JPS5815495B2 - Polyion Complex Seihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel polyion complex (hereinafter referred to as PIC) produced by reacting a polycationic polymer having an unsaturated group in its side chain with any polyanionic polymer.

Conventionally, a combination of sodium polystyrene sulfonate and polybenzyltrimethylammonium chloride [Encyclopedia of Chemical Technology Vol. 6,
2nd Edition, pp. 117-132, 1968], there are many reports on PIC, such as a report on PIC between an anionic partially substituted product of polyvinyl alcohol and a polyvinylpyridinium salt.

However, the PIC obtained by these methods has the disadvantage that it is not durable in terms of strength.

As a result of intensive research on this point, the present invention was able to solve this problem by using a polycationic polymer having a terminal unsaturated group.

Since the PIC produced according to the production method of the present invention has terminal unsaturated groups, it is more difficult to crosslink by light or heat treatment when producing dialysis membranes or ultrafiltration membranes than conventional PIC. cross-linking density, thereby allowing the cross-linking density to be increased.

This is because it has a terminal unsaturated group and does not require complicated methods such as chemical treatment.

The PIC of the present invention has many uses such as dialysis membranes, ultrafiltration membranes, electrically conductive coatings, antistatic coatings, or medical materials.

When used for surface coating of medical materials or various materials, other vinyl monomers can also be bonded to it, which is significantly different from conventional PIC.

As polyanionic polymers used in the present invention; alkali metal salts such as polystyrene sulfonic acid or sodium polystyrene sulfonate; alkali metal salts such as polyvinyl sulfonic acid or sodium polyvinyl sulfonate; polyacrylic acid, polymethacrylic acid, carboxymethyl cellulose, Common polyanions such as alginic acid or their alkali metal salts can be used.

The polycationic polymer containing a terminal unsaturated group in the present invention includes a repeating unit represented by the following general formula.

and/or [However, R1 is an unsaturated group shown below, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p is -CH
a group selected from 2-0-, q is O or 1, a group, r is 0
or an integer of 1 to 3) R2: a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R3 and R4; R3 and R4 may be different and are an alkyl group having 1 to 4 carbon atoms.

M: Vinyl compounds such as styrene or substituted styrene such as α-methylstyrene, substituted acrylonitrile such as acrylonitrile or methacrylonitrile, and there is no restriction as long as the polymer obtained from them is an electrolyte polymer.

X: A halogen atom or a hydroxyl group.

X: Any number including 0.

n: Any number of 10 or more.

] When the polyanionic polymer used is sodium polystyrene sulfonate, the present invention produces PIC with an equivalent ratio of approximately 1:1 since it is a strong electrolyte-strong electrolyte combination.

On the other hand, when the polyanionic polymer used is polyacrylic acid, the degree of dissociation of the carboxylic acid can be adjusted in various ways by adjusting the amount of aqueous alkaline solution added, so PIC with various ratios of polyanion and polycation can be produced. can.

Although the PIC obtained by the conventional method is easier to mold and form a film than the PIC produced from strong electrolyte-strong electrolyte, there are still problems in terms of strength.

However, since the PIC produced according to the present invention has a terminal unsaturated group, this problem can be solved by a crosslinking reaction during or after molding and film formation.

The production of the PIC of the present invention is simple and requires only mixing solutions of polyanionic and polycationic polymers.

That is, a polyanionic polymer and a polycationic polymer are separately dissolved in water or a water-miscible organic solvent such as methanol, ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide to form a homogeneous solution. After obtaining, the two solutions can be mixed.

The object of the present invention can also be achieved by adding solid substances into the solution of one.

However, this method is not very preferable because the composition of the resulting PIC becomes non-uniform, lacks reproducibility, and requires time for purification.

When the polyanionic polymer used is a polycarboxylic acid, an alkaline aqueous solution can be added as necessary.

The alkaline aqueous solution used in this case is one in which a hydroxide of an alkali metal such as sodium or potassium, or a hydroxide of an alkaline earth metal such as calcium is dissolved in water.

The solution concentration of the polycationic polymer and polyanionic polymer can be suitably adjusted within the range of 0.01 to 60% by weight, but is preferably in the range of 0.1 to 30% by weight.

The equivalent ratio of polycation to polyanion is preferably in the range of 0.05 to 2o.

The reaction temperature is preferably 0°C to 80°C.

The present invention will be explained in more detail below with reference to Examples, but it is not limited to these Examples.

Example 1 3 g of a polycationic polymer containing an unsaturated group represented by the following formula (% formula %) (molecular weight 1X105, degree of quaternization 53) was placed in a beaker of 21, 800 ml of distilled water was added thereto, and the mixture was stirred. A homogeneous solution was prepared by dissolving.

In another 500 ml beaker, 1.5 g of sodium polystyrene sulfonate (molecular weight 2.2×10 6 ) was added, and 400 ml of distilled water was added thereto, and the mixture was stirred and dissolved to prepare a uniform solution.

Next, at room temperature, the prepared polyanionic polymer solution was gradually added dropwise under stirring to form a white precipitate.

After the dropwise addition was completed, stirring was continued for about 1 hour, and then the white precipitate formed was separated in a furnace, thoroughly washed with distilled water, further washed with methanol, and dried under vacuum.

The infrared absorption spectrum of the product shows an absorption based on ester group at 1720 cm-1, and an absorption based on ester group at 1180 cm-1,10
Absorption based on SO2 groups was observed at 35 cm-1.

This confirmed that the obtained product was the desired PIC.

Further, as a result of elemental analysis of nitrogen, the nitrogen content was 514%, which confirmed that the PIC was almost neutral.

Examples 2-5 polycationic polymer (poly-4-vinylpyridine molecular weight 1X105) and polyanionic polymer o,
PIC was obtained by separately preparing, reacting, and treating the s% aqueous solution in the same manner as in Example 1.

The results are shown in the table. Example 6 Take 39 pieces of -(CH2-CH)- polycationic polymer shown below (molecular weight 2.7 x 104, degree of quaternization 83%) in a 21 beaker, and stir and dissolve in 700 ml of distilled water to homogenize. A solution was prepared.

On the other hand, 1.8 g of sodium polyvinylsulfonate (molecular weight: 8 x 1O3) was placed in another beaker and dissolved with stirring in 500 ml of distilled water to prepare a homogeneous solution.

A solution of sodium polyvinylsulfonate was gradually added dropwise into the stirring polycationic polymer solution.

A white precipitate was formed simultaneously with the dropping. After the addition was completed, stirring was continued for another 1 hour, and then the product was separated in a furnace, thoroughly washed with water, further washed with methanol, and dried under vacuum.

The infrared absorption spectrum of the product is 885 cm-1,83
On the other hand, the absorption of benzene ring substituted at 2Cm-1 is 1180
Absorption of SO2 group was observed at cm-1°1031032C.

It was confirmed that the resulting product had the structure of PIC.

Moreover, this PIC was neutral.

Yield was 3.2g. Example 7 122 g of the polycationic polymer used in Example 2 was
Dissolved in 200ml of distilled water.

On the other hand, polyacrylic acid (molecular weight 4.l1X105) 2
5 was dissolved in 11 distilled water.

The polyacrylic acid solution was added dropwise to the polycation solution while stirring.

This was separated into furnaces and treated in the same manner as in Example 1.

The obtained product was PIC in which the 18th group of carboxylic acid was involved in the binding.

Yield was 13g. Example 8 The reaction and treatment were carried out in the same manner as in Example 7 except that 0.15 g of sodium hydroxide was added to the polyacrylic acid solution. About 55% of the carboxylic acids are involved in binding.
It was C.

The yield was 11.0g.

Note that by changing the amount of alkali added to the polyacrylic acid solution, PICs with different ratios of polycation and polyanion can be obtained.

Claims (1)

[Claims] 1 As a polycationic polymer, the general formula % formula % [However, R1 is an unsaturated group CH2-C-(CH2)-p-(Y)-q-(Q)-r
-(However, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a group selected from -CH2-0-, q is O or 1
, r is O or an integer of 1 to 3), R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3 and R4 may be different, an alkyl group having 1 to 4 carbon atoms, X is a halogen an atom or a hydroxyl group, n is an arbitrary number of 10 or more, X is an arbitrary number including O, and M is a vinyl monomer. ] and any polyanionic polymer.