JPH0246045B2 - HORIIONKONPURETSUKUSUNOSEIZOHOHO - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyion complex (hereinafter referred to as P.
It is written as IC. ).

There are many reports on conventional PIC.
For example, (1) P. of polystyrene sulfonate and polyvinylbenzyltrimethylammonium chloride.
IC [Industrial and Engineering Chemistry Vol. 57, No. 10, Page 32] [Ind.Eng.Chem., Vol. 57, No. 10, 32,
(1965)].

(2) Polyglutamic acid and polylysine PIC Japan Chemical Journal Vol. 82, No. 5, page 597 (Showa 36
Year).

(3) PIC of anionic partially substituted product of polyvinyl alcohol and polyvinylpyridine salt (JP-A-46
−21221).

(4) PIC containing polysaccharide derivatives (Unexamined Japanese Patent Publication No. 1973-
No. 59181).

(5) A method for producing a polymer electrolyte composite derived from polyvinyl alcohol, its coating, and fibers (Japanese Patent Application Laid-Open No. 48-66004).

As described above, most of the combinations used in conventional PIC production have been organic-organic.

Generally, organic polymers are more flexible and elastic than inorganic polymers, and have considerable strength, but they have many problems in terms of stability such as heat resistance. On the other hand, inorganic materials have excellent properties in terms of stability such as heat resistance, but on the other hand, they have drawbacks such as being easily friable and having relatively low strength. In order to take advantage of the advantages of both and compensate for their disadvantages, methods are being used to introduce inorganic substances into organic polymers.

Traditionally, by introducing inorganic substances using these methods,
Although it is known that reinforcing effects such as tensile strength and reduction of elongation at break can be increased to some extent, they cannot essentially compensate for the shortcomings of each material, and many problems still remain.

The present inventors conducted intensive research on a method for introducing inorganic substances into a specific polyanionic polymer as an organic polymer in a macroscopically uniform form. PIC obtained by reacting with
found that it compensated for the above drawbacks,
This invention has been achieved.

PIC manufactured by the present invention can be used as a dialysis membrane, an ultrafiltration membrane, an industrial filler, an electrically conductive or antistatic coating material, a paper sizing agent or an antacid, an antiperspirant, a peptic ulcer treatment agent, etc. It is useful for a wide range of applications such as medical polymers.

The present invention provides a water-soluble polyanionic polymer represented by the general formula () or a water-soluble salt thereof; However, R ₁ is hydrogen or a methyl group, R ₂ is hydrogen, an alkyl group, or a halogen, Y is hydrogen, an alkali metal, an alkaline earth metal,
ammonium or amino alcohol, M is a vinyl monomer, n is any number up to 5 including 0, m is a number of 10 or more, react with basic aluminum salts represented by the general formula () in the presence of a solvent The present invention relates to a method for producing a new PIC obtained by this method.

General formula () Al _2+o (OH) _3o Xy where n is a positive number of 0<n≦18, X is an anion such as Cl, NO ₃ or SO ₄ , and y is the above anion where X is monovalent. represents 6, and represents 3 when X is the above divalent anion.

M in the general formula () is a styrene substituted product such as styrene or α-methylstyrene,
These include substituted acrylonitriles such as acrylonitrile and methacronitrile, diene derivatives such as butadiene, acrylic esters, methacrylic esters, and vinyl monomers such as vinyl alcohol. Further, the basic aluminum salts used in the present invention are, for example, an aqueous solution of an alkali hydroxide, an alkali carbonate, etc. or aqueous ammonia in an amount equivalent to or less of an aqueous solution of an aluminum salt such as aluminum chloride, aluminum bromide, aluminum nitrate, or aluminum sulfate. or by reacting an equivalent or more amount of aluminum hydroxide with an acid, or by reacting an equivalent or more of metallic aluminum with an acid.

In carrying out the present invention, a specific polyanionic polymer of the present invention may be present in the production of the above-mentioned basic aluminum salts.

Examples of solvents that can be used include water and organic solvents that are miscible with water, such as methanol, ethanol, acetone, and NN dimethylformamide. Note that the purpose can also be achieved by using a mixed system of two or more of these solvents.

In the production of PIC of the present invention, the pH of the reaction system must be 3 to 6. This is because the yield of PIC decreases in a pH range other than the above.
The selection of the concentration is also important, and special care must be taken because as the concentration of the polyanionic polymer in the PIC production of the present invention increases, the viscosity increases and the reaction with the aluminum compound becomes non-uniform.

In the practice of this invention, the concentration of the particular polyanionic polymer of the invention is from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight. On the other hand, the concentration of the aluminum compound can range from 0.01 to 80% by weight.

The reaction may be carried out by mixing a solution of an aluminum compound and a solution of a polyanionic polymer. Although the purpose of the present invention can be achieved by adding the former to the latter or vice versa, a method of adding the aluminum compound to the polymer is preferred. The temperature for mixing both liquids is 0°C to 90°C.
This can be done within the range of Preferably, the temperature is room temperature to 50°C.

The PIC obtained in the present invention was in the form of white powder or granules.

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

Example 1 Polyanionic polymer with an average molecular weight of 430,000 represented by the following formula 4.6g was dissolved in 1 part water to obtain a homogeneous solution.

After dissolving 3.3 g of AlCl ₃ in 100 ml of water, N-
67.5 ml of NaOH was gradually added to obtain a clear aqueous solution of basic aluminum chloride.

While stirring the polyanionic polymer aqueous solution, this basic aluminum chloride aqueous solution was added, and the pH of the solution was adjusted to 3.9 with N-NaOH.
After continuing stirring at room temperature for about 1 hour, white PIC was produced. After standing overnight, it was filtered through a glass filter, washed with water, and vacuum dried at 40°C.

7.3 g of white, granular P.I.C was obtained.

The S content of PIC was 9.7% and the Al content was 12.7%.

Example 2 5.2 g of a polyanionic polymer represented by the following formula and having an average molecular weight of 760,000 was dissolved in 1 part of water.

After dissolving 3.2 g of AlCl ₃ in 100 ml of water, N-
A basic aqueous aluminum chloride solution was obtained by gradually adding 66.5 ml of an aqueous NH ₄ OH solution.

After adding to the above polymer aqueous solution, N-HCl and N
-NaOH was used to adjust the pH to 3.8. After stirring for about 3 hours, white PIC was produced. After leaving it for one night,
It was filtered through a glass filter, washed with water, and dried under vacuum at 40°C. The yield of white PIC was 6.8 g.

The S content of PIC was 8.8% and the Al content was 12.1%.

Example 3 5.1 g of a polyanionic polymer represented by the following formula and having an average molecular weight of 380,000 was dissolved in 1 part of water.

Further 6.0 g of AlCl ₃ .6H ₂ O was added and predissolved. 65 ml of N-NaOH was added with stirring. The pH of the aqueous solution was 4.4. After stirring for 3 hours,
The PIC was left to stand for a day and night, filtered through a glass filter, washed with water and acetone, and dried under vacuum at 40°C. 6.9 g of white PIC was obtained. The S content of PIC is
9.8%, and the Al content was 12.6%.

Comparative Example 1 In Example 1, a mixture of a polyanionic polymer aqueous solution and a basic aluminum chloride aqueous solution was
The pH was adjusted to 8.5 using N-NaOH. After stirring for 5 hours, the mixture was allowed to stand for one day and night, but no PIC was obtained.

Comparative Example 2 In Example 1, a mixture of a polyanionic polymer aqueous solution and a basic aluminum chloride aqueous solution was
The pH was adjusted to 2.2 using N-HCl. After stirring for 5 hours,
Although it was left undisturbed for one day and night, PIC could not be obtained.

Claims (1)

[Scope of Claims] 1. A novel polyion complex characterized by reacting a water-soluble polyanionic polymer represented by the following general formula or a water-soluble salt thereof with a basic aluminum salt at pH 3 to 6 in the presence of a solvent. Production method. However, R ₁ is hydrogen or a methyl group, R ₂ is hydrogen, an alkyl group, or a halogen, Y is hydrogen, an alkali metal, an alkaline earth metal,
Amino alcohol or ammonium, M is a vinyl monomer, n is any number up to 5 including 0, m is a number 10 or more 2 The basic aluminum salt is represented by the following general formula: A method for producing the novel polyion complex according to item 1. Al _2+o (OH) _3o Xy where n is a positive number of 0<n≦18, X is an anion such as Cl, NO ₃ or SO ₄ , y is 6 if X is a monovalent anion above indicates 3 when is the above divalent anion. 3. A method for producing a novel polyion complex according to claim 1 or 2, using water or an organic solvent miscible with water as a solvent.