SU575034A3 - Method of preparing polyelectrolyte complexes - Google Patents

Description

(54)

METHOD FOR GETTING POLYUELE COMPLEXES

This invention relates to a process for preparing polyelectropite components from polymers containing sulfo groups, sulfopolymers, and polymers containing quaternary ammonium rough (ammonium polymers).

Proceedings of numerous polycomplexes obtained by ionization of sulfopolymers with ammonium polymers P).

Most of these complex polyelectrodes are obtained as a result of the reaction of sulfoolimers and ammogens, polymers that are individually soluble in water; they are prepared by mixing aqueous solutions of reactive polymers.

There is a method for preparing polyelectrolyte complexes by reacting sulfopolymers and ammonium polymers that are not individually soluble in water. These latter complex polyelectrolytes, like the previous ones, were obtained by mixing the solutions of the reacting polymers 2.

A method is proposed for producing polyelectrolyte components based on sulfopolymers and ammonium polymers that are not individually soluble in water by mixing one of these two reagents in a solid state (powder) with

Drupsch reagent, the latter can be in the form of a solution, preferably in a solvent of the final complex aolye of the electrolyte, or in solid state (powder), in a shocking case, the mixture of two powders is converted into a solution, preferably in the solvent of the final complex polyelectrolyte.

According to the proposed method, a powder with a grain size of less than 500 is used, preferably in a YuTerval of 20 and 100 μm.

Polyelectrolyte complexes (full shlexes), obtained by the proposed method, are insoluble in water and soluble in organic matter (medium n corresponds to a common form and

in which Mj and Mj mean "" lamel chains, containing groups that Moryt can be bonded to with their ears and ho and do not contain reactive groups capable of forming internal covalent bonds; ctiNreon indicates that the group g is linked to a macromolecular, represented by Mj by at least one covalent bond; the ratio m: n in polycomplex is 0.1-10. Sulfopolymer and ammonium polymer have structures II and 1И represented by the formulas {, t, n) in which MI and M; have the specified options. Z is an alkali metal or alkaline earth metal cation; A - Ion 1T1Droxyl or anion of mg of oral or organic acid of the general formula Well A; y equals 1.2 x 3; X TpsBiro 1 w 2; the symbol indicates that the nitrogen is bound to the Ashkromolecular chain of Mg at least one co-bond. In order to simplify the situation, comalex potielectrolyte, which has the formula-lAg,, t shevagog polnnon, and c1b, which has the shape of y-lg, is odikatia. ; . ,; . N®::.. ::;:; Usually, the presence of the rpjnnBpoBCK strain in the macromolecular chain improves the integrity of polymers in water. The formulas of Ni1, although about} | adz; Eot G} of wide groups, should be dissolved in water. Hb {} asgao {H1 bridges in water can be reduced, on the one hand, increase the molecular weight {of the holimer and, on the other hand, limit the number of hydrophilic groups associated with macromodecular ® chains. 8 with respect to molecular weight, it can be noted that, mainly, the specific viscosity of each polymer of formulas II should be greater than 0.01; Preferably, it is mv sdo 0.05 and 1.5 (measured prc 25 ° C in a concentration of 2 g / l in dimethylformamide). The number of podrofilnyh groups in the polymers of formulas P and 1P is less than one hydrophilic group by 12 carbon atoms, preferably, less than one hydrophilic group by 20 carbon atoms. Only groups 5 Oz and N. can be groups. Polyashun and polycation may also have a small amount of other hydrophilic groups. These hydrophilic groups can be such lower groups as carboxyl groups, sulfo groups of an acidic or salt character, phosphonic and phosphate groups, sulfamic groups; or capyne groups, such as amine salts, compounds with phosphonium or sulfonium groups; non-ionic groups, for example, hydroxyl, ethers, carbonic ester-amide. If the polyanion and the polycation contain other hydrophilic groups, in addition to the ZOn and N groups, it is desirable that these additional groups are non-ionic or have the same charge as the characteristic groups of the polymer, however, the polyanion and / or the polycation can contain up to 5 % respectively cationic and anionic groups. Sulfopolymer Aluzhet be selected from the group consisting of: 1) Schmerizayug monomer products, at least some of which contain sulfo groups; 2) products obtained as a result of the sulfonation of polymers prepared from monomers that do not contain sulfo groups. Among the Polymers of group 1, it is possible in particular to mention the products of polymerization and vinyl psh. As examples of monomers containing sulfo groups, irivesga acid (in some cases in salt form) can be used: vinyl sulfonic, propyne - 1 - sulfo - 1 - acid, allyl sulfonic, metallic subphone, allyloxyethyl sulfonic, and u)} .; vinyl benzene sulfonic acid, vischoxybenzene sulfonic acid; bromovinyl benzene sulphonic acid; (d) mestirolsulfonic acid; isopropylenol sulphonic acid; MONO-, da- and trioxyvinylbeisol sulfonic acids; isopropenylnaphthalenesulfonic acid. As examples of comonomers used in polucheshi polymers of group 1 (fragments Ts1 formula) (available pr1shesti ethylene, styrene, bromide vinyl, vinyl chloride, acrylonitrile, allilovsh alcohol, allyl and vinyl zfiry, vinyl ketones, nenasyscheshayu monocarboxylic acids and their alkyl e: or aryl esters, cyan-. (meth). acrylic glosses, asteroids of aliphatic dinear or branched monocarboxylic acids, in some cases in a partially saponified state, amides of unsaturated acids and so on. As specific examples of polymers of group 1, copolymers of acrylonitrile with metal sulfonic acid or its salts can be cited. In these copolymers, some of the fragments contributing to the acidic group 5 Oe H are usually from 1 to 30 wt.%, Preferably 4 to 20 wt.% , it is relative to the weight of the total copolymer). Other examples of polymers of group 1 are polycondensates of dacarboxylic acids and diols or diamids, at least some of which contain one or more substituents - SOIH. as specific examples of diacids, eulfo succinic and 5 sulfoisophthalic acids can be given.

Mentioned acids should be used in conjunction with other diacids, for example, aliphatic diacids such as succinic, glutaric, adiphennova, pimite, corkova, azelaic, sebacin, maleiov, fumaric; cycloalkanedicarboxylic acids such as cyclohexane — 1,4 dicarboxylic acid; aromatic acids, for example benzene dicarboxylic acids. As examples of diols, ethane is used,

propane-, pentane-, hexane-, decandoles.

As examples of diamines use

ethylamine, 1,2 - diamium propane, feland1

amine, diaminocarbazoles, etc.

As well as sulfopolymer, ammonium

Cholimers can be of two types:

1) products obtained by treating with quaternizing aieHTOM polymer (I) containing tertiary amino groups;

2) npo QTCTbi, obtained by reacting a tertiary amine with a polymer (I) containing substituents that can quaternize (convert to a quaternary ammonium salt) the indicated amine, thereby providing a bond with the polymer.

As specific examples of polymers of group I, copolymers of acrylonitrile and vinylpyridine can be given. In these copolymers, the proportion of fragments introduced by the amine monomer is obino between 1 and 50 wt.%, Preferably between 4 and 30 wt.%, Relative to the weight of the total copolymer.

Group 1 polymers can also be a co-condensation product of monomers, at least some of which contain tertiary nitrogen atoms.

As specific polymers of polycondensates containing groups with tertiary nitrogen, one can cite poly (complex ester) urethanes obtained from a diol containing a tertiary nitrogen atom, such as ethyldiethanolamine, ashtinic acid, and a diisocyanate such as 4,4-diisodanate diphenylmethane. For these polymers, the molecular weight of the intermediate poly-ester is usually from 300 to 10,000.

The quaternization agents of the tertiary amino groups, as well as the processing conditions are known. Alkyl halides and alkyl sulfates are commonly used, as well as cycloalkyl and aralkyl halides and sulfates. Preferably, alkyl, cycloalkyl and aralkyl radicals contain more than 14 carbon atoms. As examples of such quaternization agents, chlorine methyl, methyl bromide and methyl iodide, ethyl, propyl, cyclohexyl, dimethyl and distilisulfate can be given. It is also possible to use halide derivatives containing other chemical functions, such as chloroacetaldehyde.

Polymers II, capable of reacting with tertiary I amines, resulting in one of the alcohols polymers 2, are halogen-containing.

As examples of tertiary amines that can be reacted with halide-containing palimers, trialkylamines with unsubstituted alkyl radicals, such as triethylamine and other trialkylamines, in which at least one of the radicals (replaced with functional groups such as M-dialkylalkanolamines and other heteroplastic amines, for example, pyridine, picolines, lutidashes, etc., and amines with aromatic closely spaced dramas, for example, N, N-Dymetitenshn.

Commonly used algans contain 3-12 carbon atoms.

In the preparation of the proposed complex polyelectrolytes, as mentioned above, the solvent of the reagent polymers is used, which is preferably a solvent of the final complex. This solvent is preferably organic and may consist of a single solvent or a mixture of solvents.

The choice of solvent obviously depends on the nature of the various polymers used. However, more common are higher polymers that are soluble in such polar apotochol solvents such as dimethylformamide, dimetidetatasch, dimethylsulfoxyl, hexamethylphosphorotriamide, N-methylpyrrolvdon-2, sulfolane, ethylene carbonate. It is possible to name the mixtures of these solvents between themselves and / or with other organic solvents, such as ketones, esters.

in the case of a mixture of a powdered reactive polymer with a solution of another polymer that is reactive, the initial concentration of this solution of the reactive polymer affects the physical aspect of the resulting complex electrolyte. Typically, the concentration of the polymer p ipacTBope of the initial solution should be 0.25% And preferably, above 0.5% by weight

The upper limit of the concentration is determined by the requirements of a mop telescope. Usually this is before, eaten in the order of 25%, and, of course, the dima can be n higher.

Preparation of the starting polymer solution is carried out by methods commonly used for preparing polymer solutions. Usually, the polymer is initially dispersed in the solution, keeping the teleshaure relatively low (from –20 to + 20 ° С); then gradually raise the temperature until a clear and homogeneous solution is obtained. The final telterature depended on the nature of the polymer and solvent. In general, it lies between 20 and 100 ° C.

In the case of the use of a solution of the mixture of two powders of the starting polymers, it is important that the solution is graded at the analogy given above, i.e. The total fraction of dissolved psmcr in the solution should be above 0.5%, by primitive above 1%, its BepxHjdi limit is approximately 50%.

the dissolution is carried out under the same conditions as that. are given to dissolve one of the starting nolimvres in a solvent,

As regards the value of the ratio m: n indicated above, the sulfopolymer or ammonia polymer can be in excess of ions in the reactive medium. It is desirable that the ratio m: n is between 0.2 and 5.

A solution of co-complex electrolyte form NFyHbi} can be used to make films {like products.

Films or membranes obtained from solutions of complex full electrolytes prepared by the proposed method, which can be 1 FLAT, tubular, spiral or any other form, can have an isotropic or ayugzotropic structure. The membrane of the 1st isotrol structure is understood to mean a membrane that has a uniform density of the iUH structure of porosity throughout its thickness; An aniso-trisic membrane is usually understood as a membrane having a porosity gradient from one surface to another, in the limiting case, one of the surfaces can be completely devoid of pores.

Isotropic membranes usually appear when a simple solution of a complex polylecgrolite solution is applied to a suitable surface (such as a glass plate or metal; a plastic plate, a tube, a cipher band) and a subsequent removal of the solution. Anisotropic membranes can be obtained by immersing the plate, cf./vicious r. Solution of complex polyelectro., Coaguash bath (not a solvent of complex polyelectrolyte.) Typically, the coagulation bath contains water or a mixture of soda and organic liquids or aqueous solutions of spore. .

More often, complex polyelectrolytes may include fillers and / or plasticizers, which are mixed directly with the complex polyelectrolyte in solution or previously introduced into the initial sulfopolymer and / or ammonium polymer ..

The membranes can consist of a single / complex polyelectrolyte film, but there is no solonized shsh, shsh contain a reinforcing filler, such as knit or mesh, from natural or synthetic fibers.

The complex polyelectrolytes prepared by the proposed method can be used in various areas: in textile industry, in the form of fibers, fabrics or complex for processing and filaments or fabrics intended for some properties, such as ability to dye the neck, hydrophilicity , itystatichnost. These properties can be precisely selected depending on the excess of anions or cations in the complex polydrolit.

For example, membranes can be used to fractionate solutions according to ultrafiltration, osmotic inversion and dialysis techniques. These membranes, in particular when they are anisotropic, have a particularly high retention rate of macromolecules with an overall high permeability. It should be noted that heat treatment in water permits modification of the membrane membrane and change its retention zone (limit molecular weights of compounds passing through the membrane) from a high value (for example, 1 (SOO-15000) to very low (about 200- 300). These membranes combine good permeability with high mechanical strength.

Pleshy complex 1P) 1x polylectrolytes can also be used as bacteria separators.

In addition, these polyelectrolytes can be used in medicine, for example, for artificial kidney and lung, due to their dialysis ability and improved gas performance. Membranes made from these polyelectric waves are commonly used in the manufacture of prostheses or any products that must be co-octated with blood, since these polyelectrolytes have high antimicrobial properties.

Complex polyelectrolytes can also be used as artificial leather or in the manufacture of electrically conductive coatings or antistatic coatings.

The many applications mentioned above show only examples of the use of combs P-1X polyelectrolytes, but do not limit this area.

The following non-limiting examples illustrate the invention.

PRI me R I. The following compounds were introduced, or separately, into a 250 ml capacity vessel equipped with a stirrer, preparing the solution while mixing it in the container, shsh together as an already prepared solution.

19.6 g of acrylonitrile and sodium methylsulfonate copolymer powder (0.600 milliequivalent / g of sulphonate groups; granulometry: between 50 and 80 micro-viscosity measured at 25 ° C in a solution of 2 g / l, in dimethylformamide, 0.87.).

A mixture of 163.4 ml of dimethylformamide and 8, .6 ml of water. The solution is cooled to 0 ° C, 8.4 g of acrylonitrile copolymer powder and 2-methyl-5-vinylpyridia (containing 0.564 millin equivalent / g of tertiary amino groups) quantized with an excess of methyl sulfate and having a quaternization specific viscosity (added) are introduced into it. ° C in a solution of 2 g / l, in dimethylformamide) 1.6 and a grain size distribution between 50 and 80 μm. All is stirred at 0 ° C for 1 h, which allows for a thorough dispersion of the breaks of copolymer in the medium.

Claims (2)

Raise the temperature of the mixture to 20 ° C, stir for 1 h, then mix the mixture for 3 h at 65 ° C with constant stirring. The result is a clear solution. This solution is poured onto a glass plate in such a way as to obtain a 0.25 mm thick liquid film, which coagulates upon immersion from plastic and in a water bath at 20 ° C. After removing the solvent by washing with water, a membrane is obtained, which is used for ultrafilters at a pressure of 2 bar of an aqueous solution containing 1 g / lysozyme (mol. Weight 15,000) and 5.85 g / l sodium chloride, this solution is mixed on the membrane surface with Map Stirrer The flowing fluid is collected at a flow rate of 5,400 l / day m. The degree of lysozyme retention is above 90%. Example 2. A 19.6 g acrylonitrile-metallic sulphate powder copolymer powder, identical to that used in Example 1, was loaded into a grinding mill, operating with a rotating belt, identical to that used in Example 1, 8.4 g of a copolymer quater powder identical to that used in Example 1. As soon as the mixture of the two products becomes homogeneous, added with a mixture of 163.4 ml of dimethylformamide and 8.6 ml of water. Then the entire mccy is stirred for 1 hour at 0 ° C, 1 hour at 20 ° C, and 3 hours at 65 ° C. As a result, a clear solution with a viscosity measured at 25 ° C, 272 pz is obtained. From this solution, an ultrafiltration membrane is prepared according to Example 1. This membrane gives a flow rate of pure water at 2 bar equal to 4880 l / day-m. EXAMPLE 3: A grinding mill operating with a rotating year is loaded with: iO g powder of acrylonitrile copolymer with sodium metal sulfonate (0.570 millisquivalent / g sulphonate groups; grain sizes 50 and 80 µm, specific viscosity measured at 25 ° C in a solution of 2 g / l, in dimethylformamide (1.03); South of copolymer acrylonntrile powder and 2 methyl - 5 - B1 shstiridine (containing 0.570 millisquivalent / g of tertiary amino groups quaternized with excess methyl sulphate and having, after this quaternization, the specific viscosity, measured at 25 ° С in a solution of 2 g / l, in dimethyl forms and L, measured viscosity, measured at 25 ° С in a solution of 2 g / l, granulometry 50–80 µm; 0.121 g of lithium chloride. The mixture is homogenized in Example 2, then 105 ml of dimethylformamide is added at 0 ° C. The whole mixture is then stirred for 1 hour at 20 ° C and 3 hours at 65 ° C. As a result a clear solution is obtained with a viscosity measured at 25 ° C, 445 pz (the equivalent viscosity of the solution obtained by mixing individual solutions of reactive polymers under similar conditions.) Claim 1. Qioco6 for preparing polyselectrolyte complexes by mixing a polymer containing sulfo groups of sulfopolymer) from a polymer containing quaternary ammonium groups (groups) ), and {are not individually soluble in water, characterized in that, in order to simplify the technology for producing poly-complexes, one of the polymers is mixed, which is in a powdery state with another olim rum in the form of powder or solution, followed by dissolving the mixture of polymers in a solvent. 2. A method according to claim 1, characterized in that the olimer is selected from among polymers represented by the formulas fw4 {n} I M / 77 gxe where MI and Mj denote macromolecular chains linked by covalent bonds with sulfamide groups; Z is an alkali metal or alkaline earth metal cation; A is a hydroxyl ion or ashyun of a mineralic or rganic acid of the formula NuA; X is 1 or 2; y is 1,2 or 3; the symbol indicates that the nitrogen is bound to the macromolecular chain Mj by at least a normal covalent bond; the type indicates the number of units in the copolymers, and the ratio t: n in the polycomplex is 0.1-10. 3. Method according to paragraphs. 1 and 2, characterized in that they are used; polymers containing at least one hydrophilic group per 20 carbon atoms. 4. A method according to claim 1, characterized in that polymer powders are used with a granule size below 500, preferably in the range of 20-100 microns. 5. The method according to claim 1, which is based on the fact that the solvent used to prepare the polymer solution is a substance that is a solvent of the final polyelectro-complex and consists of one or a mixture of organic solvents. 6. Method pop. 1, characterized in that polymer solutions are used with a concentration lying in the range of 0.5-50% by weight. 7. The method according to claim 1, that is, so that the dissolution of the mixture of polymers in; the solvent is carried out by dispersing the powder or a mixture of polymer powders in the liquid phase at a temperature ranging from -20 to + 20 ° C, followed by increasing it to 20 ° C to obtain a clear homogeneous solution. 11 u p or p on points: 12/4/73 pop. 1-zi 5-7. 08/01/74 non, 4.5 12 Sources of information taken during examination: 1. A. S. Michaels et al., J. Phys. Ctiem. 65,961.0.1765. 2. Patent of France N2144922, class C08f 39 / 00.1973.