JPS6018698B2 - Method for producing ionically crosslinked polymers - Google Patents

Description

[Detailed description of the invention]

The present invention is a polyelectrolyte (polyelectrolyte).
It is related to. Ionically crosslinking polymers have already been described. "Rust polyelectrolytes", which are crosslinked polymers obtained by reacting two polyelectrolytes with oppositely charged ionic groups, are known, for example KIRKOTHMER, Encyclopedia of Chemical Technology, 16, p.
See PI17-133. The properties of the Tsuba polyelectrolyte are: 1) Insoluble in water and organic solvents, 2) Soluble in water, polar organic solvents, and certain ternary mixtures of strongly ionizing electrolytes, commonly referred to as ionically shielding solvents; 3} Both of the polyelectrolytes (polyanion and polycation) used as raw materials are soluble in water (cited in PI17).
2 Jackson indicates that the initial polyelectrolyte should be soluble in water to a significant extent, for example at least 1% (see US Pat. No. 2,832,746, column 2, 54-5). Jackson also indicates that it is preferable to use the initial polyelectrolyte mostly in water-soluble form (U.S. Pat. No. 2,832,747, column 7, no.
(See line 4 and column 8, lines 45-47). Alan S. Michal (e.g. Canadian Patent No. 838,717, No. 8)
Nos. 38718, 839719, 83872 and 838721) also contain polyanions and 3
Reference is made to the collar polyelectrolytes from polycations and polycations, and various auxiliaries of ion-shielding solvents intended for forming the key polyelectrolytes are described. The above-mentioned Qian polyelectrolyte is used in many fields, such as extraocular dialysis, dialysis,
It has useful properties that can be used in applications such as 3 membranes for reverse osmosis, battery separators, and medical and surgical applications. However, various publications regarding ion-shielding solvents indicate that although the insolubility of such polymers in practically all solvents is useful for the final product, the formation of the complex polyelectrolytes is extremely difficult. It shows that it is difficult to do.
In accordance with the present invention, a novel ionically cross-linked polymer, hereinafter referred to as "seni polyelectrolyte", can be formed into films and molded materials that can be molded without the use of ionically shielding solvents and has excellent properties in most applications. Used to manufacture things. The novel complex polyelectrolytes according to the invention are firstly ionically soluble in organic solvents but insoluble in water without the use of shielding solvents, and secondly, anionic and cationic polyelectrolytes which are respectively insoluble in water. Manufactured from electrolytes. More particularly, the present invention provides a method for producing a copolymer selected from acrylonitrile/methallyl sulfonic acid sodium salt copolymers and sulfonated polyarylethernosulfones, and which have the general formula A polyanion that represents a macromolecular chain bonded to the -S03e group via a bond, and the size of the molecular chain and the value of n are sufficient to make the polymer insoluble in water and soluble in organic solvents. A neutral polar organic solvent solution of the polymer, 'B} acrylonitrile/quaternized 3-vinyl-6-methyl-pyridine copolymer, and quaternized poly(
P-dimethylaminostyrene), phenoxy resins containing quaternary ammonium groups, and polyester-quaternized polyurethanes, and having the general formula (in the formula "Uml"
UL represents a macromolecular chain that is N-linked via a covalent bond, and the size of the molecular chain and the value of m are sufficient for the polymer to be insoluble in water and soluble in organic solvents, and the ratio of n/m is 0.1 to 10) is combined with a solution of a polycationic polymer in a neutral organic solvent,
A general formula characterized by separating the produced polymer of the following formula (1) (provided that the meanings of the symbols, n and m in the formula are as described above, and the n/m ratio is 0.1 to 10)
The present invention relates to a process for producing ionically crosslinked polymers which are soluble in liquid organic media in the absence of ionically shielding solvents. For brevity, the tsuba polyelectrolyte part of the formula is called the "polyanion" and the part of formula (12') is called the "polycation", and similarly,
The polymer of formula (12,) is referred to as a "sulfonic acid polymer" and the polymer of formula (12) is referred to as an "ammonium polymer." The production of the complex polyelectrolyte of the formula (1) of the present invention can be carried out using the formula (1,)
A neutral polar organic solvent solution of a sulfonic acid polymer with the formula (
It consists of mixing a solution of the ammonium polymer of 12) in a solvent that is miscible with the same solvent or the above-mentioned solvent and is compatible with the sulfonic acid polymer. The key electrolyte of formula (1) can be precipitated from the reaction medium. Generally, the presence of ionic groups in the macromolecular chain increases the hydrophilicity of the polymer. The polymers of formulas (1,) and (12) have hydrophilic groups, but on the other hand they must be water-impregnable. Water insolubility is obtained firstly by increasing the molecular weight of the polymer and secondly by limiting the hydrophilic groups that attach to the macromolecular chains and to the UUUm-. Regarding molecular weight, in general the specific viscosity of each polymer of formula (1,) and formula (12) should generally be greater than 0.01, preferably between 0.05 and 1.5 (25o
(determined in a 200°/Z solution in dimethylformamide at 10° C.). Regarding the number of hydrophilic groups, generally each formula (1,) and (1
In the polymers of 2), there will generally be less than 1 hydrophilic group per 12 carbon atoms, preferably less than 1 hydrophilic group per 2 solid carbon atoms. Quaternizing agents and conditions of use for tertiary amine groups are described in the literature. Generally, esters of inorganic acids are used, such as halides and alkyl sulfates, cycloalkyl sulfates, and aralkyl sulfates. Alkyl, cycloalkyl, and aralkyl groups preferably contain no more than 14 carbon atoms. Examples of such quaternizing agents are methyl chloride, bromide and iodide, ethyl, propyl, cyclohexyl and pendyl,
and dimethyl and diethyl sulfate. Also, halogenated derivatives containing other chemical groups such as chloroacetaldehyde can be used. In the preparation of the polymer according to the invention, the sulfonic acid polymer and the ammonium polymer as defined above are each dissolved in an organic medium. The organic medium may consist of a single solvent or a mixture of solvents. The solvent used to make the poly(sulfonic acid) solution can be different from the solvent used to make the poly(ammonium salt) solution, and the solvent for one polymer may or may not be the solvent for the other polymer. and also subjected to zero conditions in which the two solvents are miscible with each other. The choice of solvent essentially depends on the nature of the polymer. However, in general, the various polymers mentioned above are neutral (
aprotic) polar solvents, such as dimethylformamide (DMF), dimethylacetamide (DMAC)
), dimethyl sulfoxide (DMS○), hexamethylphosphotriamide (HM circle T), 2-N-methylpyrrolidone (NMP), sulfolane and ethylene carbonate. Of course, the solvent's mutual and (
or) mixtures with other organic solvents such as ketones and esters can be used. The initial concentration of the poly(sulfonic acid) and poly(ammonium salt) solutions has an effect on the physical appearance of the resulting polymer. Generally, the concentration of each starting polymer should be greater than 0.5%, preferably greater than 1%, to ensure continuity in ionically crosslinked polymers. The upper concentration limit is determined essentially by technical requirements. Generally, this limit will be on the order of 50%, but this is not critical. The preparation of poly(sulfonic acid) and (ammonium salt) solutions can be carried out according to techniques commonly used for the preparation of solutions of polymers. Usually, the polymer is heated at a relatively low temperature in the initial stage, e.g.
Disperse in a solvent kept at a temperature of 0 qo, then gradually increase the temperature until a clear and homogeneous solution is obtained. The final temperature depends on the nature of the polymer and solvent. This is generally between 20 and 100°C. 1 of the sulfonic acid polymer and ammonium polymer
One or the other may be present in excess with respect to the ionic groups in the reaction mixture. Preferably, Higa is on the o-2 side and 5. Mixing of the two solutions may generally be carried out at a temperature of 100 to 100°C. Preferably, the mixing is carried out at ambient temperature (20 to 25 qo). The formation of a complex polyelectrolyte is shown to rapidly increase the viscosity of the solution as soon as the two solutions are brought into contact. The introduction of a strongly ionized electrolyte into this new solution, which can be compared with the "ionic shielding properties" described in the prior art, results in a considerable decrease in viscosity, which, according to the common interpretation, is due to the fact that this electrolyte is a sulfonic acid polymer. This indicates that the ionic bond formed between the ammonium polymer and the ammonium polymer was at least partially broken. Solutions of the polymers of formula (1) can be used directly for the production of films or molded articles. Particularly if it is desired to produce a membrane by casting a polyelectrolyte solution, it sometimes happens that the viscosity of the solution obtained in the reaction medium is too high. It is sufficient to dilute this solution to obtain the desired viscosity. It is clear from the above that the use of ion-shielding solvents is by no means essential when using the polymers of the invention. However, it is clear that it would not be outside the scope of the invention to use strongly ionizing electrolytes that are soluble in organic media, such as lithium chloride, to reduce the viscosity of the complex polyelectrolyte solution. Films and membranes obtained from solutions of Tsuba polyelectrolytes according to the method of the present invention can be planar, tubular, spiral,
Alternatively, it may have any other shape and may have an isotropic or anisotropic structure. A membrane with an “isotropic” structure means a membrane with a dense structure or a uniform porosity throughout its thickness, and an “anisotropic”
It generally refers to a membrane that exhibits a gradient of porosity pores from one side to the other, and whose local state can be such that one side is completely free of pores. Isotropic membranes are generally obtained by simply casting a polyelectrolyte solution onto a suitable surface (such as a glass or metal plate, tube, spiral or tape) and then removing the solvent. Heterotropic membranes are obtained by immersing a plate supporting a layer of polymer solution in a coagulation bath for the polymer. Generally, the coagulation bath consists of water or a mixture of water and an organic solvent or an aqueous solution of an electrolyte. It should be understood that the complex polyelectrolyte according to the invention can contain fillers or plasticizers, which can be mixed directly into the polyelectrolyte or pre-added to the polymer and/or the initial Can be added to ammonium polymers. Similarly, the membrane may consist of a filled or unfilled polymeric film alone or may contain reinforcing materials such as woven fabrics, knitted silk fabrics, or silk based on natural or synthetic fibers. The rust polyelectrolyte of the present invention can be used in many ways, in the textile field in the form of yarns, textiles, or intended to impart certain properties such as dye affinity and hydrophilicity and antistatic properties. It can be used in processing materials for yarn, yarn, or textiles. These various properties can be adjusted as a function of the excess anionic or cationic nature of the polymer. The polymeric membranes obtained by the process of the invention can be used for fractionating solutions, especially using ultrafurnace, reverse osmosis and dialysis techniques. Said membranes, and in particular anisotropic membranes, consequently have a particularly high degree of impermeability to macromolecular substances, while having a high degree of permeability to water. Heat treatment in water changes the structure of the membrane and increases its stagnation zone (the limit of the molecular weight of compounds passing through the membrane) from high values (e.g. 10 to 15,000 L).
) should be noted that it can vary to very low values (on the order of 2 to 300). These membranes have good mechanical properties in combination with their permeability and are able to withstand the pressures of service without damage, for example during an ultrafurnace. The polyelectrolyte films of the present invention can also be used as battery separators. Also, because of the dialysis and gas permeability of the membrane, it can be used in medical applications, especially in artificial kidneys and lungs, and because its polymers have significant antithrombogenic properties, it must come into contact with blood. It can be used for articles. The polymers of the invention can also be used as artificial leathers or for the production of electrically conductive or antistatic coatings. However, it is acknowledged that such use is illustrative only. The following examples further illustrate the invention. Temperature Z is given in °C. Example 1 Solution A, having a viscosity of 145 poise in 12 months, is prepared from 9 hours of acrylonitrile-sodium methacrylate sulfonate copolymer (a,) and 41 hours of dimethyl diformamide (DMF). This copolymer, which has an ion exchange capacity of 1.265 milliequivalents (meq)/k9 and contains 1 S03Na group per 40 carbon atoms, was added to an aqueous solution containing 300 mg of sodium chloride per solution. It was produced by polymerizing a single polymer in solution. Acrylonitrile/3-vinyl-6- is quaternized with methyl sulfate at 2530 and 33 poise viscosity solution B.
Methyl-pyridine copolymer (b,) is prepared from 9 parts and 41 parts of DMF. This copolymer has an ion exchange capacity of 1.265 meq/k9 and contains one quaternary ammonium group per zero carbon atom. A non-quaternized copolymer was obtained by copolymerizing two dimethylsulfoxide-soluble monomers in the presence of azobisisobutyronitrile. The number of belts, perforated grooves, reeds, and fleas in the specific copolymer charter is equal to . Solutions A and B are mixed and immediately the copolymer (a
A solution (A, B,) of a polymer resulting from the ionic crosslinks formed between , ) and (b,) with a viscosity greater than 2000 poise is obtained. This ionic crosslinking can be illustrated by the fact that if 250 parts of lithium chloride is added to the reaction mixture, a significant increase in viscosity is observed. 2 The viscosity of solutions A and B was reduced to 120 at 25o0 by diluting with DMF.
The solution is then spread on a glass plate (300 Poise layer thickness) and the whole is immediately immersed in water at 2:0 Poise. The film peels off naturally after 3 minutes. This membrane with a total thickness of 140 r is white and opaque and has a bright side (air side) and a matte side (glass plate side). 3 Soak the membrane in water at 50 oo for 1 minute and then use for fractionation of protein solutions. For this purpose, the membrane is placed in an ultrafiltration apparatus with the bright side of the membrane facing the solution to be filtered. Filtration is carried out under a pressure of 2 bar (pressure difference upstream and downstream of the membrane). Protein opacity (de
greeolrection) and ultrafurnace overflow rate. It will be recalled that the opacity can be defined by the following numerical value: the amount of large molecules contained in the volume l of the liquid in the calciner 100 x [1 - the weight of the macromolecule in the unit volume of solution to be passed through the calciner. The nature and concentration of the protein applied and the results obtained are given below. Membranes produced according to (1) above and which can be submerged in water for 10 minutes at a temperature of 6°C have a flow rate of 0.03 m/min. Molecular weight of evening/evening) 1
It has an impermeability to dextran of 0,000. 4. The membranes described in leg 4 are tested for their antithrombogenic properties. To do this, a 4.5 skin diameter disc is cut from this loose and then 1/2 fresh human blood is placed on this desk at a temperature of 370 degrees. Shake the desk every 3M sand until the blood clots. It can be seen that clotting occurs only after 78 minutes at 370. Example 2 1 A solution A2 with a viscosity of 327 poise at 25 DEG C. is prepared from a mixture of acrylonitrile-sodium methallyl-sulfonate copolymer (a2) and DMF. The copolymer prepared in the same manner as Example 1 has an ion exchange capacity of 570 meq/kg and contains 1 -S03Na group per 94 carbon atoms. 7 at 25℃
A solution with a viscosity of 1 poise is prepared from a 9.8 poise and 43 poise DM circle of acrylonitrile/3-vinyl-6-methylpyridine copolymer (b2) which is quaternized with methyl sulfate. This copolymer has a weight of 871 milliequivalents/

It has an ion exchange capacity of 9 and contains one -N- derived SQCH3e group per carbon atom. A solution A2& of the polymer resulting from the ionic bond between the two copolymers and b2 with a viscosity of 1318 poise is obtained by mixing the two copolymers and b2. 22 Bring the viscosity of B2 to the solution to 512 poise by adding DMF. The solution diluted in this way is molded onto a glass plate (layer 300 mm thick) and the whole is soaked in water at 200 mm. After 4 minutes, the membrane peels off from the glass plate. This membrane has a total thickness of 200 mm and has the same appearance as the membrane of Example 1. This membrane, either as is or after various treatments as described below, is subjected to ultrafiltration to separate various substances (at a pressure of 2 bar unless otherwise stated).
Flow path for extraocular source filtration: 1.2 min.
12400) is 100% blocked. Membrane treated in water at 3-5 pi○ for 10 minutes, flow rate of ultrafurnace filtrate: 0. &you/min/earth, Furnace filtration characteristics: The membrane completely passes through dextran with a molecular weight of 10,000. A membrane that can be treated in water for 10 minutes at 40y-60qo. Flow rate of ultra-furnace liquid: 0.09 g/min・Mass furnace filtration characteristics: Membrane is 6
Blocks dextrin (molecular weight 10,000) with an opacity of 7%. A membrane that can be treated in water at 6-85°C for 10 minutes. Ultrafiltration flow rate: 0.0017 lumps/min. Furnace properties: Membrane shut off raffi plates (molecular weight 594) with 2% opacity. Flow rate of membrane ultrafurnace liquid that can be treated with water for 10 minutes at 1990:
0.0013 lumps/min/flour under 3 bar) Furnace properties: The membrane rejects sodium chloride with an opacity of 19%. The experiments described above demonstrate that simple treatment in water can alter the filtration properties of membranes. Example 31 Solution A with a viscosity of 41.5 poise at 25°C
3, sulfonated polyarylether/sulfone 9
Prepared from DMF and 16 blocks of DMF. A sulfonated polyarylether/sulfone with an ion exchange capacity of 830 meq/k9 was prepared according to the technique described in Example 1 of French Patent No. 204,095. A solution with a viscosity of 130.5 poise at 25 DEG C. is prepared from 5.08 poise of a phenoxy resin containing quaternary ammonium groups and 90% of DMF. A modified phenoxy resin with an ion exchange capacity of 1470 meq/k9 was treated with a phenoxy resin initially treated with epichlorohydrin and trimethylamine according to the technique described in Example 1 of French Patent Application No. 70 No. 22,514. Manufactured by reaction. Mix solutions A3 and B3 to obtain 169.5 poise solution B3. 2. Cast a portion of this solution (A3&) onto a glass plate (layer 300 μm thick) and then submerge the plate in water at 26o. The membrane that peels off from the support after 3 minutes is examined for thrombogenicity according to the technique of Example 1, 4. Blood clotting occurs only after 35 minutes. 3. Another portion of solution A3& is cast onto a glass plate (layer 150 μm thick) and the plate is then placed in the open at 60° for 2 hours. A transparent film with a thickness of 70 μm is prepared, and its mechanical properties are as follows: Tensile strength: 600k9/Elongation at break: 85% (50 rib length and 6.5 rib width test Example 4 (Measurements carried out in pieces) Example 4 1 A solution with a viscosity of 10 poise at 25° C. was prepared from the sulfonated polyarylethernosulfone used in the previous example (830 meq/k9) and 32% DMF. do. A solution with a viscosity of 60 poise at 25 °C and 5.262 °C and 21 °C of the acrylonitrile/quaternized 3-vinyl-6-methyl-pyridine copolymer used in Example 1 was prepared.
Manufactured from MF. The two solutions are mixed and a high viscosity Nagisa solution B4 is obtained. 2. Dilute solution A4& by adding DMF and cast the solution onto a glass plate (layer thickness 300 μm). 2 boards? immersed in water. After 5 minutes, the membrane separates from the support. The 200r thick film is white and has a shiny surface and a matte surface. 3. During the ultrafurnace, under a pressure of 2 bars, this membrane has a flow rate of the ultrafurnace liquid of 1 g/min and blocks 100% of IJZ sozum, egg albumin and bovine alpmen. 4 When this membrane is kept in contact with blood as described in Example 1, coagulation of the blood occurs only after 98 minutes. Example 5 21
A solution having a viscosity of 250 and 61 poise is prepared from 14 blocks of the acrylonitrile/sodium methallyl-sulfonate copolymer of Example 1 and 86 blocks of DM circles. 2
? A viscosity B5 of 22 poise is prepared from 9.16 poise of the acrylonitrile/quaternized 3-vinyl-6-methyl-pyridine copolymer used in Example 1 and 56 poise of DMF. Mixing the two solutions introduces ionic crosslinking between the two copolymers and increases the viscosity of the mixture to 335 poise. 2. The resulting solution is cast onto a glass plate (layer 300 r thick) and then immersed in water at 250 ml. The film obtained after 3 minutes, 200 m thick, has a matte surface and a raised surface. The membrane is soaked in water at 50° for 10 minutes. During the thermofurnace, this membrane inhibits 100% of bovine alpine meso, ovalbumin and lithosm and exhibits a flow rate of the thermofurnace fluid of 1 block/min·block (2 bar pressure). Example 6 1 2? Example 1 Solution A6 with a viscosity of 366 poise
A copolymer of 17 and 83 mm (into solution) is prepared from DMF. Solution B6, having a viscosity of 195 poise at 250 poise, is prepared from 17 poise of the copolymer of Example 1 (solution B,) and 83 poise DM. Mixing the two solutions creates ionic bridges between the polymers and increases the viscosity of solution A6& to 1700 poise. The viscosity is brought to 671 poise by adding lithium chloride in 9 of 2411. A 200 mm thick membrane is prepared by coagulation in water at 250 mm as described above. During the ultrafurnace, under a pressure of 2 bar, this membrane stops the lithosm, egg albumin and bovine alpine to 100% and exhibits a flow rate of the ultrafurnace liquid of 0.8/min. 3 Solution A-6 was cast into a mold (after reducing the viscosity to 671 poise) and then left in an oven at 600°C for 2 hours to remove the solvent.The resulting 100A thick film was transparent. and uniform. This film has the following mechanical properties: In dry form: Tensile strength: 676 k9/elongation at break: 17% In wet form: (after 2 hours in water at 250 °C) Tensile strength:
362 k9 / elongation at break: 6% Example 7 Solution A7 with a viscosity of 87 poise at 1 25 °C was mixed with 17 poise of the copolymer of Example 1 (solution A,) and 83 poise of DMF.
Manufactured from the ground. Solution B7 with a viscosity of 2.5 poise at 250° C.
Manufactured from lumps. This polyester-polyurethane with an ion exchange capacity of 2.234 meq/k9 is disclosed in French Patent Application No. 70.
It is obtained by quaternizing a polymer called Polymer A in No. 18568 with methyl sulfate. Mixing B into the solution yields a solution of the ionically crosslinked polymer, the viscosity of which is 110 poise. 2 Spread this solution on a glass plate (300 mm thick).
Casting and then partially drying (2 hrs. under nitrogen flow)
? 5 minutes). Immerse the board in water (2000). The membrane separates after 5 minutes. This 150 mm thick film has a shiny side and a matte side. In an ultrafurnace under a pressure of 2 bar, this membrane has 100% inhibition of bovine alpmen and has a flow rate of 0.44 kg/min. 3. Pour solution A7B onto a glass plate and wait 2 hours for 60 hours.
The 60 mm thick film obtained by processing in an oven at
Tensile strength: 455k9/Elongation at break: 33% In wet form: (after immersion in water at 25o): Tensile strength: 117k9/Elongation at break: 19.5% Examples 8-14 Introduction ( Q) an acrylonitrile nonodium metharyl sulfonate copolymer with a specific viscosity of 0.862 and an ion exchanger of 4 meq/k9; and secondly, (8)
A series of experiments were carried out using an acrylonitrile/3-vinyl-6-methyl-pyridine copolymer that was quaternized with methyl sulfate (specific viscosity: 1.6, ion exchanger: **540 meq/k9). A 14% solution in a mixture of DMF/water (95-5% by weight) is prepared with the copolymer. Membranes are prepared from mixtures of the solutions (in different proportions) according to the recipe described in Example 1 (paragraph 2). The water temperature is 25
℃ and the peeling time is about 1 minute and 3 minutes. In the table below, the proportion of copolymers in a mixture of two copolymers, the excess cation obtained, the flow rate of water (equal/min.) through the membrane under 2 bar at 2 and the lithosm solution ( Nac
] in a 0.1M aqueous solution (concentration 1 ta') is shown below. (1) -250〃thick film (2) -100〃thick film (3) -270〃thick film (4) -150〃thick film (5) -80〃thick film Examples 15-191
In Example 3, a membrane is prepared by coagulation according to the technique of Tonami Hagi. The starting polymer used in this example was Solution A.
The proportions of 3 and B are such that there is an excess of positive (10) or negative (-) charge (expressed in milliequivalents of dry film/unit). This membrane has a shiny (delicate) side and a matte (porous) side. 2 Membranes prepared according to Example 3 (paragraph 2) were continuously treated with water (250°C for 2 hours),
Aqueous HCI solution (0.0 states) (2 hours at 250 °C),
Deionized distilled water, sodium hydroxide solution (0.0 arc)
, and again with distilled water, and the membrane is finally washed with physiological fluid (5 days at 37o). The physiological fluid used has the following composition: Sodium chloride 5.845 Potassium chloride 0.224 Magnesium chloride (Mother's day 20) 0.152 Sodium acetate ($LO) 5.171 Calcium chloride (Mother's day 20) 20) 0.33〃3 Perform a blood hydration test with this membrane. The test is carried out under the following conditions: the membranes are stacked in the shape of a cornet, with the dense side on the inside (a cone with a base diameter of 7 and a height of 6 skins) and immersed in a water bath kept thermostatically at 37 °C. Place it in a glass cone that can be used as a book. Thirty minutes before performing the test, fill the cornet with a solution of physiological fluid. When performing the test, drain the physiological fluid and inject 0.5 liters of freshly drawn human blood into the cornet from a denuded vein with a polystyrene syringe equipped with a vertical aqueous needle. Shake the glass cone every 3 parts of sand. Determine the elapsed time between the moment when the blood comes into contact with the material of the cornet and the moment when the blood remains attached to the base of the cornet when the cone is turned upside down. To facilitate comparison, a control test is performed on each blood sample, in which the blood is placed directly into a glass cornet. Four experiments (14 control experiments) are carried out on each membrane and the average difference in clotting times (Δt) for the membranes to be tested and measured with a glass cone is determined. The following results were obtained: Examples 20 to 25 Acrylonitrile/sodium metallyl sulfonate copolymer with an ion exchange capacity of 1100 meq/k9 and quaternary with methyl sulfate having an ion exchange capacity of 1100 meq/k9 Acrylonitrile/3-vinyl-6
-Methyl-pyridine copolymer is used. In both cases, the solvent is DMF and the proportion of each copolymer solution has an excess of positive or negative charge (milliequivalents of dry film/
The ratio is such that there are The membrane is prepared according to Example 1, paragraph 2, by coagulation.
The membranes of Examples 15-19 were used in Examples 15-19, except that the washing with sodium hydroxide solution was replaced with washing with NaCI.
Process in the same manner as in paragraph 2). The tables below are: membrane excess anionic or cationic, staining affinity (0 indicates no dye attachment, 10 indicates attachment), and blood compatibility test (Examples 15-1).
9) is shown. The acid dye is Alizarin Blue (600 c/d) of water. The basic dye is Astrazone Blue (9/600 of water). Examples 26-34 The polymers of Examples 20-25 are used. The relative proportions of each polymer in solution are such that an excess of ions is present. The membrane is prepared by casting the mixture of the solution onto a glass ramp and then drying for 600 hours for one hour under a vacuum of 40 degrees Hg. After drying, the membrane was heated to 370°C for one week.
and place it in water. The sample temperature is 60o or 100o for 8 minutes or 1500o.
Heat treated in distilled water for 1 minute. The membrane is washed with physiological fluid (5 days at 37). The results obtained are shown in the table below. Examples 35-37 These examples illustrate the preparation of bell polyelectrolytes using other neutral polar solvents. Example 35 Dimethyl sulfoxide (DMSO) as a neutral polar solvent
) was used. A 16% DMSO solution of a copolymer of acrylonitrile and methallylsulfonate sodium salt having an ion exchange capacity of 0 meq/k9 was prepared by quaternizing acrylonitrile and 3-vinyl-6 to an ion exchange capacity of 570 meq/k9. -14% DM of copolymer with methylpyridine
Mixed with SQ solution. A white, uniformly shaped key polyelectrolyte film was easily obtained from this DMS○ solution. The flow rate of distilled water through this membrane at 20° C. and under a differential pressure of 2 bar was 1.8 min/min. This membrane has a molecular weight of approximately 150
100% inhibition of lysozyme with 00. Example
36 A rust polyelectrolyte was prepared from a sulfonated polysulfone having an ion exchange capacity of 830 meq/k9 and a polyester polyurethane quaternized with dimethyl sulfate having an ion exchange capacity of 830 meq/k9. The polyester polyurethane is the same as that used in Example 7, and the sulfonated polysulfone is the same as that used in Example 3. A 20% solution of each polymer in dimethylformamide was prepared and the two solutions were mixed. Membranes were prepared from the final solution. When this membrane was placed on a glass slope, it turned white and the flow rate of distilled water at 20°C and 2 bar differential pressure was 0.025'/min/ground. Example 3
Poly(paradimethylaminostyrene) quaternized with acrylonitrile nomethallylsulfonic acid sodium salt copolymer having an ion exchange capacity of 7570 meq/kg and dimethyl sulfate having an ion exchange capacity of 570 meq/k9. ) and produced a neutral polyelectrolyte.

Claims (1)

[Scope of Claims] 1 (A) selected from acrylonitrile/methallyl sulfonic acid sodium salt copolymer and sulfonated polyarylether/sulfone, and which have the general formula ▲ mathematical formula,
There are chemical formulas, tables, etc.
is a value sufficient to show that the polymer is soluble in water and organic solvents), and (B) acrylonitrile/quaternary
selected from graded 3-vinyl-6-methyl-pyridine copolymers, quaternized poly(P-dimethylaminostyrene), phenoxy resins containing quaternary ammonium groups and polyester-quaternized polyurethanes; Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (■ in the formula represents a macromolecular chain bonded to the N(+) group via a covalent bond, and the size of the molecular chain and the value of m are based on the polymer. is a value sufficient to indicate water insolubility and organic solvent solubility, and the n/m ratio is from 0.1 to 10). , there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ that are characterized by separating the produced polymer of the following formula (I) ▼ (However, the meanings of the symbols n and m in the formula are as above. , and the n/m ratio is 0.1 to 10),
A method for producing ionically crosslinked polymers soluble in liquid organic media in the absence of ionically shielding solvents.