CS228123B2 - Alloy of polymers and method of its manufacture - Google Patents

Description

The invention relates to a polymer alloy stable and homogeneous at high temperatures and to a process for its production.

It has already been proposed to produce moisture absorbing and / or swelling polymers from unsaturated carboxylic compounds, for example maleic anhydride, by polymerizing a carboxylic monomer with a crosslinking agent, for example an unsaturated polyethylene compound. Polymers of this kind have been used as synthetic gums for the production of sticky or gel-like aqueous compositions.

As is known, certain weakly crosslinked polymers with a large number of hydrophilic units for ab? sorption and binding of liquids. Such polymers, for example, slightly crosslinked, partially hydrolyzed polyacrylamides, have been recommended as components of disposable diaper filling materials, bed liners and other similar sanitary items, due to their ability to retain much more aqueous liquids under pressure than the same amount of cellulose wadding. or similar material. However, the use of such highly water-swellable polymers has created difficulties in depositing polymers after saturation with an aqueous liquid. It would be desirable to have a substantially water-swellable, water-insoluble fiber-shaped polymer.

In addition, it is generally desirable to have polymers having an adjustable moisture absorption capacity.

Furthermore, water-rich and / or water-absorbing substances obtained by other binder reactions, such as the reaction between polyisocyanates and polyols, are known. In addition, many sensitive plastics have been developed. or swellable based on water-soluble polymers such as polyacrylic acid, polyacrylamide and derivatives thereof, combined with or without natural hydrophilic polymers such as starch, cellulose and derivatives thereof.

These compounds are known as synthetic hydrogels. In many cases it is produced in the form of powders, fibers, granulates, foils and so on. They are also used for medical and sanitary purposes.

These substances, like many other known water-soluble or water-degradable packaging materials, have considerable drawbacks. In particular, the processability at higher temperatures (from 120 to 209 ° C) common in thermoplastic processing often causes great difficulties. This is particularly the case when the side group polymers are heated to an elevated temperature. The crosslinking reaction often results in the loss of the originally thermoplastic character, so that continuous processing at high temperatures also becomes very difficult or impossible.

On the other hand, in many hydrophilic polymers, the range of melting or softening in most cases - such as polyvinyl alcohol, cellulose, starch and derivatives - is very extensive or none at all. In these cases, conventional methods of thermoplastic processing cannot be used, or only with great difficulty.

In addition, crosslinking reactions or dehydration occur commonly, whereby the original structures are irreversibly altered.

From the foregoing, there appears to be a need for synthetic polymers with hydrophilic properties (starch, proteins, cellulose) that can be prepared and processed according to existing thermoplastic processing methods (extrusion, compression, injection, film extrusion, calendering, and so on) they experienced inappropriate irreversible changes or reactions.

It is an object of the present invention to provide a process for the preparation of hydrophilic synthetic polymers, by which the drawbacks of the known processes are effectively eliminated.

The essence of the polymer alloy according to the invention consists in that it consists of a first component consisting of a copolymer of mlalein anhydride with a monomer selected from the group consisting of styrene and methyl vinyl ether containing 95 to 20 molar percentages of anhydride groups, the remainder being protolyzed to introduce hydrogen atoms. polyvinyl acetate, cellulose esters, polyacrylates, and polymethylacrylate, both of which are present in the alloy in an amount corresponding to the weight ratio of the first component to the second in the range of 0.01 to 100, the molecular weight of each component being in the order of 10 ^{4 6} to 10 and the components are connected by hydrogen bonds.

The process of preparing the polymer alloy according to the invention consists in first preparing a solution of the first component in an organic solvent, to which a second component is then added, wherein the first component is partially or completely protolyzed before or after the second component is added by protolyzing agents. removes the solvent, wherein both the first component and the second component have a molecular weight of the order of 10 ⁴ to 10 ®.

Generally, the first component has a highly polar characteristic, yet is insoluble in water. However, by the action of water, depending on the pH and temperature, it becomes a water-soluble polymer due to the formation of free carboxyl groups or carboxylate ions. Water solubility is a function of pH.

For the desired purposes, both the first component and the second component must have a molecular weight of the order of at least 10 ⁴ .

A very important aspect of the present invention in the preparation of this homogeneous polymer alloy is the fact that, generally speaking, high molecular weight different chemical structures are either not at all or barely homogeneously miscible in all proportions. The preparation of homogeneous polymer alloys is generally impossible or very difficult. It has surprisingly been found that the styrene-maleic anhydride copolymer as the first component and polyvinyl acetate. The triacetate (cellulose, cellulose acetobutyrate, polyeltylacrylate or poilymethyl methacrylate as second components are miscible in all ratios below a certain temperature).

This is due to the slight interaction between the types of polymers representing the first and second component of the polymer alloy of the present invention. However, segregation or phase separation occurs at a certain temperature. This temperature is referred to as the critical temperature Tc, and is a function of the molecular weight of the components and the ratio of the haze to each other.

In addition, it has been found that miscibility at high temperatures (100-200 ° C) is controllable by increasing the physical interaction (association) of the polymer components.

This increased interaction may be accomplished by partial hydrolysis (generally protolysis) of the first component before or after the addition of the second component. Protolysis forms carboxyl groups in the first component that form hydrogen bridges to associate the first and second components.

It is important that the first component is prepared or protolyzed after it is dissolved in an organic solvent to ensure a homogeneous reaction. Among the polymers used as second components in the polymer alloy of the invention, polymers with ester side groups such as polyvinyl acetate, cellulose esters, polyacrylates and / or polymethacrylates are particularly suitable.

An illustrative example of the polymer alloys of the present invention is an alloy consisting of copolymers of styrene and maleic anhydride (first component) and polyvinyl acetate (second component). On this alloy, the main effects of the invention, the so-called solvent alloying, will be demonstrated.

An exemplary embodiment of the invention is shown in the drawings, wherein Fig. 1 is a graph of increasing the critical separation temperature Tc for the polyvimyl acetate / styrene maleic anhydride Jaiko function of water concentration and protolysis time and temperature. protolysis at 75 ° C in solutions containing equal parts by weight of the polymer components constituting the polymer alloy of the invention, and Figure 3 is a graph of swelling of the polymer alloys of the invention.

The method of evaporating the solvent or drying forms an important part of this invention. It should be designed in such a way that the above increased interaction is maintained. The gradual preparation methods are as follows:

A mixture of both polymers, i.e. copolymers of styrene maleic anhydride and polyvimylation of phthalite, is prepared from solution, for example in buitanone (methylityl ketone). Previously, the copolymer is prepared separately by so-called solution polymerization, from alkene, for example styrene, and maleic anhydride, or is already dissolved as a finished polymer. After polymerization to a given molecular weight, partial protolysis is performed by adding some water or alcohol to the polymer solution. Protolysis is accelerated by heating and catalysts. Therefore, constant heating of the styrene solution and maleic anhydride increases the critical temperature.

After protolysis, polyvinyl acetate is added to the solution, either in solid form or as a solution in butanone, whereupon mixing occurs.

Although the concentration of the solution is not essential, for practical reasons a solution with about 20 percent polymer content is prepared. The dissolution method used is of major importance for achieving an optimum degree of homogenization. The association of the two types of polymers (the first and second components) in the solution makes it possible to achieve the casting effect in a short time in the maximum and effective range. The degree of association of the first and second components was increased by partial hydrolysis (protolysis of the copolymers as described above).

The solid homogeneous polymer alloy can then be obtained by drying in which the solvent is evaporated (distilled) in a closed system at a temperature ranging from 100 to 200 degrees Celsius (generally 130 to 160 ° C).

Distillation or drying may be accelerated by reducing the pressure (for example from 1 to 50 mbar)

66.66 kPa). Drying is carried out in a closed system for the following reasons:

(1) Solvent recovery.

(2) Drying should be carried out in an atmosphere with a certain degree of moisture. Absolutely dry surroundings should be avoided. The reason for this requirement is that copolymers with anhydride groups which are hydrated or hydrolyzed in whole or in part are converted into a cyclic anhydride structure by dehydration, which is a reversible reaction:

-O «

OH

C '* i

OH from 120 ° C and higher in dry atmosphere

The result is reduced association, and phase separation may again occur.

For this reason, drying should take place under very specific conditions. Surprisingly, it has been found that under certain drying conditions there is no reduction but rather an increase.

(3) Drying may also be combined with hydration or hydrolysis.

The increase in water content also occurs during

A solution of polyvinyl acetate with a co-polymer of styrene and maleic anhydride at 20 ° C with a critical temperature of, for example, 100 ° C

The critical temperature rises above 100 ° C as a result of rapid water protolysis.

(4) In addition to the reason set out in point 3, it is clear that all types of added reactive functional groups, such as drying, because butanone boils at 80 ° C and water at 100 ° C, and therefore, some fractionation occurs.

In combination with a rapid increase in temperature during drying, a rapid conversion of anhydride groups to carboxyl groups occurs in a closed system.

The relationship between the temperature and the state of the resin in the drying apparatus is as follows:

Temperature

100 120 150 170 ° C turbid —► clear —► dry end product

The concentration of H ₂ O increases, for example, with alcohols, they can be chemically bonded during drying using residual anhydride groups. According to the reaction equation below, rapid protolysis reaction occurs in the semiester apparatus during drying at elevated temperature.

(2)

C ~~

I c - // + ROH

I O

C-c-OR ¹ S °

O - C - OH (5) It is also possible to add the most diverse substances before drying: plasticizers, modifiers, excipients, fillers, pigments and dyes, lubricants, biologically active substances and so on.

The resulting polymer alloys have the following properties: thermoplastic, clear, densities of about 120-130 kg. m ' ³ , softening and processing temperature in the range of 100 to 200 ° C, excellent resistance to aliphatic hydrocarbons, oils and fats, solubility in lower alcohols and ketones, swelling in aromatic hydrocarbons.

The mechanical properties of the polymer alloys of the invention are a function of the molecular weights of the two components and the ratio of the first and second polymer components to each other. For example, a high polyvinyl acetate content reduces the modulus of elasticity or increases the elongation at break (see Table A). The module (or stiffness) can be further reduced by the addition of plasticizers and / or other modifiers (see Table B).

Test of the tensile strength of a film sample (polymers of styrene-maleic anhydride polymers and vinyl acrylate poles); tape (1.5 cm wide) in the longitudinal direction. Permanent length 10 cm; drawing speed 3 cm / min; thickness approx. 0.1 mm.

Composition Permanent deformation stress a / b-SMA / - I MPa / PVAc Diameter S.O.

Ultimate stress MPa

Diameter S. O.

Modulus of elasticity MPa

Diameter S. O.

Elongation at break%

Diameter S. O.

Copolymer No. 10

10/90 13.53 0.88 11.08 0.78 686.46 196.13 250 40 20/80 20.69 0.78 13.63 0.49 1078.33 117.68 90 40 30/70 41.67 1.47 40.20 7.84 1667.13 245.16 6 3.2 40/60 - - 47.75 0.39 1471,00 294.20 2.3 0.2 Kopoly- No. 9 10/90 9.51 0.29 9.90 0.29 637.43 196.13 294 8 20/80 18.14 0.88 13.19 0.15 1029.73 3) 27.47 220 25 30/70 33.63 0.88 19.71 0.98 1613.10 196.13 35 9 40/60 - - 46.09 3.92 2039,51 117.68 2.6 0.3

SMA = styrein-maleic anhydride PVAc = polyvinyl acetylate S. O. = standard deviation

Table B

Effect of emollients; a polymer ratio of about 1: 1 (50/50); The plasticizer content is about 30 percent

Emollient Ultimate stress MPia Stress on permanent deformation MPa Module elasticity MPa Elongation at break PPA 13.24 6.96 294.20 220% SPA 13.04 14.90 490,30 59 Polyethylene comparative 14.71 11.76 235.36 4001%

material

PRA = pentaerythltol diacetate dipropionate SPA = sorbitol triacetateotropropioinate

The novel type of polymer alloys of the present invention can be processed using conventional melt extrusion processes as well as devices or processes for casting from organic solvents. The films can be manufactured according to known film blowing processes. The extrudates and granules can be obtained by standard procedures.

The fibers can be prepared by conventional methods, for example, melt monofilaments by dry or wet spinning processes based on direct coagulation from organic solvents in water or aqueous solutions.

All of the novel compositions of the present invention have the advantage that they are melt-extrudable, either alone or in combination with suitable plasticizers, which in this case may be labeled as being reasonably compatible with polymer blends which do not cause undesirable exudate formation. , phase separation, reaction formation, and so on.

The polymeric substance contains both hydrophobic and hydrophilic groups. This is manifested in the typical chauakeristics of these types of polymer alloys, that is, their biasability, especially in water. Swelling in polymer blends results in the mixing of polymer components on a molecular scale (- alloying), as well as a strong interaction between different types of polymers.

In addition, the polymer alloy has the characteristics of polyanhydride resins. The presence of the anhydride group causes the alloy to be reactive even in solid form, so there is the possibility of secondary chemical reactions.

Reactions are possible, for example, with water, alcohols, ammonia, amines, epovis compounds and the like [see reaction equation (2) above]. Secondary sessions were used to improve the processability of the alloy during processing (compare extrusion).

Several percent of a fatty alcohol, such as giearyl alcohol, was added to the polymer solution prior to hardening. The formed sitearyl esters act as internal, non-separating lubricants during processing.

In this way, a large number of variations have been made in terms of both chemical and physical properties (cf. secondary reactions). Thus, both the hydrophilic and hydrophobic characteristics can be increased or suppressed.

This is especially true for reaction with water. Polymer alloys are dry when stable. The same generally applies when substances are stored under normal atmospheric conditions with respect to temperature and relative humidity (50 to 60 percent).

Prolonged exposure to air with a high content, moisture or direct contact with water leads to the gradual conversion of the anhydride group into the free ditoarboxylic acid structure. This increases the polarity (hydrophilic character), while the modulus (brittleness), measured when dry, also increases. As a result of the reaction of the polyanhydride to a polyacid or a polyelectrolyte, the substance is stable hydrogels. The degree of non-swelling in water is a function of the stop ionization of the polymer alloy (ratio of polymers) to the pH of the aquatic environment.The maximum swelling occurs, for example, at pH = 6-8, and minimal swelling at pH = 2 to 3. reversible and comparable to known behavior of proteins such as gelatin, keratin and the like in water.

Accordingly, the hydrogel has the characteristic properties of a polyelectrolyte and can also act as a hydrogel in the form of a hydrogel as an ion exchanger that binds metal ions with greater numbers, such as calcium, copper, grain and cadmium. Hydrogens and xerogels produced by hydrolysis from a polymer alloy are stable due to the extensive interaction of the second component with the hydrolyzed or ionized first component.

The very rapid conversion of a polyanhydride polymer alloy into a hydrogel polyelecifrolyt can be accomplished with strong bases such as sodium or potassium hydroxide, especially ammonia, aqueous ammonia solutions, and organic amines. Crosslinking occurs in reactions with b1- or polyfunctional compounds, such as glycols, diamines, polyamines, etc. The degree of swelling of the hydrogels can be varied by their modification resulting from reactions with mono- and multifunctional reactive compounds.

The polymer alloys of the present invention can serve to produce synthetic products with a variety of properties.

The fabric may be in the form of granular, fibrous, foil, powder and other known in polymer processing technology. Of particular interest is the conversion into hydrogel (or polyelectrolyte) properties by the action of water.

Particularly important is the use of a fibrous or powdered substance in the form of a polyelecfrolyte or a salt for moisture absorption.

It is also possible to use the hydrogels formed by secondary reactions in conventional procedures such as R-exchangers.

As mentioned above, polymer blends are brought to swelling in the presence of water after they have been reacted with ammonia and organic or inorganic bases.

Thus, polymer alloys are particularly suitable for producing polymer blends for the regular release of active ingredients, for example by the action of water. Both the rate and the degree of swelling will affect the rate of removal of the additive components, thereby allowing controlled removal. The rate of evacuation is of course also a function of the shape and size of the particles of the polymer blends (grains, powders, foils, fibers, etc.). The active substances may contain such phaco insecticides, fungicides, herbicides, generally biocides, pheromones and so on, repellents for pests, plant diseases or insect and / or other harmful plants. Another option is to control from 226123 interfering with pharmacologically active substances. When polymer alloys are prepared in fibrous form, they can be converted after the secondary reaction by treatment with ammonia, amines, free bases, and so on into fibers with high water-swellability or moisture absorbability.

Finished, water-insoluble and water-swellable fibers are suitable for many purposes. These fibers may be primarily used in the production of absorbent layers for medical material.

The invention may equally be used in the form of films, films or thin sheets or tapes and so on. The swellability or absorbency is primarily a function of the ratio of the two polymers in the alloy. The increased concentration of the first component increases the swellability after secondary hydrolysis and / or ionization to the hydrogel structure.

During the preparation of the polymer alloy, it is also possible to add fillers such as carbon black, chalk, fibers and so on.

The addition of a foaming agent during preparation may also be advantageous in order to obtain a porous structure.

The invention also includes novel high temperature and homogeneous polymer alloys made from a first component consisting of one or more high molecular weight polymers and a second component consisting of one or more high molecular weight polymers capable of interacting with hydrogen, both the components are connected to each other by hydrogen bridges by total or partial protolysis of the first component.

The novel polymer alloys of the present invention comprise, as a first component, one or more high molecular weight copolymers, namely an unsaturated alkene monomer and mialeinanhydride, and, as a second component, polymers containing ester groups.

The first component in the polymer alloy of the present invention is typically a styrene-maleic anhydride copolymer, while the second component is typically polyvinyl acetate, cellulose ester, polyacrylate or polymethacrylate.

In addition, the polymer alloy of the present invention may contain an additional component and / or substances. Examples of the additional component may be either an active ingredient such as an insecticide, fungicide, herbicide and the like, or a reactive component to modify the polymer alloy during its preparation, or a foaming agent. Fillers such as carbon black, chalk, fibers and the like can be added as alloy additives.

Example 1

Preparation of styrene-malelraanhydride copolymer in methyl ethyl ketane as a solvent (i.e. solution polymerization). In a 50-liter vessel, the following ingredients are gradually blended: 30 liters (25 kg) a few years ago of lketone (butanone), 3120 g of styrene, 3000 g of maleic anhydride, and

7.5 g of azo-bia-isobuityroinitrile catalyst. The vessel is equipped with a heating jacket, thermometer, mixer and thermal protection device. Content se. it is heated with stirring and kept at a certain temperature for a certain time.

Example of heating mode

Heating to 60 ° C for 1 hour, then holding at 60 ° C for 2 hours, then holding at 70 ° C for 1 hour, and finally holding at 80 ° C for 3 hours. The total polymerization time is about 7 hours. Viscosity approx. 0.045 Pas. The solids content is about twenty percent. Critical separation temperature Tc = 41 ° C (measured with a polyvinyl acetate solution; see Example 2 and Fig. 1j). The degree of polymerization can be varied by varying the catalyst concentration and the reaction temperature.

The measurement of the intrinsic viscosity allows approximately the determination of the molecular mass.

Molecular weight, generally m = 10 ⁴ to 10 ⁵ , 10 000 to 100 000. A solid polymer can be obtained by solvent evaporation or precipitation in an excess of methanol.

Example 2

Partial hydrolysis of the styrene-maleic anhydride copolymer of Example 1 in solution. Partial hydrolysis to increase critical separation temperature Tc.

The critical separation temperature Tc is the phase transition temperature and was measured by mixing approximately equal parts of a 20% solution of the copolymer in butianoine, and a solution of polyvinyl acetate or cellulose triacetate, or cellulose acetobutyrate, or polyethylene acrylate (prepared in the laboratory). At critical temperature Tc, this mixture suddenly became cloudy due to separation (see melting point, determination of boiling point j.

After completion of the styrene-mialeinanhydride polymerization as described in Example 1, 0.1, 0.5 L and 2 weight percent water were added to the polymer solution samples with vigorous stirring (the water content of the total solution thus being about 0.1, These water-containing solutions were heated to 75 degrees Celsius for 20 to 30 hours, during which the critical separation temperature Tc was determined for the sample mixtures and the polyvinyl acetate solution. Fig. 1 shows protolysis and thus the increase in the critical separation temperature Tc for the polyvinyl acetate / styrene-maleic anhydride mixture as a function of the water concentration and the protolysis time at 75 ° C. that for the polyvinyl acetate / styrene-maleate anhydride mixture was

226123 found 'critical temperature separation of Tc = 100 ° C buiíamonu after 40 days of storage solution styrene-nialeinanhydrid one percent water at 20 ³ C while using a solution of a styrene-malečnanhydrid two percent water, and when heated to 75 ° C was achieved critical separation temperatures Tc = 100 ° C already after 8 hours.

At various times, after heating to 75 ° C and thus at different times of protolysis, samples of a copolymer solution containing one percent by weight of water rent were mixed with 20% cellulose triacetate or cellulose aceitobutyrate and polyethylene acrylate solutions, and the critical temperature of the Tc separation was detected. .

Example 3

Preparation of polymer alloy (ratio 30:70).

kg of the 20% copolymer solution of Example 1 was protolyzed with 10 g of water at about 75 to 80 ° C for about 16 hours. The critical separation temperature Tc then rose to 100-110 ° C. The following substances were mixed with this protolyzed copolyrner solution in a 50 liter container:

19.6 kg methyl! yl ketoin, 4.66 kg of polyvinyl acetate. The polyvinyl acetate is a suspension or bead polymerate.

The polyvinyl acetate (solid) was dissolved with gentle stirring to give a clear solution.

Mixing temperature about 15 to 20 ° C, total weight of the polymer alloy 34,30 kg, solids content twenty percent. The ratio of styrene-maleic anhydride / polyvinyl acetate 30: 70 missions. It is of course possible to mix with certain solutions of polyvinylacetate in methyl ethyl ketone. Pre-dissolved polyvinyl acetate has the advantage of rapid mixing with copolymer solutions. Of course, it is possible to quickly obtain all the desired polymer ratios according to Example 3.

Drying: About 1000 kg of the polymer alloy of Example 3 was dried using an industrial film dryer. Previously, approximately 2 kg of sitearyl alcohol (as internal non-separable lubricant; C18H18OH) was mixed into this solution to improve the processability of the solid alloy during its own processing. Prior to drying, a variety of materials can be added (as desired) to the polymer alloy solution: plasticizers, lubricants, stabilizers, modifiers, biologically active agents, dyes and pigments, fillers, and so on.

In Example 4, a fatty alcohol, i.e., stearyl alcohol (lubricant) is added to improve the extrusion properties of the dry polymer alloy.

Example 4

Using the drying apparatus of Example 3, the following drying tests were performed:

Experiment No. Charge Temperature Pressure kPu kg / h wall ° ^: C

1 75 cca 160 40 2 60 cca 160 53.33 3 60 cca 180 53.33 4 50 cca 180 66.66 5 75 cca 180 26.66 Content solids the printout was about 98

procenit. The initial critical separation temperature Tc was about 100 ° C. An additional percentage of water was added to about 1000 kg of a mixture of

of solid alloy Alloy appearance kg / h of polymer polymer 17 kalná 14 slightly cloudy 15 Dec clear 12 clear 18 slightly cloudy

of Example 3, and then stirred for 2 hours at 70-80 ° C. As a result, the critical Tc inia separation temperature increased more than 140 ° C.

Experiment no.

Charge kg / h

Wall temperature ° C

Pressure kPa

Yield of solid polymer alloy kg / h

Appearance of polymer alloy

(optimum) 7 75 cca 160 40 16 clear slightly cloudy (too far) 60 cca 190 26.66 15 Dec (Tc decreases again) (drying too

thoroughly)

These examples clearly show that a homogeneous polymer alloy is obtained only under special conditions.

Example 5

Starting with the polymer alloy solution of Example 3, drying tests were also carried out in a closed cylindrical dryer whose capacity was much smaller. Horizontal adjustment; two rollers with screw. Charge about 7 kg / h (20% solution); wall temperature 140-150 ° C; pressure 40 to 53.33 kPa; polymer alloy yield of about 1.5 kg / h; appearance - slightly cloudy. The resulting polymer alloy was in the form of an endless extrusion having a solids content of about 98 to 99 percent. Residual moisture content 0.5 to 1 percent. The extrudate could be granulated immediately after cooling.

Example 6

Test with a polymer alloy solution with a critical separation temperature Tc of 80 ° C. The dryer of Example 5 was filled with a polymer alloy solution prepared from a solution of the copolymer of Example 1 and polyvinyl acetate in a ratio of 30:70. Drying was carried out under the conditions of Test 5 of Example 4. The extruded product was now totally white, opaque and heterogeneous Compared to the clear extruded products, the products according to Example 6 were not used.

Example 7

Test to demonstrate an increase in the critical separation temperature Tc during drying (homogeneous and clear end product). To the polymer solution of Example 1 was added two percent water (based on total weight), and the mixture was heated to about 80 ° C for 8 hours. The critical separation temperature Tc was now 90 ° C. Then it was mixed with polyvinyl acetate and meityleitylketone. The ratio of polymers was 50:50. Drying in the apparatus of Example 5 was carried out under the following conditions: charge 5 kg / h; temperature 150 degrees Celsius; (pressure 53.33 kPa; yield 1 kg / / h; appearance - colorless to light yellow, clear. Example 8)

Properties of the solid polymer alloy prepared according to Example 3. Density 1200 to 1300 kg ur ³ . Modulus of elasticity depending on moisture content and mixture ratio 196.13 to

980.66 MPa (viscous to hard).

The granulate can be processed in standard gas extruders (twin-screw, allowing further reduction of residual moisture or solvent content. Thermal stability 1 to 2 hours at 150 ° C, slight increase in viscosity. At 1 hour at 190 ° C some degree of crosslinking; Moisture absorption at high humidity (100% relative humidity), about 5 percent for 30/70 alloy, about 10 percent in boiling water after 1 hour, and under normal conditions the material is stable and permanently thermoplastic.

Example 9

Preparation of blown foil (from polymer alloy and plasticizer). The polymer alloy solution was prepared according to the described method and in the composition 50/50 styrene-maleic anhydride / polyviinylationite (1: 1). The critical separation temperature Tc of the polymer alloy exceeds 120 ° C.

About 10 percent (based on dry matter) of glycerin triacetate was added before drying. After drying according to Example 5, a granulate was obtained from which a blown film was prepared according to the prior art process.

Foil properties: thickness 50 to 60 μΐη, modulus of elasticity 196,13 to 294,20 MPa; elongation 200 to 250 percent; a nia stress of about 9.8 MPa. The elasticity of the polymer alloy films is to a large extent a function of the moisture content of the material and / or the environment. Moisture sensitivity can be controlled by procedures described otherwise based on the nature of emollients, modifiers and the like.

Example 10

As Example 9. Polymer ratio 30:70. Plasticizers: 5 percent dibutyl phthalate (based on polymer amount).

Example 11

Preparation of fibers (wet spinning). The polymer alloy solution was prepared in butanone. The solids content of the solution was approximately 40 percent. Solution viscosity 35 to 40 Pa.s. Using known techniques, the polymer alloy solution was spun from the spinning liquid by extrusion into water at a temperature of about 20 ° C as a coagulation bath. The spinneret is provided with 15 holes with a diameter of 0.05 mm. The extruded solution formed monofilament fibers that could be wound continuously.

The resulting fiber strand had about 5 to 8 diets (g / 10,000 m) after treatment at 65 percent relative humidity, and the moisture content ranged from 2 to 3 percent at 20 ° C. (dtex - unit of fineness of fibers).

Example 12

Melt spinning test.

From the granulate obtained in Example 7, a fibrous polymer alloy was prepared by known melt spinning techniques using a suitable apparatus. The fibers may be recovered by post-treatment with ammonia or organic amines (thereby acquiring the properties of an electrolyte), thereby obtaining a high water-absorbability depending on the ratio of the polymers. The swelling capacity (AV) can range from 10 to 100 g water / g polymer alloy in deionized water. In the form of a polyelectrolyte (in the form of polyionites), the fibers have ion exchange properties.

Example 13

To a 20% solution of the polymer-butainone polymer alloy of Example 3 was added: 10 percent chloro-vinyl phosphate, calculated on the solid polymer content, and dried under the conditions described in Example 4, Test # 3 to give 1.6 kg of dry molding. was then granulated. A portion of the granules was ground to a powder. The granules, as well as the powder, were used as a regulating agent, such as a soil insecticide. The rate of active substance removal can be controlled by partial or complete ionization of the polymer alloy, for example with water, ammonia, bases or other protolyitic agents. In addition, the rate of removal can also be controlled to reduce the surface area of the release surface. As shown in Examples 5 and 6, as well as in Examples 2, 3, 4 and 7, homogeneous mixing (i.e., casting) is only possible if the drying was performed at a temperature below the critical separation temperature Tc of the polymer blend. The solid mixture can be detected by converting the mixture into hydrogel by ionization in water at pH 7.0 to 7.5.

Example 14

Preparation of the hydrogel and the Alloy of polymers prepared according to Example 4 (Experiment No. 3, 4 or 6) can be converted to a solid hydrogel by dilute 1% ammonia or other bases.

Example: about 4 grams of the extruded product (plates about 4 x 2 x 0.5 cm) were immersed in about 1 hour in a 1% ammonia solution. Preliminary swelling takes about 24 hours. Thereafter, the swelling is continued in neutral water, which is replenished until the maximum swelling is reached (final pH value 7.0 to 7.5). For stable ¹ hydrogel, the maximum swelling in neutral water was up to about 25 to 30 times the original dry mass; the water content of the hydrogel was about 96 to 97 percent (30:70 polymer alloy).

b) The polymer alloy material was prepared as follows: solutions of the vinylic laceitate, cellulose triacetate, polyethylene acrylate (synthesized in the laboratory) and polymethylacrylate in butanian solution as a second component (total amount about 20 percent) were mixed with styrene-maleic anhydride copolymer solution in butainone according to of Example 1 as the first component that was partially protolyzed to critical separation temperature Tc values below 100 ° C.

Solid polymer alloys were prepared by drying the respective polymer blend at a temperature of about 70 to 80 ° C. All solid samples were clear, no detachment occurred. From these products, solid polymer alloys (films of about 0.5 mm thickness) were sputtered with hydrogels according to Example 14a). Equilibrium uptake of water or degree of swelling (AV i in water having a pH of about 7.0 to 7.5) was measured as a function of the ratio of the first to the second component (Fig. 3).

Volume expansion (AV) is also a function of the ratio of the first and second components, as well as the entire molecular structure, commercial quality, and physico-chemical properties of the second component. It is clearly shown that the commercial grade hydrophilicity of various polymer alloys can be controlled by mixing more or less the first component into the polymer alloy.

Claims (8)

CLAIMS 1. Polymer alloy, stable and homogeneous in high iteploft, characterized in that it consists of a first component consisting of a copolymer of maletinhydride with a monomer selected from the group consisting of styrene and methyl vinyl ether containing 95 to 20 mol% of anhydride groups, the remainder being protolyzed for the introduction of hydrogen atoms as well as the second polymer component selected from the group consisting of polyvinylation phthalate, cellulose esters, polyacrylates and polymethacrylates, both present in the alloy in an amount corresponding to a weight ratio of 0.01 to 100, the molecular weight of each component being IO systems INVENTION range ^{from 4} to 10 ⁶ and the component are joined by hydrogen můcitky. 2. A polymer alloy as claimed in claim 1 comprising an additional foaming agent. 3. The polymer alloy of claim 1 comprising an additional ingredient consisting of an active ingredient, such as an insecticide, fungicide, herbicide, and the like. 4. A polymer alloy as claimed in claim 1 comprising an additive formed from a filler such as carbon black, chalk, fibers and the like. 5. A process for the preparation of a polymer alloy as claimed in claim 1 or any of claims 2 to 4, comprising first preparing a solution of the first component defined in item 1 in an organic solvent, to which a second component defined in item 1 is added thereto; the component is partially or completely protolyzed before or after the addition of the second component by the action of protolyzing agents, after which the solvent is removed, wherein both the first and second components have a molecular weight of the order of 10 ⁴ to 10 ⁶ . 6. The process of claim 5 wherein the protolyzing agent is water, a goat, an alcohol or an amine containing from about 1 to about 10 carbon atoms. 7. A process according to claim 5 or 6, characterized in that the solvent is removed by evaporation at 100 to 200 [deg.] C. in a closed system, while ensuring a degree of moisture between 0.1 and 0.5 weight percent during evaporation, and recovering the solvent. . 8. The process of claims 5 and 7, wherein the removal of the solvent is carried out at 130-100 [deg.] C under a reduced pressure of 1.33- 66,66 kPa.