based on the weight of the whole monomeric approach. When a Persulfattyp initiator is used is the addition of an emulsifier often required and the lack of only one small amount, for example, less than about 0.5% Emulsifier, can sometimes be beneficial, for example from the cost point of view and lower sensitivity of the dried Coating against moisture, in particular in a humid atmosphere. The mean particle size or the average particle diameter of these dispersed polymers may be at about 0.03 to 3 microns or even bigger. If here from the  Particle size is the talk, so will always be on the mean weight diameter reference. This Value is in the ultracentrifuge determined. A description of this method is in the "Journal of Colloid Science 15", (1960) pp. 563-572, J. Brodnyan. In general is the molecular weight of these emulsion polymers high, for example, is the average viscosity molecular weight at about 100 000 to 10 000 000, in the Usually above 500 000. Suitable weight ratios of the components are 10 to 70%, preferably 10 to 50% of the soluble polymer and 30 to 90%, preferably 50 to 90% of the latex polymer (on a solids basis). The polymers of the aqueous dispersions are insoluble in the aqueous medium at a pH of 3 to 11th  

All parts and percentages are by weight; unless expressly stated otherwise is.

In the examples, the following abbreviations are used for the monomers used:

BA - butyl acrylate MMA - Methyl methacrylate AA - acrylic acid S - styrene ON - acrylonitrile HEMA - Hydroxyethyl methacrylate MMA - methacrylic acid BMA - butyl methacrylate EA - ethyl acrylate IBMA - Isobutyl methacrylate MHELAE - linseed oil acids MHESAE - Soy acids MHESAFAE - safflower oil acids MHEDCAE - dehydrated castor oil acids MHETAE - Tungölsäuren MHESTAE - stearic acid - non-drying acid HELAE N-hydroxyethyl-linoleic acid amide ester HESAFAE - N-hydroxyethyl-saffloroleic acid amide ester

The prepolymers listed in the following table, having a solids content of 85 to 90%, were by solution polymerization in ethylene glycol monobutyl ether and esterification after polymerization with the dry oil N-methyl-N- ( β- hydroxyethyl) amide of a portion of the copolymerized unsaturated acid been prepared. The details of the synthesis are shown in Table I and a typical procedure is shown in Table III.

Table I

At higher levels of drying oil, the molecular weight decreases of the uncured polymer somewhat too.

The polymers of average viscosity molecular weight of about 40,000 require significantly less functional groups of drying oil, about 20% for good curing properties, whereas polymers of molecular weight of about 20,000 for effective hardening about 40% to groups of drying oil need.

The cure rate is a function of the type of drying oil. In addition, the curing efficiency depends also of the type of drying oil and its Amount off. Some polymers that are styrene or acrylonitrile contain, have a slightly reduced curing rate. Analogous polymers, the hydroxyethyl methacrylate included, show an increased Cure rate.

The mean molecular weights determined and reported here generally agree with molecular weight determinations through the GPC match. In some cases, the GPC molecular weights of the methylated prepolymers determined, wherein the methylation was carried out for the acidity of the copolymer for more reliable Reduce measurements. "Prepolymers" are the polymers before esterification with the Hydroxyethylamides of drying oils. The prepolymers also become backbone polymers or base polymers  called. The indicated molecular weights were from in addition to the molecular weights of the prepolymers Molecular weight of the drying oil. In an example (F), the GPC molecular weight became determined directly on the methylated finished polymers. The good match between E and F indicates that few links between the chains of the drying oil during the esterification after the Polymerization arise.  

Table II

Comparison of molecular weight values by two different methods

The solution viscosities of water-soluble copolymers can substantially by the addition of an additional solvent be reduced. It was found that (a) the solubility parameter and the hydrogen bonding class an additional solvent on no influence the efficiency in the reduction of the solution viscosity by the additional solvent and (b) under the better additional solvents (acetonitrile, isopropanol, Isobutanol), acetone, methyl ethyl ketone) all about are equal in reducing the viscosity. Other suitable additional solvents are ethylene glycol monobutyl ether, Diethylene glycol monobutyl ether and diacetone alcohol.

After completion of the esterification one should approach Cool as soon as possible, otherwise gelation can occur. Humiliation of the temperature can be Achieve by adding the azeotropic mixture of water and xylene during the esterification cooling and by subsequent Removal of azeotropes by application a vacuum without supplying additional heat. The Esterification temperature and time are also essential. If a temperature of 165 ° C is used, the Esterification to be completed in a much shorter time, for example, 10 minutes to a well usable gel-free To have time, whereas in an esterification at 145 ° C reached a much longer gel-free time if the esterification also over a period of 45 minutes is performed. Other factors leading to the length contributing to the period of absence are the salary of the polymer according to the invention of copolymerized  Acid, because of a lower content of acid gives a longer gel-free time, and the total solids content the composition, since products of lower solids content have a longer gel-free time. Another factor is the nature of the drying oleic acid. The chronological order the sensitivity to gelation is like follows: dehydrated castor oil <tung oil <linseed oil logo CNRS logo INIST Saffron oil Soy stearic acid. Additives that suppress the gelling effect are sometimes useful. Such additives include carboxylic acids and aniline. Examples of suitable acids are monochloroacetic acid and benzoic acid.

sample calculation

It will be the relative weight ratios of a BA / MMA / MHELAE / AA copolymer, the by reaction of a carboxyl-containing base polymer with N-methyl-N-hydroxyethyl-linoleic acid amide, was produced.

A prepolymer of composition 35.86BA / 50.19MMA / 13.95AA (calculated Tg = 8 ° C) is added at 20.59%, based on the weight of the prepolymer, (N-methyl-N-hydroxyethyl-linoleic acid amide) (MHELA ) implemented. As a result, 100 g of the prepolymer were reacted with 20.59 g of N-methyl-N-hydroxyethyl-linoleic acid amide.

72 × 0.0611 = 4.40 g AA in 0.0611 mol
18 × 0.0611 = 1.10 g H₂O in 0.0611 mol

Weight of MHELAE units of formula V: 20.59 + 4.40 - 1.10 = 23.89 g

Finished composition

The polymer compositions according to the invention were calculated in a similar way.  

Example 1 Preparation of 40BA / 30MMA / 20MHELAE (flaxseed oil) / 10AA with a Mv of about 40,000

A monomer mixture was made from the following materials manufactured:

parts butyl acrylate 326.0 methyl methacrylate 244.6 acrylic acid 110.4 mercaptoethanol 3.4

It then became an initiator solution of the following substances manufactured:

parts ethylene glycol monobutyl 35.4 tert-butyl peroctoate 13.6

In a reaction vessel equipped with a stirrer, condenser, a nitrogen purifier and two apparatus for gradual addition was set up, were the following Materials given:

parts ethylene glycol monobutyl 88.0 monomer 40.8

The reaction was heated to 110 ° C and 6% of the initiator solution was added. After 15 minutes, the addition of the remainder of the monomer mixture and the initiator solution was recorded, which was then added over four hours at a temperature of 110 ± 30 ° C. After these additions, a mixture of 1.8 parts of tert-butyl peracetate and 5.8 parts of ethylene glycol monobutyl ether was added to the batch and its temperature increased to 170 ° C. The resulting acrylic base polymer (47.87BA / 35.91MMA / 16.21AA) had a calculated Tg of 7 ° C. At 170 ° C, a mixture of 134.5 parts of N-methyl-N-hydroxyethyl-linseed oil fatty acid amide and 65.0 parts of xylene was added. The temperature dropped to 153 ° C. During the next 45 minutes, maintaining the temperature at 150-155 ° C, 76 parts of a biphasic clear solution were distilled from the batch by applying a partial vacuum. After the distillation, the reaction was cooled to 95 ° C and a mixture of 68.5 parts of 28% aqueous ammonia and 600 parts of deionized water was added to the reaction while stirring vigorously. The reaction was removed from the reaction vessel at 75 ° C and placed in a glass container where it cooled to room temperature.

The product obtained was a clear aqueous solution having a solids content of 51.4% and a viscosity of 281,000 cps. The average viscosity molecular weight was determined to be 42,300. A thin film (25 to 75 μm) of the solution of this polymer containing 0.1% Co ⁺⁺ (as cobalt II acetate) became tack-free within 5 hours and hardened to a slightly yellowish, in a week at room temperature Alkali insoluble film. The glass transition temperature of the cured film was about + 20 ° C.

example 2 Preparation of 40BA / 30MMA / 20MHELAE (linseed oil) / 10AA with a Mv of about 80,000

The procedure of Example 1 was repeated, but the mercaptoethanol was reduced to 1.7 parts. The product obtained was a clear aqueous solution having a solids content of 50.7% and a viscosity of 342,000 cps. The average viscosity molecular weight was determined to be 80,000. A thin film of this material cured in a manner similar to the film of Example 1 and had a Tg of about 25 ° C in cured form.

example 3 Preparation of 20BA / 42MMA / 30MHELAE (flaxseed oil) / 8AA with a Mv of about 20,000

It became a monomer mixture of the following materials manufactured:

parts butyl acrylate 181.5 methyl methacrylate 379.5 acrylic acid 120.5 mercaptoethanol 6.8

This monomer mix (26.6BA / 55.7MMA / 17.7AA) gives a prepolymer with a calculated Tg of about 43 ° C. An initiator solution is prepared from the following starting materials:

parts ethylene glycol monobutyl 35.4 tert-butyl peroctoate 40.8

The following materials were placed in a reaction vessel given with a stirrer, a nitrogen purifier, a cooler and two apparatuses for the gradual addition was equipped:

parts ethylene glycol monobutyl 88.0 monomer 40.8

The batch was heated to 142 ° C and 6% added to the initiator solution. There was an exothermic Reaction, by which the mixture on 151 ° C heated. This temperature was maintained for 15 minutes and then the remainder of the monomer mixture and the initiator solution over four hours at a temperature of 150 ± 3 ° C was added. 15 minutes after completion of these additions became a mixture of 8 parts tert-butyl peracetate and 5.8 parts of ethylene glycol monobutyl ether added. The temperature was at 150 ± 2 ° C held for another 15 minutes and then one Mixture of 224 parts of N-methyl-N-hydroxyethyl flaxseed oil amide and 69.0 parts of xylene gradually in the course of 15 minutes, with the temperature at 150 ± 2 ° C was held. The temperature was left slowly rise to 155 ° C over the course of 30 minutes and  It distilled 30.0 parts of a two-phase clear Liquid from the batch at atmospheric pressure. After distillation, the batch was cooled to 95 ° C and a mixture of 50.3 parts 28% aqueous ammonia and 587 parts of deionized water was added to the batch with good stirring. The Approach was at about 70 ° C from the reaction vessel removed and placed in a glass container where you can Let it cool to room temperature.

The product obtained was a clear aqueous solution, referred to as copolymer 3 solution, having a solids content of 53.1% and a viscosity of 11,230 cps. The average viscosity molecular weight of the copolymer was 22,500. A thin film (25 to 75 μm) of the copolymer solution containing 0.1% Co ⁺⁺ (as cobalt II acetate) became tack-free over five hours cured in two weeks at room temperature to a slightly yellow, alkali-insoluble film having a Tukon hardness of about 1.5 and a glass transition temperature of about 25 ° C.

It was a pigment preparation using a commercial Cowles dissolver, which has a high rotational speed and manufactures the following materials:  

When incorporating the TiO₂ in the liquid starting materials became a very smooth pigment preparation receive. The mixture was mixed with the Cowles mixer with a peripheral speed of 1067-1219 m / min stirred for 30 minutes. The preparation was then submerged Using a standard stirrer diluted as follows:

parts Pigment preparation A 34.5 Copolymer 3 solution with 25% GF containing 0.1% Co ⁺⁺ (as acetate) on total polymeric solids 65.5

The resulting paint had a viscosity of 2700 cP, a pH of 8.5 and after mounting at 60 ° a gloss of 80 (determined according to ASTM D 523-85) with a slightly yellowish tinge. The time to reach the tack-free state was much better than that of commercial ones Substances based on solvent-borne alkyd resins with similar gloss properties.  

When omitting the dispersant was obtained completely satisfactory pigment preparation. It the following starting materials and quantities were used:

Pigment preparation B parts Copolymer 3 solution 53.6% GF 12.5 deionized water 20.7 TiO₂ pigment 66.8

This mix was also used with the Cowles dissolver with a peripheral speed of 1067- 1219 m / min to disperse the pigment. The resulting preparation was quite smooth and settled produce much sooner than the usual semi-glossy Pigment preparations. The preparation was with further water-soluble polymers diluted as follows:

parts Pigment preparation B 34.5 Copolymer 3 solution, 25% GF with 0.1% cobalt II acetate on total polymer solids 65.5

This paint had an approximate volume content of solids of 30% and a pigment volume concentration of 25% with a viscosity of 1750 cP at pH from 8.5 a good passability with a good Flow and flow behavior, an excellent Gloss and a slight yellowish tint.  

It is also possible to use conventional propylene glycol / polyelectrolyte dispersant-containing preparations are used. In such case, the soluble polymer replaces the latex at dilution. A typical pigment preparation has the following composition:

As in the other cases, became a Cowles resolver used for the preparation of the preparation.

The dilution was carried out using a standard Stirrer performed and there were the following materials used:

parts Pigment preparation C 27.3 deionized water 5.6 Copolymer 3 solution, 30% GF 67.1

It was the metallic dry matter in the copolymer 3 solution varies according to the following table:  

The resulting paints showed a very good Gloss and a particularly good gloss depth at 20 ° gloss measurements. These are summarized in the table below with measurements of gloss at 60 ° and viscosity and the pH of the paint composition:

A review of a commercial latex showed at 60 ° a gloss of 65; the value at 20 ° would typically at 20 to 25 are.

An additional variant with good gloss properties is a blend of the water-soluble polymer with a conventional acrylic latex (EA / MMA / MAA 57/42/1) on a 20/80 basis. The following materials were used:

parts Pigment preparation C 33.2 deionized water 6.8 Latex, 46.5% GF 39.5 Copolymer 3 solution, 30% GF with 0.1% Co ⁺⁺ 20.5

This paint showed a 20 ° / 60 ° gloss of 31/80, which was not as good as the paints, containing only the water-soluble polymer, but was much better than the gloss of a paint without the copolymer 3 according to the following composition:

parts Pigment preparation C 36.1 Latex, 46.5% GF 57.3 propylene glycol 5.0 Trimethyl-1,3-pentanediol monoisobutyrate 1.6

The 60 ° gloss of this preparation was 65. Typical comparison values similar formulations were 28.

example 4 Preparation of 20BA / 42MMA / 30MHESAE (soybean) / 8AA polymer with an Mv of about 20,000

The procedure of Example 3 was repeated except that an equal amount of N-methyl-N-hydroxyethyl soybean oil amide was used in place of N-methyl-N-hydroxyethyl linoleic acid amide. The product obtained was a clear aqueous solution having a solids content of 53.4% and a viscosity of 19,000 cps. The acid titer of the copolymer was 1.13 meq / g of the polymer. A thin film (25 to 75 μm) of this polymer solution containing 0.1% Co ⁺⁺ (as cobalt II acetate) cured in two weeks at 60 ° C to a slightly yellow, alkali-insoluble film with a Tukon Hardness of about 2.0.

example 5 Preparation of 40BA / 20MMA / 20MHELAE (flaxseed oil) / 20AA polymers with an Mv of about 20,000

The procedure of Example 3 was repeated, but the amounts were changed as follows: butyl acrylate 326 parts, methyl methacrylate 163 parts, acrylic acid 191.5 parts, mercaptoethanol 3.41 parts, N-methyl-N-hydroxyethyl-linseed oil amide 134.5 parts, aqueous ammonia 138 parts and deionized water 542 parts. The acrylic backbone polymer (47.9BA / 24MMA / 28.1AA) has a calculated Tg of 8 ° C.

The product of this process was a clear aqueous Solution with a solids content of 50.7% and a Viscosity of 14 500 cP. The average viscosity molecular weight was determined to be 21,000.  

example 6 Preparation of 20BA / 42MMA / 30MHELAE (flaxseed oil) / 8AA polymer with a Mv of 20,000; Neutralization with triethylamine

The procedure of Example 3 was repeated, but were 111.1 parts of triethylamine instead of 28% pure Ammonia solution used and the deionized water was lowered to 526.6 parts. The product obtained was a slightly turbid aqueous solution with a Solids content of 53.6% and a viscosity of 11 650 cP. A thin film (25 to 75 μm) of this Polymers cured in a similar manner to the polymer of example 3.

example 7 Preparation of 5BA / 42MMA / 45MHELAE (flaxseed oil) / 8AA polymers with an Mv of about 20,000

The procedure of Example 3 was repeated, changing the starting materials as follows: butyl acrylate 53.8 parts, methyl methacrylate 456.0 parts, acrylic acid 172.4 parts, N-methyl-N-hydroxyethyl linseed oil amide 403 parts, 28% aqueous ammonia 66 , 7 parts and deionized water 571 parts. The acrylic backbone polymer (7.9BA / 66.8MMA / 25.3AA) had a calculated Tg of 84 ° C.

The product obtained was a cloudy aqueous solution having a solids content of 56.7% and a viscosity of greater than 100,000 cP; (Copolymer 7 solution). A thin film (25 to 75 μm) of this polymer solution containing 0.1% Co ⁺⁺ as cobalt acetate cured to a yellow, alkali-insoluble film having a Tukon hardness of about 3.0 and a Tg of about 50 ° C for two weeks at 25 ° C.

The copolymer 7 solution became a preferred pigment preparation for these water-soluble carriers that only Pigment, polymer and water contained incorporated. Such a preparation lacks a coalescing Solvent, wetting agent and dispersants. The preparation had the following Composition:

Pigment preparation D parts Copolymer 7 solution 25% GF 49.2 deionized water 1.6 TiO₂ pigment 49.2

The preparation became common with a Cowles dissolver Made way. Then the preparation became diluted with more water-soluble polymer and it were different amounts of the metal-containing desiccant added. The general composition of this The test series was as follows:  

These paints had pH values, viscosities, gloss values (82 to 94) and other properties consistent with the prior art paints of the invention. In addition, the alkali abrasion resistance was measured according to ASTM D 2486-79 using a Gardner scrubber with 0.454 kg load, 1% commercial detergent solution based on sodium lauryl sulfate and alkylarylsulfonate and 500 cycles. The 60 ° gloss was determined before and after the abrasion test. The substrates were 0.17 mm thick spreads on black polyvinyl chloride strips. Paint # 7-1 (no desiccant) was completely removed from the strip after drying for 3 days in the air; after a week, 30% of the film was removed. After one day of air drying, the gloss of Coating No. 7-4 (0.5% Co ⁺⁺ ) changed from 92 to 81 after the 500 cycles of scrub test, whereas after 7 days of air drying, the gloss changed from 89 to 82 or 8% changed. Two days drying time were sufficient at a level of 0.25% Co ⁺⁺ to keep the gloss at 90%.

example 8 Preparation of 30BA / 40MMA / 20MHELAE (flaxseed oil) / 10AA polymers with an Mv of about 40,000

The procedure of Example 1 is followed except that the amount of butyl acrylate is changed to 245 parts and of methyl methacrylate to 327 parts. This change occurred at the end of the addition of the monomer mixture to the reaction vessel. This monomer mix (35.9BA / 47.9MMA / 16.2AA) gives a calculated Tg of 26 ° C. After addition of the monomer mixture, the batch was heated to 150 ° C, a mixture of 1.8 parts of tert-butyl peracetate and 5.8 parts of ethylene glycol monobutyl ether was added and the temperature of 150 ° C maintained. After 15 minutes, a mixture of 134.5 parts of N-methyl-N-hydroxyethyl linoleic acid amide and 63 parts of xylene was added gradually over about 10 minutes while maintaining the temperature at 150 ± 2 ° C. The temperature was allowed to rise slowly to 155 ° C over 30 minutes and 24 parts of a two-phase clear liquid was distilled from the batch at atmospheric pressure. After distillation, the reaction was cooled to 98 ° C and a mixture of 68.5 parts of 28% aqueous ammonia and 600 parts of deionized water was added to the reaction with good stirring. The reaction was removed from the reaction vessel at 69 ° C and placed in a glass container where it was allowed to cool to room temperature.

The product obtained was a clear aqueous solution having a solids content of 47.9% and a viscosity of 67,500 cps. The acid titer of the copolymer was determined to be 1.34 meq / g of the polymer and the average molecular weight was 58,000. A thin film of this polymer solution containing 0.1% Co ⁺⁺ (as cobalt II acetate) (Copolymer Solution 8) cured in two weeks on a slightly yellow, alkali-insoluble film having a Tukon hardness of about 2.5 and a glass transition temperature of about + 40 ° C.

From this polymer became excellent pigment preparations and paint compounds. In one Cowles Crusher was made up of the following components prepared a pigment preparation:

parts Copolymer 8 solution, 47.9% GF 25.1 deionized water 26.7 TiO₂ pigment 48.2

The preparation was mixed with another copolymer 8 solution diluted and then added water carefully, until the consistency for the painting is correct appeared. The finished mixture contained:

parts pigment preparation 66.5 Copolymer 8 solution, 23.5% GF 26.8 deionized water 6.7

This paint was in terms of their good properties, such as spreadability, gloss, flow and bleeding, comparable to the coating compositions of the copolymers 3 and 7.  

example 9 Preparation of 30BA / 40MMA / 20MHESAFAE (safflower oil) / 10AA polymers with an Mv of about 40,000

The procedure of Example 8 was used with with the exception that N-methyl-N-hydroxyethyl-safflorolamide instead of N-methyl-N-hydroxyethyl-linseed oil amide has been.

The product obtained was a clear aqueous solution with a solids content of 51.7% and a viscosity from 176 000 cP. A thin film of this material hardened in the manner described in Example 8 and indicated similar behavior, except that the hardened Movie had a lighter color.

example 10 Preparation of 30BA / 40MMA / 15MHEDCAE (dehydrated castor oil) / 5MHETAE (tung oil) / 10AA polymers with an Mv of about 40,000

The procedure of Example 8 was used, with the Except that a mixture of 168 parts of N-methyl-N- hydroxyethyl dehydrated castor oil and 56 parts N-methyl-N-hydroxyethyl tungungamide instead of 224 Share N-methyl-N-hydroxyethyl-linseed oil amide used has been.

The product obtained was a clear aqueous solution having a solids content of 48.7% and a viscosity of 257,000 cps. The acid titer of the copolymer was determined to be 1.37 meq / g of the polymer. A thin film (25-75 μm) of this polymer containing 0.1% Co ⁺⁺ (as cobalt II acetate) became tack-free over five hours and hardened to a slightly yellow, alkali-insoluble in six days Film with a Tukon hardness of about 3.4.

example 11 Preparation of 30BA / 40 styrene / 20MHELAE (flaxseed oil) / 10AA polymers (Mv about 40,000)

The procedure of Example 8 was repeated except that styrene was used in place of methyl methacrylate to give a polymer (35.9BA / 47.9S / 16.2AA) with a calculated Tg of 26 ° C.

The product obtained was a clear aqueous solution having a solids content of 49.7% and a viscosity of 304,000 cps. The acid titer of the copolymer was 1.44 meq / g of the polymer. A thin film (25-75 μm) of this polymer containing 0.1% Co ⁺⁺ (as cobalt II acetate) cured in six weeks at 25 ° C to a slightly yellow, alkali-insoluble film with a Tukon- Hardness of about 7.5.

example 12 Polymer of 43BA / 27AN / 20MHELAE (flaxseed oil) / 10AA (Mv about 40,000)

The procedure of Example 8 was used except that the content of butyl acrylate was increased to 350 parts and 221 parts of acrylonitrile were used instead of methyl methacrylate. The backbone polymer (51.4BA / 32.4AN / 16.2AA) had a calculated Tg of 0 ° C.

The product obtained was a clear aqueous solution with a solids content of 49.4% and a viscosity of 490 000 cP. A thin film (25 to 75 μm) of this Polymer cured to six in six weeks at 25 ° C slightly yellow, alkali-insoluble film with a Tukon hardness of about 5.0.

example 13 Polymer of 27BA / 34MMA / 20MHELAE (flaxseed oil) / 14HEMA / 5AA (Mv about 40,000)

The procedure of Example 8 is followed except that the monomer mixture has the following composition: butyl acrylate 200 parts, methyl methacrylate 277 parts, hydroxyethyl methacrylate 114.7 parts, acrylic acid 69.5 parts and mercaptoethanol 3.4 parts. The aqueous ammonia was reduced to 34.4 parts and the deionized water increased to 634 parts. The backbone polymer (32.3BA / 40.7MMA / 16.8HEMA / 10.2AA) had a calculated Tg of 27 ° C.

The product obtained was a clear aqueous solution having a solids content of 49.2% and a viscosity of 465,000 cps. The acid titer of the copolymer was 0.83 meq / g of the polymer. A thin film (25-75 μm) of this polymer containing 0.1% Co ⁺⁺ (as cobalt II acetate) cured in two weeks at 25 ° C to a slightly yellow, alkali-insoluble film with a Tukon Hardness of about 2.5.

example 14 70BMA / 20MHETAE (tung oil) / 10MAA polymer (Mv about 40,000)

The procedure of Example 8 was used with the following exceptions: 1) the monomer mixture (83.4BMA / 16.6MAA) giving a calculated Tg of 38 ° C consisted of the following components: butyl methacrylate 568 parts, methacrylic acid 113 parts, mercaptoethanol 3.4 parts; 2) instead of N-methyl-N-hydroxyethyl-linseed oil amide 129.9 parts of N-methyl-N-hydroxyethyl tungungamide were used; 3) the aqueous ammonia and deionized water were changed to 57.1 parts and 630 parts, respectively, and 4) an additional 500 parts of ethylene glycol monobutyl ether was added to the final polymer solution.

The product obtained was a clear solution with a Solids content of 40.2% and a viscosity of 3370 cP. The copolymer had an acid titer of 1.14 meq / g of the polymer.

A thin film (25 to 75 μm) of this polymer containing 0.1% Co ⁺⁺ (cobalt II acetate) cured in two weeks at 25 ° C to a slightly yellow, alkali-insoluble film with a Tukon- Hardness of about 10 and with a glass transition temperature of about 60 ° C.

example 15 Polymer of 40BA / 40MMA / 10MHETAE (tung oil) / 10AA (Mv about 40,000)

The procedure of Example 8 was used with the following exceptions: 1) the monomer mixture consisted of the following components: butyl acrylate 297 parts, methyl methacrylate 297 parts, acrylic acid 87.2 parts, mercaptoethanol 3.4 parts; 2) instead of N-methyl-N-hydroxyethyl linoleic acid amide, 61.2 parts of N-methyl-N-hydroxyethyl tungungamide were used, and 3) the aqueous ammonia and deionized water were changed to 62.5 and 548 parts, respectively. The 43.6BA / 43.6MMA / 12.8AA acrylic prepolymer had a calculated Tg of 14 ° C.

The product obtained was a clear solution having a solids content of 48.8% and a viscosity of 308,000 cps. A thin film (25-75 μm) of this polymer containing 0.1% Co ⁺⁺ (as cobalt II acetate) cured in two weeks at room temperature to a slightly yellow alkali-insoluble film of Tukon hardness about 1.5.

A polymer from 10BA / 27.5BMA / 40iBMA / 10MHETAE / 12.5AA had similar properties.

Comparative Experiment A Polymer from 20BA / 42MMA / 30MHESTAE (stearate) 8AA (Mv about 20,000)

Here is a saturated fatty acid according to the US-PS 35 90 016 used.

The procedure of Example 3 was repeated with 456 g of a 49.2% solution of N-methyl-N-hydroxyethyl stearamide in xylene instead of N-methyl-N-hydroxyethyl-linseed oil amide in xylene solution. The product was a turbid solution, which became clear when heated to 60 ° C. The solids content was 53.4%. The viscosity at room temperature was 37,000 cP. A thin film (25 to 75 μm) of this polymer solution containing 0.1% Co ⁺⁺ (as cobalt II acetate) remained indefinitely soft, sticky and soluble in alkali.

Comparative Experiment B

This comparative experiment is a repetition of Example 16 of US Pat. No. 3,590,016. The acrylic prepolymer (89.4MMA / 10.6MAA) with a calculated Tg of above 105 ° C. is reacted with the hydroxyethylamide of saffurfo fatty acids to give a polymer of the Composition 79.2MMA / 14.5HESAFAE / 6.3MAA arises.

The example was as described in the US-PS carried out, with the exception that before the last dilution with water and KOH the approach was divided into two parts. Part was with KOH / H₂O, as stated, neutralized and the other part with an equivalent amount of ammonia / Water.  

After the PS, the prepolymer is used as a Solution (column 12, line 45), but emerged in the repetition of the example a heterogeneous Mixture. The mixture eventually became supplements of the amide and the solvent homogeneous.

The following overview summarizes the results:

Comparative Experiment C Finished composition 35.80 S / 56.65 HELAE / 7.54 AA HELAE - hydroxyethylamine olamide ester

Example 17 of US-PS 35 90 016 was repeated, with the exception that before the last dilution with water (column 13, Line 30) the approach was divided into three parts. Part A was neutralized and diluted with KOH / ~0.25 equivalents on polymeric acid and with water while stirring, diluted. One received while a polymer dispersion. Part B became like that first part dealt with, except that an equimolar Amount of ammonia used instead of KOH has been. Again, a polymer dispersion was obtained. Part C was with a full equivalent diluted in ammonia (based on polymeric acid) and just with so much water that a clear solution with a total solids content of about 47%.

Both dispersions were very unstable. Within A strong sedimentation was observed for 18 hours. Besides, the smell was from all three samples extremely strong. It is a characteristic one Mercaptan search and this one is likely on the used during the polymerization attributed to tert-dodecylmercaptan.

The results are summarized below:  

Oven resistance (10 days / 60 ° C)

Table III

Examination of the hardening

Values for the curing of the polymers used in the comparative experiments B and C were prepared are from Table IV  to see. The last product is a polymer according to the invention.

Conclusions Comparative Experiment B

The samples prepared in this experiment are out unsatisfactory for the following reasons:

• a) the film is too hard and too brittle;
• b) it does not cure sufficiently to be satisfactory To achieve alkali resistance;
• c) the sample neutralized with KOH has a bad one Hydrolytic resistance, as from the elevated Acid titer after heat aging emerges.

Comparative Experiment C

The dispersed samples were unsatisfactory because of their poor sedimentation stability. The samples sedimented so fast that their investigation could not be completed. The solubilized variants of this experiment show satisfactory cure and hydrolytic stability. However, the unpleasant odor of this solution and the excessive hardness and color of the cured film preclude use of this polymer.

Claims (4)

1. A water-soluble, air-oxidatively curable polymer having a carboxyl content of 0.5 to 3 meq / g of the polymer and an average viscosity molecular weight of 20,000 to 80,000 and optionally the carboxyl groups in the form of salt groups with ammonia or a volatile Amine and wherein a cured film of the polymer has a Tg of 10 to 65 ° C, characterized in that it contains

• (A) 5 to 60 parts by weight of units of the formula I.
• (b) 10 to 50 parts by weight of units of one or more of the monomers ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, isobutyl acrylate and isopropyl acrylate,
• (c) 20 to 70 parts by weight of units of one or more of the monomers methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isopropyl methacrylate, acrylonitrile, isobutyl methacrylate, styrene and vinyl toluene, and
• (d) 8 to 15 parts by weight of units of one or more of the acids acrylic acid, methacrylic acid, maleic acid and itaconic acid,

wherein (a), (b), (c) and (d) 100 parts by weight and R¹ = H, (C₁ to C₅) alkyl, halogen, -CN or -CH₂COOR, -COOR or -CH₂COOH and R (C₁ to C₈) alkyl; R³ is -H or (C₁ to C₈) alkyl; R⁴ is an unsaturated, air-curable radical and R⁵ = -H, -COOH, -CONR₂ or -COOR and wherein the radical the residue of a drying oleic acid derived from one or more of the following oleic acids: tung oil, linseed oil, dehydrated castor oil, safflower oil, conjugated safflower oil, soybean oil and citric acid. 2. Polymer according to claim 1, characterized in that the remainder is derived from a blend of from 50% to 90% by weight of one or more dehydrated castor oil, safflower, conjugated safflower or soybean acids blended with 10% to 50% by weight of tung oil acids. 3. Use of an alkaline aqueous solution of the polymers according to claim 1 or 2 in the blend with a polymer latex for Applying to a substrate, wherein the latex polymer in this aqueous solution is not soluble and the soluble polymers and the latex polymer in the ratio of 10 to 70 parts soluble Polymer to 30 to 90 parts of latex polymer based on solids available.