KR20000067991A - Process for Preparing Water-Dispersible Polymer Blends - Google Patents

Abstract

The present invention relates to a process for preparing a water dispersible polymer blend comprising a polyamide and a second polymer by polymerizing an polyamide, at least one ethylenically unsaturated monomer, a polymerization initiator and, if desired, an aqueous dispersion or solution comprising an emulsifier. will be.

Description

Process for Preparing Water-Dispersible Polymer Blends

The present invention relates to water dispersible polymer blends of polymers consisting of polyamides and ethylenically unsaturated monomers, methods of making and uses thereof.

US 4,946,932 describes the preparation of water dispersible polymer blends of polymers prepared from polyesters or polyesteramides and ethylenically unsaturated monomers produced by free radical polymerization. Such blends are used in paints, adhesives or other coatings. The disadvantage of this blend is that it does not form a transparent polymer film. Another disadvantage is that the polyester or polyesteramide component is hydrolyzed, which limits its manufacture and use.

US 5,277,978 describes the use of sulfate- and sulfonate-containing polyesters as protective colloids for stable polymer dispersions. This document recommends the use of only 0.5 to 10% protective colloids based on ethylenically unsaturated monomers. This document cautions because using too much of the protective colloid can adversely affect the properties of the dispersion.

A clear transparent film is obtained. As is known from US 4,946,932, cloudy films are obtained when using relatively large amounts of polyester.

EP 0 687 459 describes cosmetic compositions comprising an aqueous dispersion of polyesters of ethylenically unsaturated monomers. The resulting aqueous dispersion can be used to produce a homogeneous and transparent film only if a plasticizer is also added. Such dispersions further have the disadvantage of being unstable to hydrolysis due to the polyester.

It is an object of the present invention to prepare water dispersible polymer blends having the following properties suitable for use as coatings, cosmetics and pharmaceutical compositions, finishing of adhesives, fibers and leather and as paper coatings:

1) to form a clear and clear film without the addition of plasticizers,

2) film formation takes place at room temperature without the use of plasticizers,

3) Use a polymer that is stable for hydrolysis.

We are directed to a process for preparing water-dispersible polymer blends of polyamides and second polymers by polymerizing an aqueous dispersion or solution comprising polyamide and at least one ethylenically unsaturated monomer, a polymerization initiator, and preferably a polymerization emulsifier. Found to be accomplished by

Suitable polyamides for the preparation of water dispersible polymer blends are virtually all conventional water dispersible and water soluble polyamides. Especially preferred

a1) 0-99 mol% of C2-C12 monoaminocarboxylic acid or its lactam,

a2) 0.5 to 50 mol% of at least one diamine having 2 to 18 carbon atoms,

a3) 0-49 mol% of sulfonate-functional carbon atoms having 12 to 12 carbon atoms, and

a4) from 0.5 to 49 mol% of dicarboxylic acids having 2 to 16 carbon atoms.

Suitable monomers a1) are lactams of such monoaminocarboxylic acids or such acids known in the preparation of polyamides, for example, ω-aminoundecanoic acid, ε-caprolactam, laurolactam, caprylolactam or enantho Lactam.

Particularly suitable monomers a2) are substituted or unsubstituted aliphatic, cycloaliphatic or aromatic diamines. Examples of suitable diamines are alkylenediamines or cycloalkyldiamines such as 1,2-diaminocyclohexane, 1,5-pentanediamine, 4,4'-diaminodicyclohexylmethane, 2,2'- (4,4'-diaminodicyclohexyl) propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane or preferably hexamethylenediamine. Other suitable are piperazine, 2,2,4-trimethylhexamethylenediamine, 2-butyl-2-ethyl-1,5-pentanediamine or 4,7-dioxadecane-1,10-diamine, 2-methylpenta Methylenediamine and isophoronediamine.

Suitable sulfonate-functional monomers a3) are salts of ammonium groups in which sulfonate groups are substituted or unsubstituted with alkali metals (eg lithium, sodium or potassium) or with 1 to 4 aliphatic or aromatic groups. It is in form. Suitable sulfonate-functional monomers are salts of aliphatic or aromatic dicarboxylic acids (eg sulfosuccinic acid or 5-sulfopropoxyisophthalic acid), preferably using the sodium salt of 5-sulfoisophthalic acid. .

Examples of suitable monomers a4) are aliphatic dicarboxylic acids, for example sebacic acid, azelaic acid or dodecanedicarboxylic acid, preferably adipic acid or sebacic acid. Examples of suitable aromatic dicarboxylic acids are isophthalic acid or terephthalic acid, which can also be substituted, for example tert-butylisophthalic acid and 3,3'- or 4,4'-biphenyldicar Acids, 3,3'- or 4,4'-diphenylmethanedicarboxylic acids, 3,3'- or 4,4'-diphenylsulfone dicarboxylic acids, 1,4- or 2,6- Naphthalenedicarboxylic acid or 2-phenoxyterephthalic acid.

From monomer groups a1) to a4) it is possible to use both individual monomers and mixtures of monomers in the same group.

Particularly suitable ethylenically unsaturated monomers for the second polymer of the water dispersible polymer blend include olefins of up to 4 carbon atoms (eg ethylene), vinyl-aromatic monomers of up to 10 carbon atoms (eg styrene, α-methylstyrene, ortho-chlorostyrene or vinyltoluene), vinyl and vinylidene halides (eg vinyl chloride and vinylidene chloride), esters of vinyl alcohol with monocarboxylic acids having 1 to 18 carbon atoms (eg , Vinyl acetate, vinyl propionate, vinyl-n-butyrate, vinyl laurate and vinyl stearate), preferably α, β-monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 6 carbon atoms, in particular acrylic acid , Methacrylic acid, maleic acid, fumaric acid and itaconic acid generally with 1 to 12, preferably 1 to 8 and especially 1 to 4 carbon atoms Esters of ol (e.g., methyl, ethyl, n-butyl, isobutyl and 2-ethylhexyl esters of acrylic acid and methacrylic acid, dimethyl maleate or n-butyl maleate), the aforementioned α, β-monoethylene Nitriles of systemically unsaturated carboxylic acids (eg acrylonitrile or methacrylonitrile), and conjugated dienes having 4 to 8 carbon atoms (eg, 1,3-butadiene and isoprene). Monomers other than those mentioned, which are polymerized alone to produce a water soluble homopolymer, are usually included only as modified monomers, which are less than 50% by weight, generally 0 to 15% by weight, based on the total amount of monomers used. %, And preferably in amounts of 1 to 10% by weight. Examples of such monomers are α, β-monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 6 carbon atoms and their amides, for example acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, acrylamide and Methacrylamide, vinylsulfonic acid and its water soluble salts, vinylphosphonic acid, its salts and esters with alcohols of up to 4 carbon atoms, and n-vinylpyrrolidone, 2-hydroxyethyl acrylate, 3-hydroxy Propyl acrylate or dimethylaminoethyl acrylate.

In addition, alone or one or more vinyl, acrylic and / or methacryl monomers, silicon-containing monomers and macromers, fluorine-containing monomers (eg perfluorooctyl methacrylate or 1,1,1, 3,3,3-hexafluoroisopropyl methacrylate).

The crosslinking monomer is used in an amount of 0 to 15% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight, based on the total amount of the monomers used; After drying the polymer, these monomers undergo a crosslinking reaction which can be effected by heat treatment, preferably by addition of a catalyst (eg, a proton donor such as maleic acid, diammonium hydrogen phosphate or ammonium nitrate). Examples of such monomers are n-alkylolamides of α, β-monoethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms, of which N-methylolacrylamide and N-methylolmethacrylamide are preferred. Crosslinking monomers can also be used as esters or ether esters of acrylamidoglycolic acid and methacrylamidoglycolic acid and ethers thereof, alcohols such as alkanols having 1 to 12 carbon atoms (e.g. acrylamidomethoxyacetic acid, Methyl acrylamido hydroxyacetate, methyl acrylamidomethoxyacetate, methacrylamidomethoxyacetic acid, methyl methacrylamidohydroxyacetate, methyl methacrylamidomethoxyacetate, the corresponding butyl and butoxy derivatives, Butyl acrylamidobutoxy acetate and butyl methacrylamidobutoxy acetate). Also suitable are ammonium salts of (meth) acrylamido acids.

Free radical aqueous graft polymerization can be carried out in the presence or absence of a regulator. Examples of suitable modulators are mercapto compounds such as metcaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan. Other suitable modulators are allyl compounds, such as allyl alcohol.

Conventional additives may be added to the polymer dispersion. These are generally added after the end of the polymerization. There may be crosslinking materials which cannot be mixed by polymerization, and they may generally be present in amounts of 0.1 to 5% by weight. Where the polymer comprises free carboxyl, suitable compounds are those which can crosslink such groups, for example basic compounds of polyvalent metals such as zinc oxide, calcium oxide or the corresponding hydroxides, acetates or carbos Nates or the corresponding mixed salts. Suitable compounds are also those which crosslink any hydroxyl present, for example, di- and polyfunctional inorganic acids and acid derivatives such as alkali metal trimethaphosphates, alkali metal polyphosphos, which are oxychlorides. Nate or alkali metal tetraborate, di- and polyfunctional organic acids (eg adipic acid, citric acid, 1,2,3,4-butanetetracarboxylic acid, cis-1,2,3,4-cyclopentane Tetracarboxylic acids), derivatives of di- and polyfunctional organic acids (e.g., anhydrides or mixed anhydrides), e.g., diacetyladipic acid, acetylcitric acid anhydride, acid chlorides (e.g. cyanuric chloride) Dazolides and guanidine derivatives), di- and polyfunctional isocyanates (eg hexamethylene diisocyanate, 2,4-diisocyanatotoluene), di- and polyfunctional alkylating agents (eg epichlorohi Lean, β, β'-dichloroethyl ether, diepoxide, various aldehyde or aldehyde derivatives (eg formaldehyde, acetaldehyde, acrolein, 2,5-dimethoxytetrahydrofuran, or glutaraldehyde). In addition, formaldehyde, glyoxal, melamine, phenol and / or urea based concentrates are suitable, of which formaldehyde and formaldehyde-containing crosslinker systems are less suitable because of toxicological effects.

Suitable polymerization initiators for the novel preparation of water dispersible polymer blends are all capable of initiating free radical aqueous emulsion polymerization. These may be peroxides (eg alkali metal peroxodisulfates, ammonium peroxodisulfates or H ₂ O ₂ ) or azo compounds.

Also suitable are mixed systems consisting of one or more organic reducing agents and one or more peroxides and / or hydroperoxides (eg, tert-butyl hydroperoxide and sodium hydroxymethanesulfinate or hydrogen peroxide and ascorbic acid). Adequacy is a small amount of metal compounds that are soluble in the polymerization medium and their metallic components that may be present in a number of valence states (e.g. ascorbic acid / iron sulfate (II) / hydrogen peroxide, where ascorbic acid in many cases is sodium hydroxymethane). Sulfinate, sodium sulfite, sodium hydrogen sulfite or sodium metal bisulfite, hydrogen peroxide may be replaced with tert-butyl hydroperoxide or alkali metal peroxodisulfate and / or ammonium peroxodisulfate) It expands to the mixing system it contains. Generally the amount of free radical initiator system used is from 0.1 to 2% by weight, based on the total amount of monomers to be polymerized. Particular preference is given to using ammonium and / or alkali metal peroxodisulfate alone or as part of a mixed system as initiator.

Further suitable initiators are oil soluble initiators such as organic peroxides (eg tert-butyl peroxy-2-ethylhexanoate), percarbonates or diazo compounds.

The novel process can be carried out with or without emulsifiers. Suitable surface active materials are mainly protective colloids and emulsifiers, otherwise they are usually used as dispersants which are anionic, cationic or nonionic in nature. A detailed description of suitable protective colloids is found in Houben-Weyl, Methoden der organischen Chemie, Volume XIV / 1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, 411-420. As the surface active substance, it is preferable to use only an emulsifier having a molecular weight of usually less than 2000, unlike a protective colloid. Of course, when using a mixture of surface active substances, the individual components must be compatible with each other, and if this is not clear, several preliminary experiments can be checked. Preferably, anionic and nonionic emulsifiers are used as surface active materials. Examples of common emulsifiers are ethoxylated fatty alcohols (ethoxylation degree (EO): 3 to 50, alkyl: 8 to 36 carbon atoms), ethoxylated mono-, di- and trialkylphenols (EO: 3 to 50, alkyl : 4 to 9 carbon atoms, ethoxylated alkanol (EO: 4 to 30, alkyl: 12 to 18 carbon atoms), ethoxylated alkylphenol (EO: 3 to 50, alkyl: 4 to 9 carbon atoms), sulfosuccinic acid Alkali metals and alkyl sulfates (alkyl: 8 to 12 carbon atoms), alkylsulfonic acids (alkyl: 12 to 18 carbon atoms), alkyldiphenyl oxide sulfonic acids (alkyl: 12 to 18 carbon atoms) and alkyl- of the dialkyl esters of Alkali metal salts and ammonium salts of arylsulfonic acid (alkyl: 9 to 18 carbon atoms), and corresponding acids. Other suitable emulsifiers are described in Houben-Weyl, loc. cit., 192-208. Suitable emulsifier materials are generally used in amounts of from 0 to 5% by weight, preferably from 0.1 to 1% by weight, based on the amount of polymerized monomers.

The novel process is preferably used to produce polymer blends containing at least 10% by weight, in particular at least 40% by weight, based on the total weight of the polymer.

The present invention further provides a water dispersible polymer blend that can be prepared using the novel process described above. Particularly suitable polymer blends are those comprising a polyamide content of 10% by weight, based on the total weight of the polymer.

Such polymer blends can be used in a number of applications, such as adhesives, the manufacture and finishing of paper, cosmetics, in particular to the skin and nails, pharmaceutical preparations, the production and finishing of textiles, film formers for leather finishing, metals, Suitable as protective transparent, colored coating materials for mineral materials (eg bricks and concrete), fiber-containing or organic materials (eg wood, cardboard, textiles, asphalted cardboard) and plastics.

A recognized advantage of the novel polymer blends is that transparent films can be formed with a variety of polymers even at high polyamide contents. Transparent films can be obtained within a wide range of multiconcentrates to free radical addition polymers. Such compositions have the advantage that polymers that are otherwise incompatible in nature can be bound. This allows the properties of the aqueous dispersions to be finely adjusted. Thus, it is possible to obtain an aqueous redispersible film and to produce a waterproof film. In addition, pigment-compatible dispersions can be obtained through suitable mixing of polyamides and ethylenically unsaturated monomers; Solvent resistant films (eg THF-resistant films) can also be obtained.

Another recognized advantage is that even polyamides having glass transition temperatures above the film-forming temperature can form excellent films at room temperature without the addition of plasticizers.

Polymer blends obtainable by the novel process of the invention are generally fine hybrid dispersions having an average particle size of less than 150 nm.

The invention is further illustrated by the following examples.

<Example 1>

Preparation of Polyamide

The following monomer mixture in 1300 ml of water was charged to a 10 L experimental autoclave:

645 g of sodium 5-sulfoisophthalate, 598 g of isophthalic acid, 1116 g of 50% strength hexamethylenediamine solution, 190 g of 2,2,4-trimethylhexamethylenediamine and 787 g of AH salt. The autoclave was heated to 200 ° C. over 3 hours while the formed stream was removed by distillation. This temperature was kept unchanged for an additional hour. It was then increased to 280 ° C. over 1 hour. Post-cooling was then carried out in a nitrogen stream for 2 hours. The melt was then discharged through the die, cooled in the air layer and granulated.

The resulting polyamide had a viscosity number (VN) of 45 and a glass transition temperature of 143 ° C. when measured according to DIN 53 246 (0.5% concentration solution of copolyamide in 96% sulfuric acid).

<Example 2>

Preparation of Polyamide

As described in Example 1, polyamide was obtained from 840 g of sodium 5-sulfoisophthalate, 521 g of isophthalic acid, 1458 g of 50% strength hexamethylenediamine solution, 710 g of epsilon -caprolactam and 1200 ml of water. .

The glass transition temperature of the polyamide was 149 ° C.

<Example 3>

Preparation of Polymer Blends

140 g of polyamide from Example 1 were dispersed with stirring at 80 ° C. to 850 g of water. 54 g of methyl methacrylate and 6 g of butanediol bisacrylate were then added dropwise with stirring for 1 hour. Stir at 80 ° C. for 1 hour before adding 1 ml of t-butyl peroxy-2-ethylhexanoate (Trigonox 21 S, manufactured by Akzo) as a free radical initiator to the resulting mixture It was. The polymerization was then carried out for 6 hours with nitrogen passing through the batch. The resulting dispersion was cooled down and passed through a nylon filter.

<Examples 4 and 5>

Preparation of Polymer Blends

Examples 4 and 5 were carried out according to the same method as in Example 3.

Polyamide The amount of water Monomer Particle size Polydispersity Example 4 140 g of polyamide of Example 1 850 g Methyl methacrylate 50 g + butanediol bisacrylate 10 g 46.2 nm 0.18 Example 5 140 g of polyamide of Example 1 850 g 30 g of n-butyl acrylate 30 g of methyl methacrylate 46.1 nm 0.13

<Example 6>

Preparation of Polymer Blends

A mixture of 619.3 g of water, 40 g of polyamide of Example 2, 2.67 g of sodium lauryl sulfate (15% concentration solution) and 1.6 g of 25% concentration sodium hydroxide solution was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 200 g of butyl acrylate

200 g of methyl methacrylate

Feed stream 2: 99.1 g of water

4 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 14.4 g (25% concentration)

<Example 7>

Preparation of Polymer Blends

A mixture of 889.1 g of water, 60 g of polyamide of Example 2, 2 g of sodium lauryl sulfate (15% concentration solution) and 1.2 g of 25% concentration sodium hydroxide solution was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 150 g of butyl acrylate

150 g of methyl methacrylate

Feed stream 2: 99.1 g of water

3 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 10.8 g (25% concentration)

<Example 8>

Preparation of Polymer Blends

A mixture of 984.5 g of water, 112 g of polyamide of Example 2, 1.87 g of sodium lauryl sulfate (15% strength solution) and 1.12 g of 25% strength sodium hydroxide solution was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 140 g of butyl acrylate

140 g of methyl methacrylate

Feed stream 2: 99.1 g of water

2.8 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 10.1 g (25% concentration)

<Example 9>

Preparation of Polymer Blends

A mixture of 1006.3 g of water, 200 g of polyamide of Example 2, 1.33 g of sodium lauryl sulfate (15% concentration solution) and 0.8 g of 25% concentration sodium hydroxide solution was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 100 g of butyl acrylate

100 g of methyl methacrylate

Feed stream 2: 99.1 g of water

2 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 7.2 g (25% concentration)

<Example 10>

Preparation of Polymer Blends

A mixture of 1606.3 g of water, 400 g of polyamide of Example 2, 1.33 g of sodium lauryl sulfate (15% concentration solution) and 0.8 g of 25% concentration sodium hydroxide solution was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 100 g of butyl acrylate

100 g of methyl methacrylate

Feed stream 2: 99.1 g of water

2 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 7.2 g (25% concentration)

<Example 11>

Preparation of Polymer Blends

A mixture of 1151.8 g of water, 40 g of the polyamide of Example 2, 2.67 g of sodium lauryl sulfate (15% concentration solution) and 1.60 g of 25% concentration sodium hydroxide solution, was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 200 g of butyl acrylate

180 g of methyl methacrylate

20 g of methacrylic acid

Feed stream 2: 99.1 g of water

4 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 14.4 g (25% concentration)

<Example 12>

Preparation of Polymer Blends

A mixture of 1016.3 g of water, 200 g of polyamide of Example 2, 1.33 g of sodium lauryl sulfate (15% strength solution) and 0.8 g of 25% strength sodium hydroxide solution was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 100 g of butyl acrylate

90 g of methyl methacrylate

10 g of methacrylic acid

Feed stream 2: 99.1 g of water

2 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 7.2 g (25% concentration)

<Example 13>

Preparation of Polymer Blends

A mixture of 1131.8 g of water, 40 g of the polyamide of Example 2, 2.67 g of sodium lauryl sulfate (15% concentration solution) and 1.60 g of 25% concentration sodium hydroxide solution, was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 400 g of methacrylate

Feed stream 2: 99.1 g of water

4 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 14.4 g (25% concentration)

<Example 14>

Preparation of Polymer Blends

A mixture of 1006.3 g of water, 200 g of polyamide of Example 2, 1.33 g of sodium lauryl sulfate (15% concentration solution) and 0.80 g of 25% concentration sodium hydroxide solution was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 200 g of methacrylate

Feed stream 2: 99.1 g of water

2 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 7.2 g (25% concentration)

<Example 15>

Preparation of Polymer Blends

A mixture of 1131.8 g of water, 40 g of the polyamide of Example 2, 2.67 g of sodium lauryl sulfate (15% concentration solution) and 1.60 g of 25% concentration sodium hydroxide solution, was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 400 g of vinyl acetate

Feed stream 2: 99.1 g of water

4 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 14.4 g (25% concentration)

<Example 16>

Preparation of Polymer Blends

A mixture of 1006.3 g of water, 200 g of polyamide of Example 2, 1.33 g of sodium lauryl sulfate (15% concentration solution) and 0.80 g of 25% concentration sodium hydroxide solution was heated to 85 ° C. and 5 weight of feed stream 1 %, 10% by weight of feed stream 2 and 10% by weight of feed stream 3 were added. After starting the metered addition of the residues of feed streams 1, 2 and 3, the initial polymerization was carried out at 85 ° C. for 15 minutes. The stream was added continuously for 2 hours (feed stream 1) and 2.5 hours (feed streams 2 and 3). The polymerization was then continued at 85 ° C. for 1 hour.

Feed stream 1: 200 g of vinyl acetate

Feed stream 2: 99.1 g of water

2 g of sodium peroxodisulfate

Feed stream 3: 100 g of water

Sodium hydroxide 7.2 g (25% concentration)

Summary of Results from the Examples:

Example SC *) pH Particle size Polydispersity Example 6 34.2 7.8 98.8 nm 0.12 Example 7 24.4 7.9 70.4 nm 0.09 Example 8 24.5 7.7 75.6 nm 0.26 Example 9 24.7 5.3 59.7 nm 0.31 Example 10 24.4 4.8 65.7 nm 0.08 Example 11 24.5 6.4 102.5 nm 0.01 Example 12 23.2 4.3 57.5 nm 0.27 Example 13 23.5 6.9 136.7 nm 0.09 Example 14 24.4 4.3 88.7 nm 0.34 Example 15 24.7 5.7 216.1 nm 0.04 Example 16 24.1 4.9 147.4 nm 0.15 *) Solids content of the dispersion according to DIN 53 189

<Example 17>

Use of polymer blends as adhesive when laminating aluminum on paper

20 g of water and 3 g of thickener (30 wt% aqueous solution of acrylic acid and acrylamide based copolymer, emulsified in aliphatic petroleum fraction) are stirred, for example, in 100 g of aqueous polymer dispersion from Examples 7, 11 or 12 It was. 2 g / m² (dry) of this laminated adhesive was applied to the matte side of 0.015 mm thick matte aluminum foil on one side. Buxine paper (80 g / m²) was wound on the wet layer of the adhesive and dried for 3 minutes at 50 ° C. before cutting the substrate obtainable in this way into a mold of 200 mm × 30 mm. The test was performed after 24 hours.

Good strength aluminum-paper bonds have been found.

<Example 18>

Use of polymer blends as binders for nonwovens

The binder used was 96 wt% ethyl acrylate and 4 wt% acrylamidoglycolic acid, 45% solids, with the polymers prepared in Examples 6-10.

The fibrous web was solidified with the polymer according to a known method (Ullmann's Enzyklopadie der technischen Chemie, 4th Edition, Vol. 23, 1983, 738-742). Treatment of the web followed by drying and heating yielded a bonded fiber web.

A nonwoven fabric with good drainage properties was obtained.

<Example 19>

Use as a hair setting agent

(Percentage is weight)

Setting formulation 1

25% of the aqueous dispersion from Example 4,

Perfumery, coloring and preservative 0.2%,

Prepared by mixing 74.8% of water.

Setting formulation 2

15% aqueous dispersion from Example 5,

1.5% copolymer of 60% by weight N-vinylpyrrolidone and 40% by weight vinyl acetate,

Perfumery, coloring and preservative 0.2%,

Prepared by mixing 83.3% of water.

The resulting formulation showed a good setting effect.

<Example 20>

(Percentage is weight)

75% of the dispersion from Example 6 was mixed with 1% colored pigment and 24% water.

A glossy, well adhered film was obtained.

<Example 21>

Binders for Paper-Coating Compositions

60% concentration paper-coating composition

China clay 5PS (kaolin) 80 g,

20 g of omialite 90 (choke),

0.2 g of Polysalz S (dispersant for low molecular weight polyacrylic acid, kaolin and chalk),

Aqueous dispersions of Examples 6 to 10 (calculated on a dry basis), comprising 55% by weight of n-butyl acrylate, 43% by weight of methyl methacrylate and 2% by weight of acrylic acid, 50% solids content, 11.5 g

0.6 g of the trademark Blancophor PSG-fl (fluorescent bleach), and

Trademark Sterocoll D (calculated on a dry basis), 0.3 g of (aqueous dispersion of acrylic acid rich in acrylic ester polymer, thickener),

water.

Paper-coating compositions with good coating properties were obtained.

Claims (11)

A process for polymerizing a polyamide, at least one ethylenically unsaturated monomer, a polymerization initiator and, if desired, an aqueous dispersion or solution comprising an emulsifier to produce a water dispersible polymer blend of the polyamide and the second polymer. The method of claim 1 wherein the polymer blend comprises more than 10% by weight of polyamide. The method of claim 1 wherein the polyamide is a1) 0-99 mol% of C2-C12 monoaminocarboxylic acid or its lactam, a2) 0.5 to 50 mol% of at least one diamine having 2 to 18 carbon atoms, a3) 0-49 mol% of sulfonate-functional carbon atoms having 12 to 12 carbon atoms, and a4) 0.5 to 49 mole% of dicarboxylic acids having 2 to 16 carbon atoms. The method of claim 1 wherein the second polymer consists of monomeric n-butyl acrylate, methyl methacrylate or methacrylic acid or mixtures thereof. A water dispersible polymer blend obtainable by the method of claim 1. Use for the coated paper of the polymer blend of claim 5. Use for use in the cosmetic formulation of the polymer blend of claim 5. Use for use in the hair protection composition of the polymer blend of claim 7. Use for nail polish of the polymer blend of claim 7. Use of the polymer blend of claim 5 as an adhesive. Use of the polymer blend of claim 5 as an adhesive for nonwovens.