Water-soluble stitched protective colloids, the method of obtaining stabilized by protective colloids aqueous dispersions of polymers, aqueous polymer dispersions and redispersible in the water composition of polymer powders

 

(57) Abstract:

Describes stitched water-soluble protective colloids for aqueous dispersions of polymers having a molecular weight less than 500 000, containing at least 20 wt.% Monomeric units containing sulfoxylate or sulphonate groups, b) 4-80 wt.% Monomeric units containing N-methylol - or N-alkoxymethyl group) of 0.1-20 weight. % hydrophobic monomer unit from the group of water-insoluble ethanobotany compounds and hydrophobic end groups of residues initiators or molecules, regulators, and the number, expressed in wt.%, specified relative to the total weight of the copolymer, and a part of the Monomeric units containing sulfoxylate/sulphonate groups, optionally up to 50 wt.% in terms of the weight amount of monomer units (a) may be substituted Monomeric units g) containing carboxyl groups, or Monomeric units d) containing amide groups. Describes a method of obtaining a stable protective colloids aqueous dispersions of polymers by radical polymerization ethanobotany monomers by the method of suspension or emulsion polymerization in the presence of minicompetition polymer powders as a binder for coatings, plaster and paint materials, in particular pigmented paints and varnishes; as adhesives and binders for wood, paper, textile and nonwovens; as a binder in the manufacture of paper and manufacture of press-masses and molded products; as a binder for use in the construction industry, in particular as additives to concrete, construction adhesives, building solutions, filler weights and masses, contributing to the filling. 5 S. and 6 C.p. f-crystals, 1 table.

The invention relates to stapling protective colloids, method of polymerization ethanobotany monomers with the use of stitched protective colloids, as well as to get their assistance to the polymers, respectively dispersions of polymers and their application.

Stabilization of dispersions of polymers using protective colloids and surfactants are known. A review of stabilizers can be found, for example, in G. Schulz "Die Kunststoffe", Izd-vo S. Hanser Verlag, 1964, or in J. C. Jonson "Emulsifiers and Emulsifying Techniques" Noyes Data Corp., Park Ridge, New Jersey, 1979, and in the encyclopedia of Ullmann (Ullmann, "Encyklopadie der technischen Chemie", 4th ed., volume 10, published by Verlag Weinheim, 1980).

These compounds are characterised by the presence in the molecule rasprostranenna assumption these surfactants are located primarily in the boundary layer between the polymer particles and the aqueous solution. Therefore the total surface of the system, and thus, ultimately, and properties of the polymer dispersion are largely determined by these stabilizers. Thus the choice of an appropriate emulsifier ultimately determines the desired target properties of the polymer dispersion.

The use of surface-active polymers as protective colloids are also often described in the patent literature in recent years. In contrast to the classical polymeric protective colloids, such as polyvinyl alcohol, cellulose derivatives or gelatin, developed new methods of synthesis, and as protective colloids used water-soluble polymers with ionic groups, the so-called polyelectrolytes.

From DE 4212768 (US 5385971) known unsaturated polyester from the group of polyethylene glycol ethers of maleic or fumaric acid, which is used to stabilize emulsions of polymers. Thus obtained dispersion polymers have a high frost resistance and resistance to the action of electrolytes. In DE-A 4304014 (WO-A 94/18249) described a method for continuous polymerization of acrylic polymers with a low degree of polymerization in aqueous medium. Obtained in this way the floor is rigid of these products is a definite thickening action, what is undesirable for many purposes of use.

Stabilization of dispersions using electrolytes are also known from DE 2540468 (GB-A 1551126), where there is a high stability of the dispersion to the action of salts and shear stresses. In WO 92/03482 described oligomeric carboxylic acids used as stabilizers for emulsion polymerization of the radically curable monomers which are particularly suitable for the production of binders for printing inks. In the US 5314943 declared dispersion binder designed for use in the textile industry. Described in this publication dispersion polymers stabilized with protective colloid containing carbonisation group. This system, as I believe, has the ability to quick cure.

To obtain a binder, ensuring the formation of extremely stable polymer films, for example, when using as the adhesive means or coatings are often used in aqueous polymer dispersion stitched polymers. Widely used for stapling polymers with N-mediafunctions links of comonomers as cross-linking groups. Such stitched polymers known, is by increasing the proportion of N - metallforschung links in the polymer. Therefore, in the prior art, it was proposed to increase the crosslinking efficiency of such polymers with the help of special methods of obtaining (EP-B 205862) or polimerizuet comonomers with blocked N-metrostanciya (EP-A 261378).

Thus, proceeding from this prior art, the invention was based on the task to obtain polymers or aqueous dispersions of polymers, which could form a polymer film having a high mechanical strength and high resistance to water and resistance to solvents.

This problem was solved by getting a water-soluble, having the properties of protective colloids stitched polymer having embedded in the molecular chain, capable of zameshivanii functional group, in particular N-Mediagroup.

Water-soluble polymers with a high content of NMA (N-methylolacrylamide) tend to have high molecular weight and, consequently, to the high viscosity of the aqueous solution. Water-soluble acrylic compounds such as acrylic acid or used as cross-linking agent N-methylolacrylamide have a tendency to very high polymerization degree, which significantly limits the group of particularly high molecular weight (MB > 1000000) terpolymers from 30-95% dimethylacrylamide (DMA), 0.1-10% N-methylolacrylamide (NMA) and 4-50% acrylamidoglycolate AMPS) and their use as rheological additives in oil production.

Another disadvantage of polyelectrolytes based on water-soluble monomers is that such polyelectrolytes are often incompatible with the polymer dispersion and an aqueous solution of the polyelectrolyte is separated from the dispersion of the polymer in the form of serum.

It has been unexpectedly found that by copolymerization of N-methylolacrylamide with acrylic compounds containing sulfoxylate or sulphonate group, you can provide a product with a significantly lower molecular weight. In addition, it has been unexpectedly found that when copolymerization only small amounts of hydrophobic copolymers are significantly lower surface tension and lower viscosity.

This object is achieved stitched water-soluble protective colloids for aqueous dispersions of polymers having a molecular weight of less than 500000, containing

a) at least 20 wt.% Monomeric units containing sulfoxylate or sulphonate group,

s of monomer units from the group of water-insoluble ethanobotany compounds and hydrophobic end groups of residues initiators or molecules regulators, moreover, the number, expressed in wt.%, specified relative to the total weight of the copolymer, and

some of monomer units containing sulfoxylate/sulphonate groups, optionally up to 50 wt.% in terms of the weight amount of monomer units (a) may be substituted Monomeric units g) containing carboxyl groups, or Monomeric units d) containing amide groups.

Preferred are stitched water-soluble protective colloids containing:

a) 70-87% wt. Monomeric units containing sulfoxylate or sulphonate group,

b) 12-25 wt.% Monomeric units containing N-methylol - or N-alkoxymethyl group,

in) 1-5 weight. % hydrophobic monomer unit from the group of water-insoluble ethanobotany connections.

As the monomer unit (a) colloids preferably contain 2-acrylamide-2-methylpropanesulfonate, styrelseledamot, sulfopropyl ester of acrylic acid, sulfopropyl broadcast basis of itaconic acid, vinylsulfonate or their salts of ammonium, sodium, potassium and calcium; as a monomer unit (b) include N-methylolacrylamide, N-methylolmethacrylamide, N- (isobutoxide)acrylamide, N-(isoetaceae, styrene, finalproject, isopropenylacetate, vanillaware or vinyl ester of branched monocarboxylic acids with 5-10 carbon atoms.

The task is also solved by a method of obtaining stabilized by protective colloids aqueous dispersions of polymers by radical polymerization ethanobotany monomers by the method of suspension or emulsion polymerization in which polymerization is carried out in the presence of at least one of the above-described stapling protective colloid.

It is preferable to carry out polymerization by the method of emulsion polymerization in the presence of one or more monomers from the group of vinyl esters of unbranched or branched carboxylic acid with 1-18 carbon atoms, esters of acrylic acid and methacrylic acid with unbranched or branched alcohols with 1-18 carbon atoms, vinyl aromatic compounds, vinylchloride and olefins.

The task is achieved by the aqueous polymer dispersions of polymers ethanobotany monomers, which contain 0.1 to 20 wt.% one or more of the above-described protective colloids in terms of the amount of solid is the basis of vinyl esters or polymers based on esters of (meth)acrylic acid, which, calculated on the total weight of the polymers is not necessarily contain 0.5 to 5.0 wt.% comonomeric links with a cross-linking action of the group comprising N-methylacrylamide, N-methylolmethacrylamide, N- (alkoxymethyl)acrylamide or N-(alkoxymethyl)methacrylamide with C1-C6alkyl residue.

Aqueous dispersions of polymers preferably contain a copolymer of vinyl acetate and ethylene with an ethylene content of 5 to 50 wt.% and content of from 0.5 to 5.0 wt.% one or more comonomers from the group comprising N-methylolacrylamide, N-methylolmethacrylamide, N-(isobutoxide)acrylamide, N-(isobutoxide)methacrylamide, N- (n-butoxymethyl)acrylamide, N-(n-butoxymethyl)methacrylamide.

The task is also achieved above-described aqueous dispersions of polymers used as binders for coatings, plasters and paints, in particular pigmented paints and varnishes; as adhesives and binders for wood, paper, textile and nonwovens; as a binder in the manufacture of paper and manufacture of press-masses and molded products; as a binder for use in the construction industry, in particular as dobova the

This object is achieved also redispersible in water compositions of the polymer powders obtained by spray drying the above-described aqueous dispersion of polymers which can be used in the same areas that aqueous dispersions of polymers.

In addition, preferred are stitched water-soluble protective colloids molecular weight of 500,000, containing

a) 30-87% wt. Monomeric units containing sulfoxylate or sulphonate group,

b) 12-60 wt.% Monomeric units containing N-methylol - or N-alkoxymethyl group,

C) 0.1 to 10 wt.% hydrophobic monomer unit from the group of water-insoluble ethanobotany compounds and hydrophobic end groups of residues initiators or molecules, regulators, and the amount in wt.% specified relative to the total weight of the copolymer.

Especially preferred are stitched water-soluble protective colloids molecular weight of 500,000, containing

a) 70-87% wt. Monomeric units containing sulfoxylate or sulphonate group,

b) 12-25 wt.% Monomeric units containing N-methylol - or N-alkoxymethyl group,

in) 1-5 weight. % hydrophobic monomer vel initiators or molecules regulators, moreover, the amount in wt.% specified relative to the total weight of the copolymer.

Suitable Monomeric units (a) are, for example, water-soluble radically polymerized ethylenevinylacetate compounds that contain sulfoxylate or sulphonate group-SO3M, where M represents H, alkali metal ion, ammonium ion or alkali earth metal ion. Preferred 2-acrylamide-2-methylpropanesulfonate (AMPK), styrelseledamot, sulfoalkyl ether (meta)acrylic acid, sulfoalkyl broadcast basis of itaconic acid, preferably in each case with C1-C6alkyl residue, vinylsulfonate and their ammonium salts, salts of alkaline or alkaline-earth metals. Particularly preferred 2-acrylamide-2-methylpropanesulfonate (AMPK), styrelseledamot, sulfopropyl ester of acrylic acid, sulfopropyl broadcast basis of itaconic acid, vinylsulfonate and their salts of ammonium, sodium, potassium and calcium.

Suitable Monomeric units (b) are, for example, water-soluble radically polymerized ethylenevinylacetate compounds that contain N-Mediagroup (-NH-CH2OH) or their esterified derivatives (-NH-CH2OR, g is salutogenetic)acrylamide (IBMA), N-(isobutoxide)methacrylamide, N-(n-butoxymethyl)acrylamide (NMA). Especially preferred of these N-methylolacrylamide, N-(isobutoxide)acrylamide.

Suitable monomer units) are radically (co)polymerized ethylenevinylacetate compounds, the solubility of which in water at a temperature of 23oC less than 2 wt.%, and hydrophobic end groups of residues initiators or molecules regulators, in each case with more than 8 carbon atoms. Preferred esters of acrylic acid or methacrylic acid with more than 3 carbon atoms, such as methyl methacrylate, vinyl aromatic hydrocarbons, such as styrene or vinyltoluene, olefins, such as ethylene or propylene, vinylchloride, such as vinyl chloride, vinyl esters of aliphatic carboxylic acids with more than 2 carbon atoms. As of the end groups of the molecules of the regulators preferred dodecylphenyl the rest of dodecylmercaptan. Especially preferred methyl methacrylate, styrene, finalproject, isopropenylacetate (1-methylphenylacetic), vanillaware, vinyl esters of branched monocarboxylic acids with 5 to 10 carbon atoms, such as VeoVa9Ror VeoVa10R.

Suitable monomane connection which contain a carboxyl group-COOM, where M represents H, alkali metal ions, ammonium or alkaline-earth metals. Preferred acrylic acid, methacrylic acid, crotonic acid, taconova acid. Suitable monomers d) containing amide groups are water-soluble radically polymerized ethylenevinylacetate compounds that contain amide group-CONH2. The preferred acrylamide and methacrylamide, particularly preferred acrylamide.

The definition of "water-soluble" means that the solubility in water at a temperature of 23oC is at least 10 wt.%. Molecular weight is the average weight, determined by gel chromatography (GPC) using polystyrenesulfonate sodium as standard.

Getting the protective colloids according to the invention is carried out preferably by radical polymerization in aqueous solution at the reaction temperature preferably in the range from 40 to 80oC. the Polymerization can be carried out with pre-loading of all or individual components of the reaction mixture or Preboot part reagent is out without downloading it.

The initiation is carried out using commonly used for these purposes generators radicals, which are preferably used in quantities of from 0.01 to 3.0 wt.% in terms of the total weight of the monomers. Examples thereof include ammonium persulfate and potassium, hydrogen peroxide, peroxodisulfate potassium, sodium and ammonium. If necessary, these radical polymerization initiators can also normally combined with 0.01 to 1.0 wt.%, in terms of the total weight of the monomers, the redox agent, and in this case, the polymerization can be carried out at lower temperatures. Suitable for these purposes are, for example, formaldehydeinduced alkali metals and ascorbic acid. However, in cases of redox initiation preferably one or both of the redox component of the catalyst dosing during polymerization.

Required for polymerization range of pH values, which, as a rule, 2,5, can be adjusted in the usual way using reason or conventional buffer salts, such as phosphates or carbonates of alkali metals. To provide the desired molecular weight of the polymers in the process, the chloride and hydrocarbons.

In one particularly preferred embodiment of the apparatus beginning place of the mixture of comonomers a), b), C) and optionally d) and e) in aqueous solution and heat the mixture to the reaction temperature. Upon reaching the temperature of polymerization perform slow dosing generator radicals and the rest of the amount of the mixture of comonomers, respectively, in aqueous solution, after which the polymerization continues until it is completed by heating the mixture up to 85-95oC.

In accordance with the preferred mode of execution in the device first upload at least one part containing sulphonate groups of the comonomers a), component usually 5-60 wt.% in terms of the total weight of the comonomers a), and part of the comonomers b) with N-methylol-functions, is usually component of 5-60 wt.% in terms of the total weight of the comonomers a), in aqueous solution, and then add the rest of the comonomers a) and b).

The copolymers preferably used in the form of their aqueous solutions. Depending on the preferred application, the solids content of regulate in the range from 15 to 25 wt.%.

Methods of obtaining stable protective colloid is pensionnoi or emulsion polymerization are the polymerization is carried out in the presence of one or more protective colloids molecular weight of 500,000, containing

a) at least 20 wt.% Monomeric units containing sulfoxylate or sulphonate group,

b) 4-80 weight. % of monomer units containing N-methylol - or N - alkoxymethyl group,

C) 0.1 to 20 wt.% hydrophobic monomer unit from the group of water-insoluble ethanobotany compounds and hydrophobic end groups of residues initiators or molecules-regulators

moreover, the number, expressed in wt.%, stated in terms of the total weight of the copolymer and

moreover, the part containing sulfoxylate/sulphonate groups of monomer units, optionally up to 50 wt.%, in terms of the weight amount of monomer units (a) may be substituted containing carboxyl groups Monomeric units g) or containing amide groups of the Monomeric units d).

The polymerization is carried out in the presence of one or more monomers from the group of vinyl esters of unbranched or branched carboxylic acid with 1-18 carbon atoms, esters of acrylic acid and methacrylic acid with unbranched or branched alcohols with 1-18 ATO is implementing vinyl esters are vinyl acetate, finalproject, vinylboronate, vinyl 2-ethylhexanoate, vanillaware, 1-methylphenylacetic, vinylbilt and vinyl esters of branched monocarboxylic acids with 5 or 9-10 carbon atoms, for example, VV5R, VeoVa9Ror VeoVa10R. Particularly preferred vinyl acetate.

The preferred esters of methacrylic acid or esters of acrylic acid are methyl acrylate, methyl methacrylate, acrylate, methacrylate, propylacetate, propylbetaine, n-butyl acrylate, n-butylmethacrylate, isobutylacetate, isobutylacetate, tert-butyl acrylate, tert - butylmethacrylate, 2-hexyl acrylate, 2-ethylhexylacrylate. Especially preferred methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethyl hexyl acrylate.

The preferred vinyl aromatic hydrocarbons include styrene - methylsterol, chloride, styrene or vinyltoluene.

The preferred vinylchloride are vinyl chloride and vinylidenechloride.

The preferred olefins are ethylene, propylene, 1,3-butadiene, and isoprene.

To improve the solubility in water, to bind or to modify the adhesion properties of polymers in the system if necessary, you can add the kih auxiliary monomers.

Suitable auxiliary monomers to improve the solubility in water are, for example, is monoethanolamine mono - and dicarboxylic acids and their amides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, taconova acid, acrylamide, methacrylamide; ethylenevinylacetate sulfonic acids or their salts, preferably vinylsulfonate, 2-acrylamidophenylboronic and/or N - vinyl pyrrolidone.

Monomers with cross-linking action is preferably used in concentrations of 0.5-5.0 wt.% in terms of the total weight of the monomers. Examples thereof are N-methylolacrylamide, N - methylolmethacrylamide, N-(alkoxymethyl)acrylamide or N- (alkoxymethyl)methacrylamide with1-C6alkyl group, such as N-(isobutoxide)acrylamide (IBMA), N-(isobutoxide) methacrylamide (IBMA), N-(n-butoxymethyl)acrylamide (NMA), N-(n-butoxymethyl)methacrylamide (NMMA); repeatedly ethylenevinylacetate comonomers, such as etilenglikolevye, 1,3-butyleneglycol, 1,4 - butyleneglycol, propilenglikolstearat, divinerecipes, divinylbenzene, vinylmethyl, vinylacetat, alismataceae, allylacetate, diallylmalonate, diallylphthalate, di is I modification of the adhesive properties demonomanie links are, for example, hydroxyalkyl esters of methacrylic acid and acrylic acid, such as hydroxyethyl-, hydroxypropyl - or hydroxyethylacrylate or-methacrylate, and also compounds such as diacetonitrile and acetylacetoneiminates or-methacrylate.

Obtaining aqueous dispersions of the polymers is carried out according to the method of the aqueous emulsion polymerization or by the method of the aqueous suspension polymerization in the presence of 0.1-20 weight. %, preferably 0.1 to 5.0 wt.%, accordingly, calculated on the total weight of the monomers, of one or more stitched protective colloids according to the invention. It is preferable to operate by the method of emulsion polymerization, which is explained in more detail below.

The polymerization temperature generally is 35-95oC, preferably 40-80oC. the Polymerization can be conducted on a periodic scheme, in which all components are loaded into the reactor immediately, and the method of dosing, where individual or multiple components fed into the apparatus in the course of polymerization. Preferred is a mixed type: pre-loading and subsequent metered flow.

The latter can be done separately (prostream the emulsification.

Stitched protective colloids can be downloaded immediately or make their submission during the reaction or to distribute between the initial load and subsequent dosed feed. Stitched protective colloids in the form of their aqueous solutions are preferably added during the reaction. Such a flow can be constant speed or at variable speeds. For the application of system initiators fair the same principles as for other components of the reaction.

If, for example, is used gaseous components of the reaction, the emulsion polymerization can also be performed at elevated pressures. If, for example, operate at high pressure using such monomers as vinyl chloride or ethylene, preferably a pressure of from 5 to 100 bar. The determining factor is, for example, the target number of ethylene, which must be subjected to polymerization.

Used according to the invention stitched protective colloids can be used both individually and in combination with emulsifiers and/or other protective colloids. In accordance with a preferred perform in addition to stitched protective colloids according to the invention will Supplement what their" emulsifiers can be considered an anionic emulsifiers, cationic and non-ionic type. If the polymerization is carried out in the presence of emulsifiers, the amount is preferably up to 4 wt.% in terms of the total weight of the monomer phase. It is preferable to use anionic emulsifiers and nonionic type. Used for the purpose specified emulsifiers are, for example, ethoxylated fatty alcohols with a C8-C36alkyl groups and the degree of amoxilonline (EA-degree) from 3 to 50; ethoxylated mono-, di - and dialkylphenol4-C10alkyl groups and the degree of EO from 3 to 50; alkali metal salts of di-C4-C12alilovic esters sulfonterol acid. Acceptable salts of alkali metals and ammonium8-C12of alkyl sulphates, ethoxylated alkanols with12-C18alkyl group and with a degree in EE from 3 to 30, ethoxylated WITH4-C10ALKYLPHENOLS with a degree in EE from 3 to 50, WITH12-C18alkylsulfonyl,9-C18alkylarylsulphonate and sulfonates of ethoxylated linear and branched C8-C36alilovic alcohols with a degree in EE from 3 to 50.

Suitable protective colloids, which if necessary can be used in addition to stitched C is, ethers of cellulose, such as methyl-, methylhydroxypropyl-, hydroxyethylcellulose, carboxymethylcellulose.

Initiating the polymerization is carried out using used in emulsion polymerization of water-soluble thermal initiators or a combination of redox initiators. Examples of thermal initiators are organic peroxides, such as tert-butylhydroperoxide, the hydroperoxide has been studied, or peroxodisulfate, such as peroxodisulfate potassium, peroxodisulfate ammonium, or hydrogen peroxide, or azo compounds such as azodiisobutyronitrile. As redox initiators preferably used hydrogen peroxide, tert-butylhydroperoxide, peroxodisulfate potassium or peroxodisulfate ammonium in combination with hydroxyethylmethacrylate, ascorbic acid or sodium sulfite as a reducing agent. It is advisable to increase the reactivity of the system initiated by adding ions of metals of variable valency. Preferably used ions of Fe2+or CE2+. The amount of initiator is preferably from 0.01 to 1.0 wt.% in terms of the total weight Menominee agents. Usually they are used in quantities of from 0.01 to 5.0 weight. % with respect to the polymerized monomers and fed into the system separately or pre-mixed with the reagents. Examples of such substances are dodecylmercaptan, mercaptopropionic acid, methyl ester mercaptopropionic acid, isopropanol and acetaldehyde.

Obtained by the method according to the invention aqueous dispersions containing solids in an amount of from 30 to 75 wt.%, preferably from 40 to 65 wt.%.

The aqueous polymer dispersions of polymers of ethanobotany monomers contain 0.1 to 20 wt.%, in terms of the content of solid material in the polymer stitched protective colloids according to the invention.

These dispersions of the polymers can be prepared by the available technology according to the invention. Furthermore, aqueous dispersions of the polymers according to the invention can also be prepared by adding to the received conventional methods of polymer dispersions of 0.1-20 wt.%, preferably 0.1 to 5 wt.%, accordingly, in terms of the content of solid material in the polymer stitched colloid according to the invention. If additional supplementation is protective colloid according to the invention can be the

Preferred polymer dispersions of the following polymers:

Preferred polymers obtained by using vinyl ether, contain as monomer units, in each case relative to the total weight of the polymer:

50-100 wt.% vinyl ester, in particular vinyl acetate;

50-95 weight. % of vinyl ester, in particular vinyl acetate, and 5-50 wt.% -olefin, in particular ethylene;

20-79 weight. % of vinyl ester, in particular vinyl acetate, and 1-30 wt.% ethylene and 20 to 49 wt.% vinyl chloride;

50-75 wt.% vinyl acetate, 1-30 wt.% vanillaware or vinyl ether-branched carboxylic acid, in particular vinyl ether acid "Versatic" and 5-40 wt.% ethylene;

70-99 wt.% vinyl acetate and 1-30 wt.% vanillaware or vinyl ether - branched carboxylic acid, in particular vinyl ether acid "Versatic";

70-99 weight. % of vinyl ester, in particular vinyl acetate, and 1-30 wt.% the acrylic ester, in particular n-butyl acrylate or 2 - ethylhexyl acrylate;

50-75 wt.% vinyl acetate, 1-30 wt.% the acrylic ester, in particular n - butyl acrylate or 2-ethylhexyl acrylate, and 5-40 wt.% ethylene;

30-75 wt.% vinyl acetate, 1-30 wt.% vanillaware or vinyl ether-fu is s, in particular n-butyl acrylate or 2-ethylhexyl acrylate, and 5-40 wt.% of ethylene.

Preferred polymers obtained with esters of (meth)acrylic acid as a monomer unit containing, in each case calculated on the total weight of the polymer:

35-65 weight. % of methyl methacrylate, 65-35 wt.% n - butyl acrylate and/or 2-ethylhexyl acrylate;

35-65 weight. % styrene and 65-35 wt.% n-butyl acrylate and/or 2-ethylhexyl acrylate.

Especially preferred are polymers of the aforementioned composition, obtained with the help of vinyl esters and esters of (meth)acrylic acid, which contain 0.5 to 5.0 wt.%, in terms of the total weight of the polymers, comonomeric units having a crosslinking action, from the group comprising N-methylolacrylamide, N-methylolmethacrylamide; N-(alkoxymethyl)acrylamide or N-(alkoxymethyl)methacrylamide with C1-C6alkyl groups such as N-(isobutoxide)acrylamide (IBMA), N-(isobutoxide) methacrylamide (IBMA), N-(n-butoxymethyl)acrylamide (NMA), N-(n-butoxymethyl)methacrylamide (NMMA).

Most preferred are copolymers of vinyl acetate and ethylene with an ethylene content of 5 to 50 wt.% and content of from 0.5 to 5.0 wt.% one or more comonomers from the methyl)methacrylamide (IBMA), N-(n-butoxymethyl)acrylamide (NMA), N-(n-butoxymethyl)methacrylamide (NMMA).

Named the aqueous polymer dispersions of polymers obtained from ethanobotany monomers, which contain 0.1 to 20 wt.%, in terms of content in the polymer solid material, stitched protective colloid according to the invention is also suitable for receiving the holder of polymer powders in water.

To obtain the holder of compositions of polymer powders water dispersive subjected to drying. It is preferable to dry dispersion method, spray drying or freeze-drying.

Most preferred is spray dried dispersions. You can apply the known device, for example, where such spraying is performed via one-, two - or multi-jet nozzles or with a rotating disk, and perform the drying, if necessary, in a heated current of the drying agent, preferably air. Typically, the temperature of the drying agent at the entrance does not exceed 250oC. the Temperature of the drying agent at the output is usually in the range from 45 to 100oC, preferably from 55 to 90oC, which depends on the setting, the composition of the polymer and the required degree . , preferably from 30 to 65 wt.%. The solid content of the material varies depending on the method of drying and the type and amount of other additives that are injected during drying. For the preferred spray drying is acceptable, it has been found that the viscosity of the entire system of about 1000 mPas.

For example, before drying the dispersion can be added auxiliary agents, contributing to the dispersion. Such additives are preferably introduced in the form of their aqueous solutions in amounts constituting preferably 5-40 wt.%, first of all, 5-20 wt.% with respect to the polymer. The optimal number is determined by the required stability of the dispersion, the glass transition temperature of the obtained polymer and the desired properties of the powder.

As auxiliary agents, contributing to the spray, along with other suitable, individually or in appropriate combination, split or modified starch, starch derivatives, cellulose derivatives and water-soluble polymers, in particular those which have a high glass transition temperature equal to at least 50oC. Examples of such widely commercially available polymers are the copolymers of vinyl alcohol (polyvinyl is; water-soluble, containing sulphonate groups condensates of melamine and formaldehyde or of naphthalene and formaldehyde; condensates of phenolsulfonic and formaldehyde; copolymers of styrene and maleic acid and/or basis of itaconic acid and their esters; water-soluble copolymers olefineverbund acids and alkenes.

As has been repeatedly established, expedient has been to use when spraying the non optimal amount of about 1.5 wt.% with respect to the base polymer. Liquid antispyware usually added to the dispersion before drying and solid can be mixed with the dry compositions of polymer powders.

To improve the stability during storage due to the high resistance to adhesion, in particular for powders with a low glass transition temperature, the resulting powder can be added preferably in an amount up to 30 wt.% with respect to the total weight of polymer components means preventing adhesion (sliianie). This preferably takes place while the powder is still in fine form, for example, while it is still suspended in the drying gas. Means of preventing the adhesion, it is possible, in particular, to serve in the dryer individual p is Otie aluminosilicates, diatomaceous earth, colloidal silica, pyrogenic silicic acid, precipitated silicic acid, microtines, light spar, kaolin, talc, cement, diatomaceous earth, calcium carbonate or magnesium hydrosilicate.

Containing stitched protective colloids polymer dispersion according to the invention or obtained from them dispersive powders suitable for use as a binder for applied coatings, plaster and paint materials, especially for pigmented paint products; as adhesives or binders for wood, paper, textile and nonwovens; as a binder in the manufacture of paper and press masses and molded products; as a binder for use in the construction industry, primarily as an additive to concrete, construction adhesives, putty, building solutions and tools that contribute to the filling.

The following examples illustrate the present invention.

Examples

Example 1

Preparation of approximately 16% polymer solution AMPK-NMA-MMA:

Preparation of dosing solution of monomers In appropriate dosing vessel is placed 459 g of water and th is g of methyl methacrylate, 180 g of 2-acrylamido-2-methylpropanesulphoacid AMPK and 69.5 g of a 45% aqueous solution of N-methylolacrylamide NMA.

In a laboratory reactor with a volume of 3 l equipped with a paddle stirrer, reflux condenser and corresponding metering devices, consistently upload: 1.28 kg of deionized water, to 54.4 g of 25% aqueous NaOH solution, 0,849 g mercaptopropionic acid IPC, 112 g of solid 2-acrylamide-2-methylpropanesulphoacid AMPK, and 36.2 g of a 45% aqueous solution of N-methylolacrylamide NMA and 2,62 g of methyl methacrylate. The solution is stirred and heated to 80oC. the Polymerization begin by dosed feed into the system within 3 hours of 2.2%-aqueous solution of persulfate ammonium DOG. 10 minutes after the beginning of the solution feeding the DOG for 2 hours to carry out the dosing of the above monomer solution. Then the polymerization continues, completing it at a temperature of 90oC. After cooling, the pH of a solution using NaOH is set to 7. Thus obtained transparent solution contains solid material in the amount of 16.1%, has a pH=7, the viscosity of 88 mPas (Brookfield viscometer, 20 rpm) and average molecular weight 162000 (GPC; polystyrenesulfonate sodium as standard), the surface tension of 5% aqueous who, the leaves: AMPK 83.5 wt.%, NMA of 14.5 wt.%, the methyl methacrylate and 2.0 wt.%

Example 2

Preparation of approximately 16% polymer solution AMPK-NMA-ST

Preparation of dosing solution of monomers In appropriate dosing vessel is placed 459 g of water and sequentially dissolving the following substances: 81,5 g of 25% NaOH solution, 0,849 g mercaptopropionic acid IPC, 4,18 g of styrene, 180 g of 2-acrylamide-2-methylpropanesulphoacid AMPK and 69.5 g of a 45% solution of N-methylolacrylamide NMA.

In a laboratory reactor with a volume of 3 l equipped with a paddle stirrer, reflux condenser and corresponding metering devices, consistently upload: 1.28 kg of deionized water, to 54.4 g of 25% aqueous NaOH solution, 0,849 g mercaptopropionic acid IPC, 112 g of solid 2-acrylamide-2-methylpropanesulphoacid AMPK, and 36.2 g of a 45% aqueous solution of N-methylolacrylamide NMA and 2,62 g of styrene ARTICLE. The solution is stirred and heated to a temperature of 80oC. the Polymerization begin by dosed feed solution within 3 hours of 2.2%-aqueous solution of persulfate ammonium DOG. 10 minutes after the beginning of the solution feeding the DOG for 2 hours to carry out the dosing of the above solution of monomers. Then the polymerization continues, the e 7. Thus obtained transparent solution contains solid material in the amount of 15.8%, has a pH=7, the viscosity of 48 mPas (Brookfield, 20 rpm) and an average molecular weight of 450,000 (GPC; polystyrenesulfonate sodium as standard), the surface tension of a 5% aqueous solution is 61,6 mn/m

The content of monomer units is: AMPK 83.5 wt.%, NMA 14,5 weight. % styrene 2.0 wt%.

Example 3

Preparation of approximately 16% polymer solution AMPK-NMA with hydrophobic modellname terminal groups.

Preparation of dosing solution of monomers In appropriate dosing vessel is placed 455 g of water and sequentially dissolving the following substances: of 80.9 g of 25% aqueous NaOH solution, 0,843 g mercaptopropionic acid IPC, 179 g of 2-acrylamide-2-methylpropanesulphoacid AMPK and 68,9 g of 45% aqueous solution of N-methylolacrylamide NMA.

Preparation of dosing solution of the regulator: In the appropriate dosing vessel in to 48.5 g of acetone dissolve of 5.39 g of dodecylmercaptan.

In a laboratory reactor with a volume of 3 l equipped with a paddle stirrer, reflux condenser and corresponding metering devices, sequentially load: 1,21 kg of deionized water, 53,9 g 25% negociate AMPK and to 36.0 g of a 45% aqueous solution of N-methylolacrylamide NMA and 1.35 g of dodecylmercaptan. The solution is stirred and heated to a temperature of 80oC. the Polymerization begin by dosed feed to the reactor over 3 hours of 2.2%-aqueous solution of persulfate ammonium DOG. 10 minutes after the commencement of injection of the solution of a DOG, into the reactor for 2 hours serves the above-described dosing the monomer solution and the dosing solution of the regulator. Then the polymerization continues, completing it at a temperature of 90oC. After cooling using NaOH establish the pH of a solution is equal to 7. Thus obtained transparent solution contains solid material in the amount of 16.3%, has a pH=7, the viscosity 49,5 mPas (Brookfield, 20 rpm) and the average molecular weight of 148000 (GPC; polystyrenesulfonate sodium as standard), the surface tension of a 5% aqueous solution is 63,9 mn/m

The content of monomer units is: AMPK 83.1 wt.%, NMA 14.4 weight. % dodecylmercaptan 2.5 wt.%.

Example 4

Preparation of a 55% dispersion of ethylene-vinyl acetate with the polymer of example 1 as a protective colloid.

Preparation of dosing solution of monomers: In dosing vessel mix 633 g of vinyl acetate and 32.4 g of butyl acrylate.

Preparation of the dosed water is mesilat to 2.94 g of 2-acrylamide-2-methylpropanesulphoacid (sodium salt, 50% aqueous solution), is 32.8 g of 48% aqueous solution of N-methylolacrylamide, 11 g polyglycolic ether isotridecyl alcohol, 5,52 g of acrylic acid and 91,4 g 16,1% aqueous polymer solution of example 1.

In a laboratory autoclave with a volume of 2 l equipped with a stirrer and corresponding metering devices, sequentially downloads: 521 g of deionized water, 2,77 g of 25% aqueous solution vinylsulfonate sodium and 1.15 g of a 30% aqueous solution of Palmyra of sulfosuccinate, 10.7 g of a 40% aqueous solution of blockcopolymer composition of the ethylene oxide-propylene oxide-ethylene oxide, of 2.21 g of 48% aqueous solution of N-methylolacrylamide, of 7.36 g of butyl acrylate and a 63.3 g of vinyl acetate. After heating the contents of the autoclave to a temperature of 45oC set pressure of ethylene equal to 60 bar, and initiate the beginning of polymerization using a 5% solution of ammonium persulfate and 2.5% aqueous solution of ascorbic acid. The speed of the dosing input initiators installed in accordance with the General time dosed feed, equal to 6 hours. Indicator of the beginning of polymerization is heat due to the exothermic reaction. 10 minutes after the start of polymerization begin dosing of monomers and an aqueous solution of emulsifier. Sovershenii polymerization reactor pressure drop and set the value of pH, approximately equal to 5.

Thus obtained polymer dispersion not containing clots, has the following characteristics: solids material: 56,1%, a pH of 4.9, the particle sizes of approximately 440 nm, viscosity: 2980 mPas (Brookfield, 20 rpm), the ethylene content in the polymer resin: 21,8 wt.%, the degree of crosslinking of the polymer film: 81,3%.

The content of monomer units is: vinyl acetate 71,4 wt.%, ethylene to 22.0 wt.%, the acrylate 4.1 wt.%, AMPK 0.2 wt.%, NMA 1.7 wt.%, acrylic acid 0.5 wt.%, vinylsulfonate 0.1 wt.%.

Example 5

Preparation of approximately 55% polymer dispersion of ethylene-vinyl acetate with the polymer from example 2 as a protective colloid.

Preparation of dosing solution of monomers: In dosing vessel mix 633 g of vinyl acetate and 32.4 g of butyl acrylate.

Preparation of dosing aqueous solution: In the dosing vessel placed 42 ml of deionized water and serially diluted and mixed to 2.94 g of 2-acrylamide-2-methylpropanesulphoacid (sodium salt, 50% aqueous solution), is 32.8 g of 48% aqueous solution of N-methylolacrylamide, 11 g polyglycolic ether isotridecyl alcohol, 5,52 g of acrylic acid and 91,4 g 15,8% aqueous polymer the metering device, sequentially downloads: 521 g of deionized water, 2,77 g of 25% aqueous solution vinylsulfonate sodium and 1.15 g of a 30% aqueous solution of Palmyra of sulfosuccinate, 10.7 g of a 40% aqueous solution of blockcopolymer composition of the ethylene oxide-propylene oxide-ethylene oxide, of 2.21 g of 48% aqueous solution of N-methylolacrylamide, of 7.36 g of butyl acrylate and a 63.3 g of vinyl acetate. After heating the contents of the autoclave to a temperature of 45oC the pressure of ethylene is set to 60 bar and the beginning of the polymerization initiated with a 5% aqueous solution of ammonium persulfate and 2.5% aqueous solution of ascorbic acid. Speed dosed feed initiators installed in accordance with the General dosing time, equal to 6 hours. Indicator of the beginning of polymerization is heat due to the exothermic reaction. 10 minutes after the start of the reaction start feeding apparatus of the dosed solution of monomers and an aqueous solution of emulsifier. The speed of dosing in each case correspond to the duration of dosing, part of 4 hours. Upon completion of the polymerization reactor pressure drop and set the pH value is approximately equal to 5.

Thus obtained polymer slurry not containing clots, is pursuing the field, 20 rpm), the ethylene content in the polymer resin: of 17.0 wt.%, the degree of crosslinking of the polymer film: 73,1%.

The content of monomer units is: vinyl acetate 76,0 wt.%, ethylene 17 weight. % butyl acrylate 4.4 wt.%, AMPK 0.2 wt.%, NMA 1.8 wt.%, acrylic acid 0.5 wt.%, vinylsulfonate 0.1 wt.%.

Example 6

Preparation of a 55% dispersion of ethylene-vinyl acetate with the polymer from example 3 as a protective colloid.

Preparation of dosing solution of monomers: In dosing vessel mix 633 g of vinyl acetate and 32.4 butyl acrylate.

Preparation of dosing aqueous solution: In the dosing vessel placed 42 ml of deionized water and successively dissolved in it and mix to 2.94 g of 2 - acrylamide-2-methylpropanesulphoacid (sodium salt, 50% aqueous solution), is 32.8 g of 48% aqueous solution of N-methylolacrylamide, 11 g polyglycolic ether isotridecyl alcohol, 5,52 g of acrylic acid and 90.3 g of 16.3% aqueous polymer solution of example 3.

In a laboratory autoclave with a volume of 2 l equipped with a stirrer and corresponding metering devices, sequentially downloads: 526 g of deionized water, 2,77 g of 25% aqueous solution vinylsulfonate sodium and 1.15 g of 30%-noid-ethylene oxide, of 2.21 g of 48% aqueous solution of N-methylolacrylamide, of 7.36 g of butyl acrylate and a 63.3 g of vinyl acetate. After heating the contents of the autoclave to a temperature of 45oC increase the pressure of ethylene to 60 bar and initiate the beginning of polymerization using a 5% solution of ammonium persulfate and 2.5% aqueous solution of ascorbic acid. Feed speed dosed initiators installed in accordance with the General dosing time, accounting for 6 hours. Indicator of the beginning of polymerization is heat due to the exothermic reaction. 10 minutes after the start of the reaction start dosing of monomers and an aqueous solution of emulsifier. The speed of dosing in each case correspond to the time of dosing, is 4 hours. Upon completion of the polymerization reactor pressure drop and set the pH value is approximately equal to 5.

Thus obtained do not contain clots polymer dispersion has the following characteristics: solids material: 55,1%, pH of 4.8, the particle sizes of approximately 320 nm, viscosity: 5150 mPas (Brookfield, 20 rpm), the ethylene content in the polymer resin: 21.6 wt.%, the degree of crosslinking of the polymer film: 88,7%.

The calculated number of monomer units t the ilen-vinyl acetate without protective colloid according to the invention.

The process of obtaining the dispersion was carried out similarly as described in examples 4-6, but without the use of protective colloid according to the invention.

Thus obtained, containing clots polymer dispersion has the following characteristics: solids material: 53,9%, a pH of 4.7, a particle size of about 310 nm, viscosity: 1380 mPas (Brookfield, 20 rpm), the ethylene content in the polymer resin is 20.9 wt.%, the degree of crosslinking of the polymer film: 73,7%.

The following example illustrates the receipt holder compositions of polymer powders by spray drying aqueous dispersions of polymers.

Example 8.

The dispersion from example 6 is mixed with 5 wt.% polyvinyl alcohol with a degree of hydrolysis of 88 mol.% and a viscosity of 4 mPas. The resulting dispersion is diluted with water to obtain a viscosity of 100-200 mPas, is sprayed through the nozzle pre-compressed under a pressure of 4 bar air and dried at a temperature of 100-140oC. Then, the resulting dried powder is mixed with 10% by weight of substances that prevent adhesion of the powder particles, on the basis of calcium carbonate or magnesium.

Technological tests

Samples of viscose staple fabric was impregnated dispers is the binding of 29.5%). Strength treated in this way tissue samples tested in transverse direction. The test is performed on dried samples, respectively, after storage for one minute in water or isopropanol. To this end stacked on each other in three bands specified tissue length of 150 mm and a width of 15 mm each and conducted their joint trial. Measurement conditions were as follows: clamp a length of 100 mm, clamping width 15 mm, measurement speed of 100 mm/min. Measured value was the value of the ultimate tensile stress, i.e. the maximum reached during the measurement of the tensile stress. The results are given in the table.

As clearly follows from the results of tests using the dispersions of examples 4-6, on the one hand, and using the dispersion of example 7 (comparative - without the use of polyelectrolyte protective colloids according to the invention), on the other hand, obtained with stitched protective colloids according to the invention can be stapled copolymers of ethylene and vinyl acetate are much higher resistance to water and solvents in comparison with stitched copolymers of ethylene and vinyl acetate, sintesio is ersi polymers, having a molecular weight of less than 500000 containing. a) at least 20 weight. % of monomer units containing sulfoxylate or sulphonate groups, b) 4-80 wt.% Monomeric units containing N-methylol - or N-alkoxymethyl group, C) 0.1 to 20 wt.% hydrophobic monomer unit from the group of water insoluble ethanobotany compounds and hydrophobic end groups of residues initiators or molecules, regulators, and the number, expressed in wt.%, specified relative to the total weight of the copolymer, and a part of the Monomeric units containing sulfoxylate/sulphonate groups, optionally up to 50 wt.% in terms of the weight amount of monomer units (a) may be substituted Monomeric units g) containing carboxyl groups, or Monomeric units d) containing amide groups.

2. Water-soluble stitched protective colloids under item 1, characterized in that they contain: a) 70-87% wt. Monomeric units containing sulfoxylate or sulphonate groups, b) 12-25 wt.% Monomeric units containing N-methylol - or N-alkoxymethyl group) 1-5 wt.% hydrophobic monomer unit from the group of water insoluble ethanobotany connections.

3. Vadora will win 2-acrylamide-2-methylpropanesulfonate, styrelseledamot, sulfopropyl ester of acrylic acid, sulfopropyl broadcast basis of itaconic acid, vinylsulfonate or their salts of ammonium, sodium, potassium and calcium; as a monomer unit (b) include N-methylolacrylamide, N-methylolmethacrylamide, N-(isobutoxide)acrylamide, N-(isobutoxide)methacrylamide or N-(n-butoxymethyl)acrylamide, and as a monomer unit in a) include methyl methacrylate, styrene, finalproject, isopropenylacetate, vanillaware or vinyl ester of branched monocarboxylic acids with 5-10 carbon atoms.

4. The method of obtaining stabilized by protective colloids aqueous dispersions of polymers by radical polymerization ethanobotany monomers by the method of suspension or emulsion polymerization, wherein the polymerization is carried out in the presence of at least one stitched protective colloid according to any one of paragraphs.1-3.

5. The method according to p. 4, characterized in that the polymerisation process is carried out by the method of emulsion polymerization in the presence of one or more monomers from the group of vinyl esters of unbranched or branched carboxylic acid with 1-18 carbon atoms, esters of acrylic acid and the systematic connections vinylchloride and olefins.

6. The aqueous polymer dispersions of polymers ethanobotany monomers, which contain 0.1 to 20 wt.% one or more protective colloids on the PP.1-3 in terms of the amount of solid material in the polymer.

7. Aqueous dispersions of polymers under item 6, characterized in that they contain one or more polymers based on vinyl esters or polymers based on esters of (meth) acrylic acid, calculated on the total weight of the polymers is not necessarily contain 0.5 to 5.0 wt.% comonomeric links with a cross-linking action of the group comprising N-methylacrylamide, N-methylolmethacrylamide, N-(alkoxymethyl)acrylamide or N-(alkoxymethyl)methacrylamide with C1-C6alkyl residue.

8. Aqueous dispersions of polymers under item 7, characterized in that they contain a copolymer of vinyl acetate and ethylene with an ethylene content of 5 to 50 wt.% and content of from 0.5 to 5.0 wt.% one or more comonomers from the group comprising N-methylolacrylamide, N-methylolmethacrylamide, N-(ISO-butoxymethyl)acrylamide, N-(isobutoxide)methacrylamide, N-(n-butoxymethyl)acrylamide, N-(n-butoxymethyl)methacrylamide.

9. Aqueous dispersions of polymers on PP.6-8, used to the juicy material; as adhesives and binders for wood, paper, textile and nonwovens; as a binder in the manufacture of paper and manufacture of press-masses and molded products; as a binder for use in the construction industry, in particular as additives to concrete, construction adhesives, building solutions, filler weights and masses, contributing to the filling.

10. Redispersible in the water composition of the polymer powders obtained by spray drying aqueous dispersions of polymers on PP.6-8.

11. Redispersible polymeric powders by p. 10, used as a binder for coatings, plasters and paints, in particular pigmented paints and varnishes; as adhesives and binders for wood, paper, textile and nonwovens; as a binder in the manufacture of paper and manufacture of press-masses and molded products; as a binder for use in the construction industry, in particular as additives to concrete, construction adhesives, building solutions, filler weights and masses, contributing to the filling.

 

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