DE2110262A1 - Process for the production of copolymer solutions and dispersions - Google Patents

Description

Bsdische Anilin- & Soda-Fabrik AG

Our reference: O.Z. 27 376 Wd / IG 6700 Ludwigshafen, March 2nd, 1971

Process for the preparation of copolymer solutions and dispersions

This invention relates to a process for the preparation of copolymer solutions and dispersions, in which the usual olefinically unsaturated monomers copolymerized with new comonomers will.

Process for the preparation of copolymer solutions and dispersions by polymerizing olefinically unsaturated ones Monomers such as acrylic and methacrylic acid esters, vinyl esters, styrene, butadiene, vinyl and vinylidene halides in diluents with the addition of polymerization initiators and optionally dispersing aids, such as emulsifiers and Protective colloids are known in large numbers. It is also known here so-called "reactive" comonomers in subordinate Amounts to be used as well. Such known reactive comonomers are, for example, olefinically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid and maleic acid and their amides and especially their N-methylolamides, N-alkoxymethylamides and N-acyloxymethylamides, monomers with epoxy groups, such as acrylic acid-1,2-oxopropyl acrylate, olefinically unsaturated Monomers with hydroxyl groups, such as 2-hydroxyethyl acrylate, as well as olefinically unsaturated monomers with hydroxyl and halogen atoms, such as 3-chloro-2-hydroxypropyl acrylate. Such However, monomers result in polymers which mostly crosslink only in the acidic pH range, or, like copolymers of 3> -chloro-2-hydroxypropyl acrylate only at pH 12 or above.

It has now been found that copolymer solutions and dispersions can be obtained by polymerizing conventional olefinically unsaturated ones Monomers in diluents with the addition of polymerization initiators and optionally dispersing aids can be prepared with advantage under conditions customary per se if the comonomers used are minor amounts

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polymerizable monoolefinically unsaturated halogen atoms copolymerized containing pyrimidine derivatives. The halogen atoms should preferably be bound to the pyrimidine ring. Chlorine and bromine atoms are the main halogen atoms Question. Of particular interest as such pyrimidine derivatives are those of the general formula

R ₁ CH-C-CONH

TR

in which R. and R.sup.1 denote a hydrogen atom or a methyl group, R.sup.4 denotes a chlorine or bromine atom and R.sup.j denotes a hydrogen atom, an alkyl group or a chlorine or bromine atom. Particularly suitable pyrimidine derivatives of this general formula are those in which R ^, represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or, preferably, a chlorine atom and R_ is a chlorine atom. Particularly suitable pyrimidine derivatives of the general formula are 2- (4'-acryloylaminophenyl) -4,5-dichloropyrimidine, 2- (3'-acryloylamino-phenyl) -4,5-dichloropyrimidine, 2- (4'-acryloylamino-phenyl) -4,6-dichloropyrimidine, 2,4-dichloro-6- (4'-methacryloylamino-phenyl) -pyrimidine, 2- (4'-acryloylamino-phenyl) -4-chloro-6-methylpyrimidine and 2- (3 ¹ -Methacryloylamino-phenyl) -4,5-dichloro-6-methylpyrimidine of interest. Such comonomers are new.

They can be prepared, for example, by adding the corresponding amino compound in a manner known per se with olefinically unsaturated carboxylic acid derivatives, especially the acid chlorides, such as acrylic acid chloride or methacrylic acid chloride, acylated in an inert solvent. N-methylpyrrolidone (NMP) is particularly suitable as a solvent. the corresponding amines can, for example, expediently be obtained from the nitro compounds by reducing the nitro group in a solvent in the presence of hydrogenation catalysts, preferably Raney nickel, or from the corresponding acylamines obtained by gentle cleavage of the acyl radical

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(DBP 1 225 788).

The polymerizable pyrimidine compounds of the type mentioned are copolymerized in the new polymerization process in minor amounts. In general, good results are obtained if their proportion is between 0.1 and 25, in particular between 2 and 20, preferably between 5 and 20 percent by weight, based on the total monomers.

Other monomers that are generally used as main monomers in the new process, ie in predominant amounts alone or as a mixture with one another, are above all olefinically unsaturated carboxylic acid esters with 4 to 20 carbon atoms, such as acrylic and methacrylic acid esters from 1 to 12, in particular 1 to 8, preferably 1 to 4, alkanols containing carbon atoms, and vinyl esters of 2 to 12 carbon atoms containing carboxylic acids, such as especially vinyl acetate, vinyl propionate, vinyl n-butyrate and vinyl laurate are of interest. Particularly suitable acrylic and methacrylic esters are, for example, methyl, ethyl and n-butyl acrylates, methyl, ethyl, η-butyl and -2-ethylhexyl methacrylates. The main monomers are also vinylaromatic compounds, in particular monovinyaromatic compounds with a benzene nucleus, such as especially styrene, also C-methylstyrene and chlorostyrenes, and vinyltoluenes, 1,3-dienes with preferably 4 to 8 carbon atoms. Atoms, such as especially butadiene, isoprene and chloroprene ¹ , also vinyl halides and vinylidene halides, such as especially vinyl chloride and vinylidene chloride, are of interest. As comonomers there are also predominantly or minor proportions of monoolefinically unsaturated mono- and / or dicarboxylic acids with preferably 3 to 5 carbon atoms, as well as their nitriles, such as especially acrylonitrile, amides such as especially acrylamide and methacrylamide, N-methylolamides, such as especially N-methylolaerylamide and N-methylol methacrylamide, N-alkoxymethylamides preferably have 1 to 4 carbon atoms in the alkyl radical, such as especially N-methoxymethylacrylamide, N-methoxymethyl methacrylamide and Nn-butoxymethylacrylamide, N-acyloxymethylamides with preferably 2 to 4 carbon atoms in the acyl radical, such as N-acetoxymethyl methacrylamide, as well as their N-alkyl derivatives with preferably 1 to 4 carbon atoms in the

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Alkyl radical, such as N-methyl acrylamide, N-methyl methacrylamide, N-ethylacrylamide and N-n-butylacrylamide. As comonomers suitable and polymerizable carboxylic acids are above all acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid in question. As comonomers are also, mostly in proportions of only 0.1 to 10, in particular from 1 to 5 percent by weight, based on the total monomers, N-vinyl lactams, such as N-vinylpyrrolidone, N-vinylcaprolactam and N ^ vinylcapryllactam, Monomers with several polymerizable double bonds, such as divinylbenzene, diallyl phthalate, ethylene glycol diacrylate and 1,4-butanediol diacrylate, vinyl sulfonic acid and their salts and esters are suitable.

Of particular interest as comonomers in the new process are in minor amounts, usually in amounts from 1 to 10, in particular from 2 to 5 percent by weight, based on the total monomers, those monomers which contain groups which, under the influence of acidic catalysts, form a Give condensation or addition reaction. Such colnonomers are those olefinically unsaturated compounds that have a carboxamide, carboximide, glyoxalmonourein, Contain N-methylol, N-methylol ether, oxy or isocyanate groups. As comonomers of this type are acrylamide and methacrylamide and their N-methylol compounds and alkoxymethyl compounds, also N-acryloylurea and N-methacryloylurea, Vinyl isocyanate and the esters of acrylic and methacrylic acid with glycidic alcohol are called.

The emulsion or solution polymerization according to the invention can be carried out under pressure, temperature and concentration conditions which are customary per se can be carried out using the usual tools. Suitable polymerization initiators are for example organic and inorganic peroxy compounds such as hydrogen peroxide, potassium persulfate and ammonium persulfate, Sodium perborate, tert-butyl hydroperoxide and ditert-butyl peroxide, acetyl peroxide, azobisisobutyric acid nitrile and azobisbutyric acid amide. Water is used as a diluent and the usual organic solvents such as liquid hydrocarbons of the petroleum ether type, benzene, toluene

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and xylenes, butyl acetate, etc. in question. The polymerization can be in aqueous solution or in solution in organic solvents or in aqueous emulsion or with emulsification of the monomers and polymers in organic diluents, such as Petroleum ether. The usual dispersing aids, such as protective colloids and emulsifiers, As for example in the book by Houben-Weyl "Methods of Organic Chemistry", Volume XIV / l, macromolecular substances (Georg-Thieme-Verlag, Stuttgart 1961, pages 192 to 208 and 411 to 420) are used in the usual amounts will.

The new polymerization process produces dispersions or solutions of polymers which crosslink particularly easily, for example at room temperature or elevated temperature can be, even in the neutral and weakly alkaline pH range. As cross-linking substances for the Polymers come, for example, polyamines, such as ethylenediamine, Hexamethylenediamine and polyethyleneimine, alcoholates of polyglycols and salts of polycarboxylic acids such as Na polyacrylate in question.

The polymer solutions produced by the new process and dispersions are suitable for such common areas of application of plastic dispersions and solutions in which crosslinking of the polymers, for example after film formation, is sought, for example for paints, as adhesive raw materials, as binders for nonwovens and paper coating slips, as varnishes and for textile and leather finishing. For such purposes, they are generally used in a mixture with crosslinking substances of the type mentioned, the amount of these crosslinking substances generally between 2 and 20 percent by weight, based on the Amount of dissolved and dispersed polymer is.

The parts mentioned in the following examples are parts by weight. '.

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example 1

A mixture of 64 parts of n-butyl acrylate, 15 parts of acrylonitrile, 10 parts of ethyl acrylate, 3 parts of N-methylol methacrylamide, 2 parts of methacrylimide, 1 part of acrylic acid and 5 parts of 2- (4 ^f -N-Äcryloylaminophenyl) -4 is polymerized. 5-dichloropyrimidine in a mixture of 150 parts of water, 2 parts of a conventionally sulfated reaction product of 40 moles of ethylene oxide with one mole of p-isooctylphenol, 0.5 part of Turkish red oil and 0.5 part of sodium persulfate at about 80 ° C. with stirring. A 50 percent copolymer dispersion is obtained, which is particularly suitable as a paint.

2 parts of hexamethylenediamine are added to 50 parts of the copolymer dispersion and a film is produced from the mixture. The film is ^{heated to 80 °} C. for 5 minutes. A film is obtained which is insensitive to solvents and water and does not swell.

Production of 2- (V -N-acryloylaminophenyl) -4,5-dichloropyrimidia

150 parts of 2- (4 ^f -aminophenyl) -4,6-dichloropyrimidine are dissolved in 500 parts of NMP. 50 parts of acrylic acid chloride are added to the solution at 20 to JO ^{0 C.} After 2 hours, the mixture is diluted with 1000 parts of ice water, the 2- (4 ^! -Acryloylaminophenyl) -4,6-dichloropyrimidine precipitating out. It is separated and washed with water. Yield 236 parts.

Example 2

The procedure is as indicated in Example 1, but 5 parts of 2- (4'-methacryloylaminophenyl) -4-chloro-6-methylpyrimidine are used as the pyrimidine derivative. A 50 percent aqueous polymer dispersion is then obtained under otherwise identical conditions, which is also suitable as a paint, and from the added addition of polyamines, such as hexamethylenediamine, water- and solvent resistant coatings can be made.

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Example 3

A mixture of 50 parts of ethyl acrylate is polymerized, 35 parts of methyl methacrylate, 2 parts of N-methylol methacrylic acid amide, 1 part acrylic acid, β parts 2- (3'-acryloylaminophenyl) -4,6-dichloropyrimidine and a polymerizable dye of the general formula

- (CH ₂ - CH ₂ -

NH - C - CH = CH

in a mixture of 150 parts of water, 0.5 part of ammonium persulfate, 2.5 parts of a sulfonated in a conventional manner a reaction product of 25 moles of ethylene oxide and 1 mole of p-isooctylphenol and 0.5 parts Turki meal oil at 70 to 90 ⁰ C. This gives a 50 percent copolymer dispersion, which is suitable, for example, as a binder for nonwovens with leather-like properties;

3 percent by weight ethylene diamine is added to the dispersion and a cotton fiber fleece is impregnated with the mixture. Excess dispersion is removed from the fleece in the usual way and dried. Several layers of the solidified fleece are laid one on top of the other and ^{pressed together at 60 °} C. under a pressure of 200 atmospheres. A violet-colored, soft, leather-like material with high tensile strength is obtained. 2- (3'-Acryloylaminophenyl) -4,6-dichloropyrimidine is prepared analogously to the information in Example 1 using 2- (4'-Aminophenyl) -4,6-dichloropyrimidine as the starting material.

Example 4

A mixture of 50 parts of n-butyl acrylic acid is polymerized, 10 parts of acrylonitrile, 30 parts of ethyl acrylate and 10 parts of 2- (4'-acryloylaminophenyl) -4,5-dichloropyrimidine with the addition of 2 parts of azobisisobutyronitrile in 300 parts

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n-butyl acetate part. 8o ° C. After the polymerization has ended and the resulting solution has cooled, 5 parts of hexamethylenediamine are emulsified in the solution. The mixture is suitable for the production of coatings. Coatings which are produced therefrom / and which ^{are heated to 100 °} C. for 5 minutes are largely crosslinked and are practically not dissolved or swollen by water and the usual solvents.

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Claims (2)

- 9 -. O.Z. 27 claims ify. Process for the preparation of copolymer solutions and ο -dispersions by polymerizing customary olefinically unsaturated monomers in diluents with the addition of polymerization initiators and optionally dispersing aids under customary conditions, characterized in that minor amounts of polymerizable monoolefinically unsaturated pyrimidine derivatives containing halogen atoms are copolymerized as comonomers. 2. The method according to claim 1, characterized in that the polymerizable monoolefinically unsaturated pyrimidine derivatives containing halogen atoms are compounds of the general formula H ₁ - - C ₂ - CONH '^> - ^% used, in which R, and Rp hydrogen atoms or methyl groups, R-, a chlorine or bromine atom and R ^ a hydrogen atom, a Alkyl group, a chlorine 'or a bromine atom. Badische Anilin- & Soda-Fabrik AQ 209838/0967