DE1942542A1 - Aqueous polymer dispersions containing p-aminobenzoic acid derivatives - Google Patents

Description

Bädische Anilin- & Soda-Fabrik AG 1942542

Our reference: O.Z. 26 331 Wd / Dh 67OO Ludwigshafen, August 20, 1969

Aqueous polymer dispersions which contain p-aminobenzoic acid derivatives.

A range of homopolymers and copolymers made from olefinically unsaturated Monomers, which are used in the form of their aqueous dispersion for a variety of fields of application, tends to form possibly colored degradation products in the light. This applies primarily to homopolymers and copolymers of acrylonitrile, vinylimidazole and 1,4-dienes, like butadiene, isoprene and chloroprene too. Polymers which contain the abovementioned monomers in copolymerized form tend e.g. in the light to yellowing. In many cases, other types of changes in the polymers also occur in the light, e.g. embrittlement through dismantling or networking. Such changes in properties are usually found in the polymers after the processing of the aqueous ones Dispersions, e.g. for impregnations, coatings and coatings, instead of and interfere with many areas of application. Disadvantageous changes in properties of this type can be found, for example, in textile finishes, leather finishes and coated paper instead of.

Attempts have been made to remedy this disadvantage by conventionally using aqueous dispersions of such polymers UV stabilizers added. However, the usual UV stabilizers are usually sparingly soluble and with the aqueous dispersions the polymers are generally poorly tolerated.

It has now been found that aqueous dispersions of polymers of olefinically unsaturated monomers do not have these disadvantages, if they contain 0.1 to 5 percent by weight, based on the polymers, of reaction products of p-aminobenzoic acid esters Contain alkylene oxides. Suitable reaction products from p-aminobenzoic acid esters and alkylene oxides can, for example, according to the information in the published documents of Belgian patent 708 159 be made. The implementation results in products of the general formula

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R '

COO - (CH - CH "- O) ₁₇ - R

H- (O- CH ₂ - CH) _x ^

H- (O- CH ₀ - CH)

R '
in the

R for a hydrocarbon residue,

R 'stands for hydrogen or a hydrocarbon radical and the sum of X, Y and Z stand for an integer from 1 to 50, where the indices X, Y and Z are each 0 or an integer. As substituents R are in this general Formula alkyl groups with 1 to 4 carbon atoms of particular importance Meaning, other hydrocarbon radicals are also possible, such as cycloalkyl groups and aryl groups, e.g. the cyclohexyl radical, the 4-methylcyclohexyl radical and the phenyl radical. With the substituents R 'are preferably hydrogen atoms; In addition, the methyl group and other hydrocarbon radicals are particularly suitable, like the ethyl, isopropyl and butyl groups, as well as the phenyl radical. The sum of the indices X, Y and Z is preferably between 10 and 50, especially between 15 and 45. The aqueous dispersions preferably contain 0.2 to 2 percent by weight of the reaction products of p-aminobenzoic acid esters and alkylene oxides.

The reaction products from the p-aminobenzoic acid esters and the Alkylene oxides can be added after or during the aqueous dispersions of the polymers from the olefinically unsaturated monomers their production are added. They can also be used, for example in the case of batchwise production of the aqueous polymer dispersions, add to the polymerization mixture before or at the start of the polymerization. In doing so, these reaction products be used in the form of aqueous slurries or mostly in the form of aqueous solutions. They often exhibit excellent Emulsifying effect.

In addition, the dispersions, for example from their preparation also contain other emulsifiers. Are suitable

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For example, the customary anionic, cationic or nonionic emulsifiers, as given, for example, in Houben-Weyl "Methods of Organic Chemistry", Volume 14/1, pages 207-208. Their proportion in the dispersions can be, for example, between 0.1 and 6 %, based on the polymers, preferably in the range from 0.5 to 2 % . The new aqueous dispersions can also contain the customary protective colloids in the customary amounts.

The content of reaction products of p-aminobenzoic acid esters and alkylene oxides is of particular interest for aqueous dispersions of such polymers, the e £, ß-olefinically unsaturated nitriles, such as acrylonitrile and / or methacrylonitrile, and / or 1,3-dienes, such as in particular Butadiene, isoprene and chloroprene, and / or heterocyclic vinyl compounds such as vinyl imidazole and / or vinyl pyridines, especially if they contain larger amounts of such monomers, ie in the case of heterocyclic vinyl compounds from about 2 percent by weight, in the case of olefinically unsaturated nitriles from about 5 percent by weight, and in the case of butadiene from about 30 percent by weight, copolymerized. Of particular interest are the additions of reaction products of p-aminobenzoic acid esters and alkylene oxides to the customary aqueous dispersions of butadiene-styrene copolymers, whose proportion of copolymerized butadiene is generally between 30 and 70 % , and of the customary butadiene-acrylonitrile copolymers, their The proportion of copolymerized acrylonitrile is generally between $ 5 and $ 50.

The homo-copolymers contained in the dispersions according to the invention can be built up entirely or partially from other olefinically unsaturated monomers. Vinyl aromatic ones come into consideration Monomers such as styrene, ot-methylstyrene and vinyl toluenes, olefinically unsaturated carboxylic acid esters, such as acrylic and / or methacrylic acid esters and / or vinyl esters, vinyl and / or vinylidene halides, such as especially vinyl chloride and vinylidene chloride, and in small proportions also <*, ß-olefinically unsaturated mono- and / or Dicarboxylic acids, which like acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid usually contain 3 to 5 carbon atoms, and optionally substituted amides of such carboxylic acids on the nitrogen atom, such as acrylamide, methacrylic

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amide, N-methylolacrylamide, N-methylol methacrylamide, N-n-butoxy- methylacryl- and methacrylamide, N-methoxymethyl acryl and -methacrylamide, maleic acid imide, maleic acid monoamide and half esters monoolefinically unsaturated dicarboxylic acids, such as maleic acid monomethyl ester and mono-n-butyl ester, also in proportions of up to about 2 percent by weight, based on the polymers, vinyl sulfonic acid, Vinylphosphanic acid and salts of these acids. The proportion of olefinically unsaturated carboxylic acids of the aforementioned type and / or their optionally substituted amides is usually between 0.5 and 5 percent by weight, based on the polymers. As far as the polymers acrylic and / or methacrylic acid esters are polymerized contain, these are preferably derived from 1 to 8, in particular from 1 to 4 carbon atoms containing alkanols, such as Methanol, ethanol, isopropanol, n-propanol, n-butanol, tert-butyl alcohol, Isobutanol, n-hexanol, 2-Ä'thylhexylalkphol or in in some cases also of cycloalkanols, such as cyclohexanol, and. 4-methylcyclohexanol. They also come in subordinate quantities Acrylic and / or methacrylic acid esters are also used as components of the polymers in question, which are substituted by polyvalent atoms, optionally by halogen atoms, in particular by chlorine atoms polyhydric aliphatic alcohols, in particular alkanediols or alkanetriols, e.g. of 2-hydroxy-ethyl acrylate and methacrylate, 3-chloro-2-hydroxypropyl acrylate and methacrylate, Ethylene glycol diacrylate, 1,4-butanediol diacrylate and methacrylate, 1,6-hexanol diacrylate and dimethacrylate, 4-hydroxy-n-butyl acrylate and methacrylate, 2,3-dihydroxypropyl acrylate and methacrylate. In minor amounts are also suitable as acrylic or methacrylic esters, allyl acrylate and methacrylate. As a vinyl ester that is included in the Polymers that can be polymerized are vinyl acetate, vinyl propionate, vinyl n-butyrate and vinyl laurate, i.e. vinyl esters of 2 to 12 carbon atoms containing saturated aliphatic carboxylic acids, of special interest. Vinyl esters of the so-called Versatic acids, vinyl stearate and vinyl acrylate are also suitable and methacrylate.

In the preparation of the dispersions, the usual radical-forming initiators, for example water-soluble organic and inorganic peroxides, such as especially sodium, Potassium and ammonium sulfate, hydrogen peroxide and acetyl peroxide,

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• and / or easily decomposable azo compounds, such as azo-bis-butyric acid nitrile, can be used and you can work under the usual pressure and temperature conditions. The presence of the Reaction products of p-aminobenzoic acid esters and alkylene oxides do not interfere.

The polymer content of the aqueous dispersions is olefinic unsaturated monomers can be varied within the usual limits and is generally between 1 and 60, in particular between 20 and 60 percent by weight, based on the aqueous dispersions. The dispersions can with customary additives, such as Pigments, thickeners ^ antifoams, etc. added and used in the usual way. Depending on the composition of the polymers they are optionally after the addition of customary additives as paints, binders for paper coating slips, Adhesives, binders for nonwovens, for textile impregnation or finishing, as a leather finishing agent or for the production of coatings, etc. suitable. Your stability, resistance to cold and mechanical stability as well as their shelf life, especially if they are in addition to the reaction products of the p-Amlnobenzoic acid esters with the alkylene oxides are still common emulsifiers Contained in the usual amounts, and are distinguished by the content of the reaction products mentioned not adversely affected. Rather, the stability of such dispersions is mostly due to their additional content of those mentioned Implementation products increased. Manufactured from the new dispersions Impregnations, coatings, coverings, etc. are characterized by particularly good resistance to aging, especially in light.

The reaction products from the p-aminobenzoic acid esters and the alkylene oxides are with those contained in the dispersions Polymers generally well tolerated. You're sweating out Films made from the coatings do not come off.

The parts given in the following examples are by weight.

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Example 1 . .-. , .. .. .... -

In a mixture of 100 parts of water, 1 part of ammonium persulfate, ~ .. ■■ 1.5 parts of lauryl sulfate and 0.5 part of a in accordance with the information in the known documents made of the Belgian Patent 159 iodine reaction product prepared from p-Aminobenzoesäureäthylester with 20 moles Ä 'thylenoxid is polymerized in emulsion in a conventional manner to 30 ⁰ C a mixture of 70 parts of butadiene, 30 parts of acrylonitrile, 3 parts of methacrylamide and 1 part of acrylic acid * to give a stable aqueous dispersion which gives on drying a thin layer of a film which does not show any discoloration within 40 hours when exposed to a "UV lamp.

In contrast, a film made from a dispersion that does not contain any additives. of a p-aminobenzoic acid ethyl ester reaction product prepared is obtained upon irradiation with the UV lamp under otherwise identical conditions after 10 hours a clear, a strong yellow color after 40 hours.

Used instead of the above-mentioned reaction product of ethyl p-aminobenzoate With 20 moles of ethylene oxide, one with 40 moles of ethylene oxide is used, all other things being equal Conditions an aqueous dispersion that gives films that ^ almost are equally lightfast.

Example 2 -

Polymerization is carried out in a mixture of idü parts of water, 1 part of lauryl sulfate, 3 parts of 30% hydrogen peroxide and 0.5 part of a reaction product of p-aminobenzoic acid ester and 50 mol of ethylene oxide prepared according to the information in the published documents of Belgian patent 70S 159 Up to 60 ° G chemically from 20 parts of n-butyl acrylate, 50 parts of butadiene, 30 parts of acrylonitrile, 1 part of acrylic acid and 3 parts of N-methylolmethaerylamide in emulsion under conventional conditions. A stable aqueous dispersion is obtained from which films are obtained werdöny äl & helm Irradiate with the UV-Lftmpe within 30 hours no discoloration: reveal. »

On the other hand wZ & m film ·, which comes from an aqueous »« Eis ^ er-siow * & £ «

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Addition of the reaction product from ethyl p-aminobenzoate was prepared in otherwise the same way, were obtained after 30 hours of exposure to the UV lamp under otherwise identical conditions Conditions a clear discoloration.

Example 3

In a mixture of 150 parts of water, one part of the sodium salt of a sulfurized reaction product of p-isooctylphenol with 25 moles of ethylene oxide, 1.5 parts of a reaction product of p-aminobenzoic acid methyl ester with 10 moles prepared according to the information in the published documents of Belgian patent 708 159 Propylene oxide and 1 part of potassium persulfate are polymerized in a conventional manner at 80 ^° C., a mixture of 20 parts of acrylonitrile, 3 parts of N-methylol methacrylamide, 5 parts of acrylic acid, 30 parts of ethyl acrylate and 43 parts of n-butyl acrylate in an aqueous emulsion. A stable 40% aqueous dispersion is obtained. Films produced from the dispersion show no discoloration within 50 hours when exposed to a UV lamp.

In contrast, films which are obtained from a p-aminobenzoic acid methyl ester show in the same way, but without the addition of the reaction product produced dispersion under otherwise identical conditions after 50 hours a clear yellow color.

Example 4

In a mixture of 150 parts of water, 1 part of a C, p - to C ₁ O - alkyl sulfonate, 1 part of potassium persulfate and 1 part of a reaction product of p-aminobenzoic acid-n prepared according to the information in the published documents of Belgian patent 708 159 propyl with 35 moles of ethylene oxide and 1 part of a reaction product of p-isooctylphenol condensed with 25 moles of ethylene oxide produced in the usual way is polymerized in a conventional manner at 65 ⁰ C a mixture of 30 parts of butadiene, 30 parts styrene, 10 parts of acrylonitrile, 2 Parts of methacrylic acid and 1 part of methacrylamide in emulsion. A stable aqueous dispersion is obtained

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sion. Films made from the dispersion show no discoloration within 40 hours when exposed to a UV lamp.

In contrast, films produced from a dispersion under comparable conditions show no reaction product from p-aminobenzoic acid esters and alkylene oxides when irradiated with the UV lamp under comparable conditions a distinct discoloration.

Example 5

In a mixture of 150 parts of water, 1 part of potassium persulfate, 2 parts of a sulfurized reaction product of 25 moles of ethylene oxide with p-isooctylpnenol and part of a reaction product of p-aminobenzoic acid ethyl ester with 40 moles of propylene oxide, polymerization is carried out in the usual manner at 85 ^° C a mixture of 63 parts of n-butyl acrylate, 10 parts of styrene, 10 parts of ethyl acrylate, 10 parts of acrylonitrile, 5 parts of methacrylamide, 1 part of acrylic acid, 1 part of N-methylol methacrylamide, 2 parts of methacrylic acid and 1 part of N-vinylpyrrolidone in emulsion. A stable aqueous dispersion with a solids content of 40 % is obtained. Films produced from the dispersion still show no yellowing in daylight after 21 days.

In contrast, films that are produced in a comparable manner from an aqueous Dispersion without content of ethyl p-aminobenzoate reaction product, but otherwise of the same composition are produced, already colored clearly yellow after 10 days.

Example 6

In a mixture of 150 parts of water, 1 part of potassium persulfate, 1 part of a sulfurized reaction product of 40 moles of ethylene oxide and 1 mole of p-isooctylphenol and 1.5 parts of a reaction < product of 1 mole of ethyl p-aminobenzoate with 10 moles of ethylene oxide is polymerized in a mixture of 45 parts of n-butyl acrylate, 2 parts of butadiene, 8 parts of acrylonitrile, 5 parts of vinylidene chloride, 5 parts of meth-

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acrylic acid, 4 parts of styrene, 1 part of methacrylamide and 10 parts Methacrylic acid ethyl ester in emulsion. You get a $ 40 Dispersion. Films made from the dispersion show none within 10 days when irradiated with a UV lamp Discoloration.

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Claims (1)

- 10 - O.Z. 26th Claim Aqueous dispersions of polymers of olefinically unsaturated monomers, characterized by a content of 0.1 to 5 percent by weight, based on the polymers, of reaction products of p-aminobenzoic acid esters with alkylene oxides, Badisehe Anilin- & Soda-Fabrik AG 109810/2098