JPS582967B2 - Polyion Complex Seihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel polyion complex, or polyelectrolyte complex.

More specifically, the present invention provides a novel polyion complex by using a polymer having quaternary ammonium methylated hydroxystyrene units as a polycation and complexing it with an arbitrary polyanion. The complex has various uses and has various advantages over conventionally known polyion complexes.

The novel polyion complex of the present invention can be used as ion adsorption resin, coating agent, artificial biological tissue,
Possible applications include microporous sponges or filters, semiconductor devices, and temperature-sensitive devices.In particular, membranes made from this polyion complex can be used as ultrafiltration membranes and dialysis membranes in artificial kidneys, artificial lungs, contact lenses, etc. It is considered to be extremely effective for the separation and purification of medical polymer materials, enzymes, proteins, nucleic acids, etc., and for wastewater treatment in the food industry, etc.

The novel polyion complex of the present invention has the following superior properties compared to conventionally known styrenic polyion complexes.

That is, (1) in addition to the ionic bond between a strong cationic group, i.e., a quaternary ammonium group, and a strong anionic group, i.e., a sulfonic acid group, a sulfomethyl group, or a sulfuric acid group, there is a hydrogen bond due to a phenolic hydroxyl group, so water The permeability is a dog, and the membrane strength when molded into a membrane is a dog.

(2) Due to the structural characteristics of the phenol group in the polymer, it is possible to easily introduce up to two quaternary ammonium methyl groups as strong cationic groups per hydroxystyrene unit, which is different from the conventional styrene-based This is a marked difference compared to the case where only one at most could be introduced.

Similarly, when a polyhydroxystyrene polyanion is used as a polyanion, up to three sulfonic acid groups, sulfomethyl groups, or sulfuric ester groups as strong anion groups can be easily introduced.

As a result, since the ion density becomes uniform, the ionic bonding force becomes large, and a polyion complex membrane with excellent water permeability and high membrane strength when formed into a membrane can be obtained.

(3) Polyhydroxystyrene, which forms the skeleton of the polycation used in the present invention, can be easily produced by a known method, and can have a molecular weight ranging from several hundreds to several million by appropriately selecting polymerization conditions. Polymers can be prepared arbitrarily, and therefore polycations with arbitrarily controlled molecular weights can be produced.

Copolymers of hydroxystyrene and other vinyl monomers such as styrene, methyl methacrylate, maleic anhydride, etc. can also be used.

Hydroxystyrene units in these polymers or copolymers can be easily tertiary aminomethylated by Mannitz reaction using a secondary amine, and the type of amine used at this time also depends on the type of amine used. Further, it can be selected arbitrarily, and the degree of aminomethylation can be easily controlled by appropriately adjusting the reaction conditions.

Tertiary aminomethylated hydroxystyrene units can be easily quaternized by Menshutkin reaction, etc.
At this time, it is also possible to adjust the ratio of the quaternary ammonium group, which is a strong cationic group, and the tertiary amino group, which is a weak cationic group, by appropriately selecting conditions.

It is also possible to add other functional groups to the polycation; for example, if you want to introduce a carboxylic acid group, you can perform a Mannitz reaction on a copolymer of hydroxystyrene and maleic anhydride, acrylic acid, acrylate, etc. Alternatively, during the quaternization reaction, a reagent having a carboxylic acid group, such as a halogenated acetic acid, can be used and introduced simultaneously with the quaternization.

As described above, due to the characteristics of the polycation used in the present invention, a novel polyion complex can be provided by chemically designing and introducing factors such as ion density, ion spacing, ion strength, and ion type.

(4) In the present invention, when sulfonated polyhydroxystyrene derived from polyhydroxystyrene is used as the polyanion, the molecular weight of the polyhydroxystyrene forming the skeleton of this polyanion can be polymerized over a wide range from several hundreds to several million. It can be arbitrarily adjusted by appropriately selecting conditions.

Copolymers of hydroxystyrene and other vinyl monomers, such as styrene, methyl methacrylate, and maleic anhydride, can also be used as starting materials for polyanions, and the introduction of sulfonic acid groups, sulfomethyl groups, and sulfuric acid groups can also be used. By appropriately selecting conditions, the degree of introduction can be easily adjusted.

Furthermore, if a copolymer containing two monomers is a compound containing a carboxyl group or a compound that can be easily induced into a carboxyl group, it is possible to introduce a carboxyl group as a weak anion. The ion density, ion spacing, ion strength, type of ions, etc. of the polyanion can be chemically designed and introduced freely, and as a result, the properties of the novel polyion complex of the present invention can be freely controlled as desired. I can do it.

(5) Since it has a phenolic hydroxyl group, it can be crosslinked by heat treatment or formalin treatment, and its crosslinking density is high.

The novel polyion complex of the present invention is characterized by the use of a novel quaternary ammonium methylated hydroxystyrene polymer or copolymer derived from a hydroxystyrene polymer or copolymer in its polycation moiety, There are no particular restrictions on the polyanion used.

In fact, polyanions include hydroxystyrene polymers or copolymers with sulfonic acid groups, sulfomethyl groups, sulfate ester groups derived from hydroxystyrene polymers or copolymers, or other polymers with sulfonic acid groups. For example, polystyrene sulfonic acid, polyvinyltoluene sulfonic acid, polyvinyl sulfonic acid, or alkali metal salts, alkali metal salts, or ammonium salts of these acid type polyanions can be used.

Among these polyanions, preferred are polyanions derived from hydroxystyrene, styrene, or vinyltoluene polymers or copolymers, and more preferred are polyanions derived from hydroxystyrene or styrene polymers or copolymers. .

As mentioned above, the polyanion to be used can be freely selected, but the polycation used in the present invention is a quaternary ammonium methylated hydroxystyrene polymer or copolymer derived from a hydroxystyrene polymer or copolymer. The use of coalescence is an essential requirement.

Polycations and polyanions derived from hydroxystyrene polymers or copolymers, which are new substances used in the present invention, are shown below.

The polycation used in the method of the present invention is represented by the following general formula.

Here, the OH group is in the para or meta position with respect to the vinyl group of hydroxystyrene, which is the starting material when synthesizing the polycation used in the present invention, in other words, the OH group is the element forming the skeleton structure of the polycation. Styrene is parahydroxystyrene or metahydroxystyrene.

R1, R2, and R3 in the above formula are linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, cycloalkyl groups, alkenyl groups, substituted or unsubstituted benzyl groups, or a combination of them. R3 can also be -CH2C00H or H, and is a halide ion or an alkyl sulfate group,
p is a value of 0 to 2, n is 3 or 3 or more, CM is a vinyl monomer in a broad sense including maleic anhydride, and 1 is an arbitrary number including O.

A novel polyanion derived from a hydroxystyrene polymer or copolymer, which is a type of polyanion used in the method of the present invention, is represented by the following general formula.

Here, p is O~2, n is 3 or 3 or more,
M is selected from the group consisting of hydrogen, ammonium groups, alkali metals and alkali metals, and R is hydrogen or -S
O3-M+, where M is the same as above, CM is a vinyl monomer in a broad sense, l is any number including O, and m is 0
or 1.

In the above formula, 10R is at the para or meta position with respect to the vinyl group of hydroxystyrene, which is the starting material for this polyanion synthesis.

The method of producing these polycations and polyanions is outside the scope of the present invention, and they are described in Japanese Patent Application No. 1987-5.
No. 4184, Japanese Patent Application No. 47-108511 and Japanese Patent Application No. 47-108512.

The method for producing the novel polyion complex of the present invention is simple and can be achieved by bringing the aforementioned polycation and any polyanion, including the aforementioned hydroxystyrenic polyanion, into contact with each other in solution using an appropriate solvent. Ru.

That is, in general, a polycation and a polyanion are separately dissolved in a solvent, preferably water or a water-miscible organic solvent such as methanol, ethanol, acetone, THF, DMF, etc., alone or in a mixture, and when the two solutions are mixed, a macromolecule is formed. The novel polyion complexes of the present invention precipitate from the solution through ionic reaction of the cations and macroanions.

Alternatively, the polyion complex of the present invention can also be obtained by dissolving a polycation and a polyanion in a ternary solvent consisting of water, water, a miscible organic solvent, an acid, a base, or a salt, and then removing the solvent. I can do it.

Since the above-mentioned ternary solvent has the ability to dissolve polyion complexes, when this ternary solvent is used, a polyion complex solution is obtained and no precipitation of polyion complexes occurs.

This solution can be used as it is as a casting solution for producing molded products such as polyion complex membranes.

Examples of water-miscible organic solvents that are one component of the above three-component solvent include alcohols such as methanol and ethanol, phenols, cyclic ethers such as THF and dioxane,
Ketones such as acetone and cyclohexanone, acetonitrile, pyridine, N-methylpyrrolidone, morpholine,
One or more polar organic solvents containing nitrogen, sulfur, or phosphorus such as DMF, DMSO, HMPA, etc. are used, and other components such as acids, bases, and salts include hydrochloric acid, hydrobromic acid, sulfuric acid, and nitric acid. Alternatively, strong acids such as trichloroacetic acid, hydroxides of alkali metals or alkaline earth metals, bases such as aqueous ammonia, and halides, nitrates, sulfates, perchlorates, persulfates of alkali metals or alkali metals, etc. salt is used.

The concentration of polycation and polyanion dissolved in the solvent is 0.01 to 80% by weight, preferably 0.1 to 10% by weight.
, and the temperature at which they are brought into contact is 0 to 100°C, preferably room temperature to 60°C, and the equivalent ratio of polycation to polyanion is 0. The composition is in the range of 1 to 10, preferably 0.25 to 4.

However, if a solution obtained using a ternary solvent is to be used directly as a casting solution, it is better to increase the concentration of the solution, in which case it is 2 to 80% by weight, preferably 10 to 80% by weight. The concentration is 50% by weight.

To produce a polyion complex, as mentioned above, it is sufficient to bring a polycation and a polyanion into contact with each other in a solution using an appropriate solvent. The purpose can also be achieved by adding and dissolving a polycation or a mixed powder of a polycation and a polyanion in the above solvent, but in these methods, when using a one-component or two-component solvent, depending on the conditions. Although it is possible, it is not common because the reaction progresses unevenly and the composition becomes non-uniform.

A particularly preferred combination of the three-component solvent is water-acetone-sodium bromide solvent and water-dioxane and D
MSO is a hydrobromic acid solvent.

The polyion complex of the present invention can also be made into a molded product; for example, a polyion complex membrane can be manufactured as follows.

The polyion complex obtained by the above method is dissolved in the above-mentioned ternary solvent at a concentration of 2 to 80% by weight, preferably 10 to 50% by weight, and used as a casting solution.

Of course, when the above-mentioned three-component solvent is used in producing a polyion complex, the solution can be used as a casting solution as it is, or by simply adjusting the concentration as necessary.

In order to remove the gas contained in this solution, it is preferable to degas it under reduced pressure at room temperature for an appropriate period of time, preferably 20 to 30 seconds.

A glass plate, preferably whose surface has been treated with silane or paraffin, using the casting solution thus obtained;
It is cast onto a smooth plate such as, and the thickness is preferably adjusted using, for example, a geezer.

Alternatively, if necessary, it may be applied to a support such as a sintered polyolefin such as Tyvek.

Thereafter, the solvent is removed for 0 to 20 hours, preferably 2 hours.
~30 minutes at a temperature of 10°C to 100°C, preferably room temperature ~
Air dry at 60°C to make the upper surface of the membrane denser than the lower surface.

It is desirable for the upper layer to be denser than the lower layer for use as a permeable membrane.

Thereafter, the polyion complex was cast on a smooth plate or support at a temperature of -10°C to +100°C.
Preferably immersed in water (pH is 1 to 13) at 0 to 60°C or in a mixed solvent of water and a water-miscible organic solvent,
A novel polyion complex membrane can be manufactured by peeling it off from a smooth plate after a certain period of time.

In addition, when a support is used, this polyion complex membrane is obtained by being supported on the support.

The above polyion complex can be crosslinked by heating or formalin treatment, for example at room temperature to 1
Heat treatment at 00°C, preferably 50-80°C, for 5 minutes to 20 hours, preferably 1-10 hours, or using formalin at 0°C to 100°C, preferably room temperature to 60°C.
The polyion complex of the present invention can be crosslinked by formalin treatment at 1 to 20 hours at <RTIgt;C.

By performing the above-mentioned crosslinking treatment, it is possible to adjust the pore diameter of minute openings present in the polyion complex.

An acid or alkali can be used as a catalyst during the crosslinking treatment, but the use of a catalyst is not always necessary.

As mentioned above, it is essential for the novel polyion complex of the present invention to use a polycation derived from a hydroxystyrene polymer or a copolymer. It is distinctive in that it includes.

There are no particular limitations on the polyanion used.

Examples and reference examples of the present invention are shown below.

Example 1 In a 1 liter beaker, 0.5 g of trimethylammonium methylated poly-p-hydroxystyrene bromide (N/p
-Hydroxystyrene units = 1.60 pieces, Br/N = 1
．． 0, 0. (η) = 0.0 at 30°C in INNaBr
84), add 250 ml of water to it, and stir thoroughly to dissolve.

O. into another 500ml beaker. 5 g of polysodium p-styrene sulfonate (Redox polymer of sodium p-styrene sulfonate, 30% in 0.1N NaBr)
[η] = 0.438) at °C and add 250 ml to it.
Add water and stir thoroughly to dissolve.

Next, when the prepared aqueous polyanion solution (sodium poly-p-styrene sulfonate) is added dropwise to an aqueous polycation solution (trimethylammonium methylated poly-p-hydroxystyrene) under stirring, a white precipitate is formed (polycation and Polyanion equivalence ratio 0.9).

After stirring at room temperature for 1 hour, the resulting polyion complex precipitate was separated, thoroughly washed with water, replaced with acetone, and vacuum dried to obtain 0.16 g of a yellow-white powdery polyion complex. .

The elemental analysis values of this are N=3.81%, S=7.47%,
N/S=1.17 and the IR spectrum is δOH and νC
12o5cm- coupled with O or νS02
1, vasSO2=1180Cm-1, νssO2=1
033-1 and 1008Cm-1, vSO=670Cm-
1. It was confirmed that this was a polyion complex in which a polycation and a polyanion were ionically bonded because the polysubstituted benzene nucleus had absorptions near 875 cm and 830 cm out of the δOH plane.

This polyion complex is water-acetone-NaB
r = 51-18-31% by weight of a ternary solvent (referred to as solvent A) and water-1,4 dioxane and DMSO-concentrated hydrobromic acid water-10-10 and a ternary component in a weight ratio of 1 to 20. It dissolves well in any of the system solvents (referred to as solvent B).

Example 2 0.7 g of the polycation used in Example 1 and 35 g of the polyanion Q were reacted in the same manner as in Example 1 (weight ratio 1.8), resulting in 0.05 g of white powdery polyion. I got a complex.

The elemental analysis values of this are N=3.85%, S=6.23%,
N/S=1.41.

Furthermore, the structure of this was confirmed by IR spectrum.

This polyion complex is difficult to dissolve in the solvent A used in Example 1, but is well dissolved in the solvent B.

Example 3 0.35P of the polycation used in Example 1 and 0.7 g of the polyanion were reacted in the same manner as in Example 1 (equivalence ratio 0.46), resulting in 0.4 g of yellow-white powdery polyion. I got a complex.

The elemental analysis values of this are N=3.20%, S=8.59%,
N/S=0.85.

Furthermore, the structure of this was confirmed by IR spectrum.

This polyion complex dissolves well in both solvent A and solvent B used in Example 1.

Example 4 Trimethylammonium methylated poly p-hydroxystyrene bromide derived from poly p-hydroxystyrene having a molecular weight of 190,000 (N units/p hydroxystyrene unit = 1.60 units, Br/N = 1.0, 0. INNaBr
[η) = o. 0.35 g of s63) and 0.7 g of the polyanion used in Example 1 were reacted in the same manner as in Example 1. Same as Example 3 with a C equivalent ratio of 0.46]
As a result, 0.4 g of yellowish white powdery polyion complex was obtained.

The elemental analysis values of this are N=3.37%, S=8.90%,
Br-0.3% or less, N/S=0.86.

This polyion complex was dissolved in both solvent A and solvent B used in Example 1, and had the same structure as the polyion complex of Example 3.

Example 5 N-N dimethyl, N benzyl, ammonium methylated poly p-hydroxystyrene chloride (N/p-hydroxystyrene units 1.60, Cl/N=1
．． 0, 0. [η)=0.10 at 30°C in INNaBr
4) and 0.5 g of the polyanion used in Example 1.
5g was reacted in the same manner as in Example 1 (equivalent ratio 0.80
) A polyion complex in the form of a pale auburn powder of 0.41 was obtained.

The elemental analysis values of this are N = 2.68%, S - 7.49%,
N/S=0.82, and the IR spectrum is δOH and ν
1216Cm coupled with CO or νS02
-1, vasSO2=1180Cm-1, vssO2=
1038cm-1 and 1009Cm-1νSO2=670
Cm-1, δCH out-of-plane of substituted benzene nucleus = 885 cm-
1 and 830 cm-1, benzyl group δCH in-plane = 1083
The structure of a polyion complex was confirmed from the fact that it had an absorption at cm-1.

This is difficult to dissolve in solvent A used in Example 1, but solvent B
dissolves well in

Example 6 0.35 g of the polycation used in Example 5 and Example 1
When 0.7 g of the polyanion used in Example 1 was reacted in the same manner as in Example 1 (equivalence ratio 0.40), a 0.502P amber colored powdery polyion complex was obtained.

The elemental analysis values of this are N=2.97%, S=7.38%,
CI=O. It was 1% or less, N/S=0.92.

Furthermore, the structure of this was confirmed by IR spectrum.

This polyion complex dissolves in solvent A used in Example 1, and also dissolves well in solvent B.

Example 7 The polyanions in the polyion complexes used in Example 3 and Example 6 were the same, but the structures of the polycations were different.

That is, the former has a trimethylammonium group, whereas the latter has a dimethyl or benzylammonium group.

In this example, the solubility of the above two types of polyion complexes in water-acetone-NaBr-based solvents was investigated in detail, and solubility equilibrium curves were obtained.

This is shown in FIG. 1 in comparison with the solubility equilibrium curve of a styrene polyion complex.

From FIG. 1, it can be seen that since the methyl group is smaller as a hydrophobic group than the benzyl group, the ion density of the polyion complex becomes higher, and it can be dissolved even in a small amount of acetone, which is an organic solvent.

Furthermore, polyion complexes with 1.6 trimethylammonium methyl groups per p-hydroxystyrene unit have a wider dissolution range than conventional styrenic (up to 1.0 trimethylammonium methyl groups per styrene unit) polyion complexes. It was concluded that.

Example 8 0.51g of the polycation used in Example 1 was added to 25ml
A polycation aqueous solution is obtained by stirring and dissolving the polycation in water.

Poly p-hydroxystyrene (TH
Sulfonated poly p-hydroxystyrene ([η] = 0.06) obtained by reacting with concentrated sulfuric acid
A polyanion aqueous solution is obtained by dissolving 0.51 g of S=17.0%) in 25 ml of water with stirring.

These two aqueous solutions are mixed with stirring at room temperature, and the mixture is further stirred and reacted at room temperature for 1 hour to form a polyion complex as a black-brown precipitate.

When this was separated, 0.95 g of solid was recovered.

The elemental analysis values of this are N=3.54%, S=7.63%,
N/S=1.06, and the IR spectrum is δOH and ν
1220C by coupling of CO or νSO2
Absorption of m-1, νassO2 = 1170 cm-1, vs
SO2 = 1043Cm-1, νsO = 647Cm-1 and 614Cm-1, polysubstituted benzene nucleus δCH out-of-plane -883
The structure was confirmed because it had absorptions of Cm-1, 836 cm-1, and 811 cm-1.

This polyion complex does not dissolve in solvent A used in Example 1, but dissolves in solvent B.

It also dissolves well in a three-component solvent (referred to as solvent C) consisting of water, 1.4 dioxane, DMSO, concentrated hydrobromic acid, and 17-17 and 17-49% by weight of water.

Example 9 One gram of poly p-hydroxystyrene having a molecular weight of 60,000 was dissolved in 20 ml of concentrated sulfuric acid, sulfonated at 100°C for 2 hours, and the partially gelled material was removed with glass wool to obtain a deep red transparent solution.

This was diluted with 50 ml of water to obtain a polyanion aqueous solution.

A polycation aqueous solution was prepared by dissolving 0.56 g of the polycation used in Example 1 in 45 ml of water.

The polycation aqueous solution and the polyanion aqueous solution were stirred and reacted at room temperature for 30 minutes to obtain 0.1 g of an amber polyion complex.

The elemental analysis values of this are N=3.49%, S=9.10%,
N/S=0.88.

Further, the structure of this compound was confirmed by ①R spectrum.

This polyion complex is hardly soluble in Solvent A used in Example 1, slightly soluble in Solvent B, and well dissolved in Solvent C used in Example 8.

Example 10 Trimethylammonium methylated poly p-hydroxystyrene bromide derived from poly p-hydroxystyrene (molecular weight 150,000) (N/p-hydroxystyrene units = 1-80, Br/N = 1.0, 0.INNa
0.5 g of [η] = 0.580) at 30°C in Br as a polycation, sulfonated poly-p-hydroxystyrene (S pieces/p-hydroxy) derived from poly-p-hydroxystyrene (molecular weight 100,000) Styrene unit = 2.
60 pieces, 0. (η)=0.4 at 30°C in INNaBr
00) 1.0 was used as a polyanion and reacted with Example 1 in the same manner (equal weight ratio 1.16) to obtain 0.8 g of a white powdery polyion complex.

The elemental analysis values of this are N=3.86%, S=8.65%,
N/S=1.02.

Furthermore, the structure of this was confirmed by IR spectrum.

This polyion complex dissolves well in both solvents A and B used in Example 1 and solvent C used in Example 8.

Example 11 0.5 g of the polycation used in Example 10 and polyp
- Sulfonated poly p-hydroxystyrene derived from hydroxystyrene (molecular weight 150,000) (S/p-
Hydroxystyrene units = 1, 85 pieces, 0. INNaB
[η] at 30°C in r = 0. 421) was reacted in the same manner as in Example 1 using 1.0 g as a polyanion (equivalent ratio 1.
32) White powdery polyion complex 0.
I got 91.

The elemental analysis values of this are N=3.24%, S=7.05%,
N/S=LO5'.

Furthermore, the structure of this was confirmed by IR spectrum.

This polyion complex dissolves well in both solvents A and B used in Example 1 and solvent C used in Example 8.

Example 12 As a solvent for producing a polyion complex membrane, the solvent C used in Example 8 (water-1,4 dioxane and DMSO = concentrated hydrobromic acid water-17-17 and 17-49 weight%) was used. A ternary solvent) was used.

As a polycation, trimethylammonium methylated poly p-hydroxystyrene bromide (N/p
-1.55 units per hydroxystyrene unit, Br/N
=I. O, 0. (η) in INNaBr aqueous solution at 30°C
=o. 4o2) was used.

Redox polymer of sodium p-styrene sulfonate as a polyanion (0.IN in NaBr aqueous solution at 30°C)
[η]=0.623) was used.

In this example, 1 g of the above polycation was placed in a 10 ml beaker, and 1 ml of the above solvent C was added thereto and uniformly dissolved, resulting in a pale white, auburn, transparent viscous solution.

One gram of the above polyanion was placed in another 10 ml beaker, and 1 ml of the above solvent C and 1 ml of water were added thereto and uniformly dissolved to form a pale yellow transparent viscous solution.

At this time, the actual ratio of polycation to polyanion is 0.90
Met.

The polyanion solution and polycation solution were uniformly mixed and stirred for 5 minutes to obtain a polyion complex solution with a concentration of 31% by weight.

Bubbles in the solution were removed by reducing the pressure at room temperature for 20 to 30 seconds.

This casting solution was poured onto a 15 cm x 10 cm smooth glass plate, and the thickness was reduced to about 0 using a chromatography geezer.
．． It was set to 1mm.

After the solvent was evaporated at room temperature for 2 minutes, the sample was gently and slowly immersed in ice water at 0°C.

After about 30 seconds, it turned whitish, and after about 5 minutes, the polyion complex film began to peel off from the smooth glass plate.

One hour after the immersion, this polyion complex membrane was immersed in water at 25°C and left as it was for 1 hour.

The thus obtained white-yellow translucent film has a water content of 62.4%.
, membrane thickness 0.140mm, water permeability 0.027ml/mi
n-cm2 (under a pressure of 1 kg/cm2).

Example 13 A polyion complex membrane was obtained in the same manner as in Example 12, except that the casting solution concentration was changed from 31% to 20%.

This is a white, slightly transparent membrane with a water content of 74.7%, a membrane thickness of 0.29 mm, and a water permeability of 0.292 ml/min-c.
m2 (1 kg/cm2 under pressure).

Example 14 A polyion complex membrane was obtained in the same manner as in Example 12, except that the casting solution concentration was changed from 31% to 15%.

This is a white opaque film with a water content of 79.3% and a film thickness of 0.
．． 53mm, water permeability 0.768ml/min-cm2
(under a pressure of 1 kg/cm2).

Examples 15-18 Similar to Example 12, the casting solution concentration was 3.
Table 1 shows the properties of polyion complex membranes obtained when the charging equivalent ratio of polycation and polyanion was varied from 0.3 to 1.8.

The relationship between the water content and water permeability of the polyion complex membranes produced in Examples 12 to 18 is shown in FIG. 2 in comparison with the styrene-based polyion complex membranes.

From FIG. 2, it can be seen that the membrane made from the polyion complex of the present invention has higher water permeability than the conventional styrenic polyion complex membrane at the same water content.

This is because the polycation from p-hydroxystyrene is p
- High ionic density due to approximately 1.6 trimethylammonium methyl groups per hydroxystyrene unit (up to 1.0 per styrene unit in conventional styrenic polycations) and phenolic hydroxyl groups It is thought that the water permeability is increased by forming hydrogen bonds.

Example 19 In the same manner as in Example 12, a polycation with a trimethylammonium methyl group introduction rate of 0.87 per p-hydroxystyrene unit and [η] of 0.450 was used, and the equivalent weight of the polycation and polyanion was adjusted. A polyion complex was prepared with a ratio of 0.71 and formed into a film with a casting solution concentration of 21% to obtain a polyion complex film.

This is a thin white transparent film with a water content of 74.8% and a film thickness of 0.
．． 115mm, water permeability 0.030ml/min-cm
2 (under a pressure of 1 kg/cm2).

Examples 20-25 Trimethylammonium methylated poly p-hydroxystyrene bromide derived from poly p-hydroxystyrene (N/p-hydroxystyrene unit=1.
71 pieces, 0. [η)=(13
43) as a polycation, a Redox polymer of potassium p-styrenesulfonate (30°C in 0.1N NaBr)
(η) = 2.79) as a polyanion and an equivalent ratio of 1
．． 0, casting concentration 20-22% by weight, casting solvent composition (water - organic solvent - concentrated hydrobromic acid water - 20%
-30-50% by weight).

Table 2 shows the properties of the polyion complex membrane obtained when the organic solvent was changed.

Example 26 0.52 trimethylammonium methylated poly-m-
Hydroquinstyrene bromide (N pieces/m-hydroquinstyrene units -1.0, Br/N=1.0, 0.INNaB
[η)=o. at 30°C in r. o7s) and 0.51 sodium poly p-styrene sulfonate (0.INNaBr
A polyion complex was prepared in the same manner as in Example 1 using [η] = 0.438) at 30°C.

0.4 g of a white powdery polyion complex was obtained.

The elemental analysis values of this were N=3.30% and S=7.72%.

[Brief explanation of drawings]

FIG. 1 shows (1) a polyion complex containing trimethylammonium methylated poly p-hydroxystyrene bromide obtained in Example 3 as a polycation and sodium poly p-styrene sulfonate as a polyanion;
) A polyion complex containing dimethyl, benzylammonium methylated poly p-hydroxystyrene chloride obtained in Example 6 as a polycation and poly-p-styrene sodium sulfonate as a polyanion, and (3) a conventional product trimethylammonium methylated. This is a solubility equilibrium curve for a water-acetone-NaBr mixed solution of a polyion complex containing polystyrene chloride as a polycation and polysodium p-styrene sulfonate as a polyanion.The solubility of (1) is a solid line, the solubility of (2) is a dashed line, The solubility of (3) is shown by the dashed line. Figure 2 shows (1) a membrane made from a polyion complex in which trimethylammonium methylated poly p-hydroxystyrene bromide produced in Examples 12 to 19 is used as a polycation and sodium poly p-styrene sulfonate is used as a polyanion, and (2) Relationship between water content (%) and water permeability of polyion complex membranes for membranes made from conventional polyion complexes, in which trimethylammonium methylated polystyrene chloride is the polycation and sodium poly-p-styrene sulfonate is the polyanion. (1) is a solid line and (
2) is indicated by a dashed line.

Claims (1)

[Claims] 1 Water, a water-miscible organic solvent alone, a binary mixed solvent of water and one or more water-miscible organic solvents, and water, one or more water-miscible organic solvents; contacting a polycation of general formula I below with any polyanion in the presence of a solvent selected from the group consisting of miscible organic solvents and ternary mixed solvents with acids, bases or salts. General formula for the production of polyion complexes, where the OH groups are in para- and meta-positions relative to one group, and R1, R2, and R3 each have 1 to 20 carbon atoms.
is a linear or branched alkyl group, cycloalkyl group, alkenyl group, substituted or unsubstituted nitrogen-containing heterocyclic group, or dialkanolamine, and R3 is -C■2
It can be C00H or H, X- is a halogen ion or an alkyl sulfate group, p has a value of O~2, and n is 3
or 3 or more, CM is a vinyl monomer, and 1 is any number including O.