JPH02140235A - Modified polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a modified polymer which is suitable for a separation membrane such as a reverse osmosis membrane, because it is made hydrophilic without adverse effect on its heat resistance by allowing to react a hydrophobic aromatic polymer bearing halogen on its chain terminals with a vinyl group- containing compound in the presence of a polymerization initiator. CONSTITUTION:A hydrophobic aromatic homopolymer containing a recurring unit of formula I, or copolymer thereof with at least one selected from the recurring units of formula II through formula IV, both of which bears halogen atoms on its chain terminals is allowed to react with a vinyl group containing compound of formula V (R1 is H; R2 is formula VI) in the presence of a radical polymerization initiator so that the vinyl group-containing compound is included more than 10wt.% whereby the subject modified polymer is obtained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a modified polymer and a method for producing the same, and more particularly to a polysulfone resin modified with a vinyl polymer and a method for producing the same. be.

[Prior Art and Problems to be Solved by the Invention] Aromatic polysulfone is widely used as an engineering resin with excellent chemical and thermal durability. Many polyaryl ether sulfone polymers are known as aromatic polysulfones, and these resins generally have the formula (I)
It is characterized by a structure containing the repeating unit shown in As expected from this structure, aromatic polysulfone has excellent durability and stability, but exhibits hydrophobic properties. As a representative aromatic polysulfone, Victrex+Union Carbide (abbreviated as UCC) is manufactured by Imperial Chemical Industries (abbreviated as ICI).
Both are commercially available under the trade name Udel from the company, but the water absorption rate of the former is 0.4% and the latter is 0.3% (both ASTM D 570), and cellulose acetate, which is known as a hydrophilic resin. The water absorption rate is less than 1/10 of that of Due to this hydrophobic property, aromatic polysulfone
There were many problems such as ``the surface is difficult to wet with water (dry)'', ``easy to get dirty'', ``resistant to static electricity'', and ``difficult to adhere''.

In order to solve these problems, various methods have been proposed for providing aromatic polysulfone with improved hydrophilicity or for treating resin products to make them hydrophilic. The most common and simple method is to mix a hydrophilic substance such as glycerin or polyethylene glycol, a surfactant, or a hydrophilic polymer with an aromatic polysulfone polymer and incorporate it into the resin, or to coat it on the resin surface. be. For example, JP-A-56-155243 proposes a method for providing hydrophilized aromatic polysulfone using a compatible blend of aromatic polysulfone polymer and polyalkylene oxide. However, such water-soluble additives are eluted and removed when the resin comes into contact with water. Therefore, it can be said that this method is suitable for the purpose of producing a porous body of aromatic polysulfone by extracting and removing additives with water, but it is not suitable as a method for obtaining essentially hydrophilized aromatic polysulfone. Ta. Furthermore, the method of coating the resin surface had to be considered inappropriate for the same reason.

As a method of adding hydrophilic polymers that do not dissolve in water,
For example, JP-A-57-50507 proposes a resin that is a blend of an aromatic polysulfone polymer and a cellulose derivative. However, because aromatic polysulfone polymers have a large molecular cohesive force, it is extremely difficult to uniformly blend different types of polymers, and even with this proposal, it was necessary to add a considerable amount of polyvinylpyrrolidone, a water-soluble polymer, as a compatibilizer. Furthermore, since water-insoluble additives are thought to have a smaller hydrophilic effect than water-soluble additives, it has been necessary to add a large amount of a different polymer to obtain a substantially hydrophilized aromatic polysulfone. Addition of such a large amount of different polymers not only causes a decrease in the heat resistance and other substances of the resulting resin, but also makes it difficult to make a uniform blend, resulting in uneven hydrophilicity of the resin product. It was thought that this would cause cracks and a decrease in strength.

On the other hand, various methods have been proposed for providing hydrophilized aromatic polysulfone by introducing hydrophilic groups or hydrophilic polymers into the aromatic polysulfone polymer itself.

For example, JP 53-], 3679, JP 5919
No. 6322 etc. have a sulfonic acid group in the polymer main chain, JP-A-59-196321 has a sulfonamide group in the polymer main chain, and JP-A-57-174104 has a polyethyleneimine polymer in the polymer main chain. We have proposed a method for providing hydrophilized aromatic polysulfones by introduction or grafting.

All of these methods are modification means in which hydrophilic groups or hydrophilic polymers are randomly bonded by covalent bonds to the aromatic rings of the main chain of the aromatic polysulfone polymer. For this reason, physical properties such as heat resistance inevitably deteriorate when compared with unmodified aromatic polysulfone polymers. Furthermore, if the proportion of hydrophilic groups introduced into the polymer is high, the hydrophilicity of the polymer main chain increases, leading to significant changes in physical properties, such as modification to a polymer that is completely water-soluble. I had to say that it was a reforming method that involved.

Therefore, in order to essentially make the resin surface hydrophilic without impairing the physical properties of the aromatic polysulfone polymer, for example, JP-A-59-186604 proposes a method of subjecting a polysulfone membrane filter to positive column plasma treatment. There is. However, such a method is a special method that is characterized by modifying only the surface of a resin that is small and relatively simple in shape, such as a membrane filter, and has been molded, and is therefore not common.

[Means to solve the problem]

As a result of intensive research in view of the above, the present inventors have found that by using a polysulfone resin modified with a vinyl polymer, aromatic polysulfone can be made hydrophilic without reducing its heat resistance or mechanical strength. They discovered this and completed the present invention.

That is, the present invention is produced by reacting a hydrophobic aromatic polymer having a halogen end in the presence of a compound having a vinyl group and a radical polymerization initiator, and containing a polymer component of the compound having a vinyl group. A modified polymer characterized in that the amount thereof is 10% by weight or more, and a hydrophobic aromatic polymer having a halogen end are reacted in the presence of a compound having a vinyl group and a radical polymerization initiator. A method for producing an aromatic polymer is provided.

The hydrophobic aromatic polymer in the present invention is ΔSTM D5
The aromatic resin must have a water absorption rate of 5% or less when immersed in water according to No. 70, and must have a halogen group at the end. Such resins include polysulfone, polycarbonate, polyphenylene oxide, polyalkylene terephthalate, etc., but polysulfone resins are preferably used, especially when repeating units represented by the following formula (I) are used. A homopolymer having or a repeating unit represented by formula (I) with the following formula (n) ~
At least one repeating unit selected from (IV)
Copolymers having species repeating units are preferred.

H3 In the present invention, the hydrophobic aromatic polymer as described above is modified by radical reaction in the presence of a compound having a vinyl group and a radical polymerization initiator.

Since a compound having a vinyl group can undergo a radical polymerization reaction, it is necessary that its polymer or a chemically treated polymer exhibit hydrophilicity. Examples of such compounds include monomers represented by the following formula (V), but are not particularly limited thereto.

(Here, R1 is hydrogen or a methyl group. Also, R2 is (n is an integer from O (valence bond) to 10. ).

(R3 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms).

OOM (M is hydrogen, or an alkali metal or basic substance that ionically bonds with the carboxylic acid ion) 0OR4 (R, is an aliphatic hydrocarbon group having 1 to 20 carbon atoms).

C0NR5R6 (R5, R6 are each hydrogen or carbon atoms 1 to 20 (II
is an aliphatic hydrocarbon group having

9 R8 (R?, R8 and R7 are each an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen ion).

(R1° is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 4 to 6, and X (El is a halogen ion).

(R++ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and XO is a halogen ion). ) The above-mentioned vinyl group-containing compounds may be used alone or as a mixture of two or more. In the final modified polymer of the present invention, it is preferable that the polymer component of these vinyl group-containing compounds is contained in an amount of 10% by weight or more.

The radical polymerization initiator used in the present invention is not particularly limited as long as it is used in ordinary radical polymerization reactions, but examples include azo compounds such as abbisisobutyronitrile, benzoyl peroxide, Diacyl peroxides such as lauroyl oxide and acetyl peroxide, dialkyl peroxides such as diaryl peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, aryl hydroperoxides or diaryl peroxides such as cumene hydroperoxide and dicumyl peroxide, and other peracids. Esters, inorganic peroxides (H
20□.

LS20e, (NL)zs20a, etc.).

In the present invention, the amount of the radical polymerization initiator added is vinyl group-containing compound/initiator - 10/1 to 1000/1.
(weight ratio) is preferable.

In carrying out the radical reaction with the hydrophobic aromatic polymer in the presence of the compound having a vinyl group and a radical polymerization initiator, known methods such as bulk polymerization, emulsion polymerization, solution polymerization, suspension polymerization, etc. can be used. A vinyl polymerization method is used, and the reaction temperature is set depending on the type of radical polymerization initiator.

The modified polymer produced by such a method may be put to practical use as a reaction mixture as it is as a coating solution or the like, or it may be further purified by reprecipitation or the like to form a resin-like material, which may be molded and used. Further, if necessary, it may be further subjected to chemical treatment to make it hydrophilic. Such chemical treatment is appropriately selected depending on the type of compound having a vinyl group. For example, in the case of a compound having an ester group, a hydroxyl group or a carboxyl group is generated by saponifying the compound with an acid or an alkali, Hydrophilic aromatic polymers can be obtained. Further, when it has an amino group, it can be used as it is, or it can be quaternized by reaction with a halogen compound to form a cationic hydrophilic aromatic polymer.

Further, the hydrophilic aromatic polymer of the present invention may be blended with other hydrophobic polymers and the like for practical use. In this case, the blend ratio is preferably adjusted so that the proportion of the hydrophilic component in the blend is 5% by weight or more.

〔Effect of the invention〕

The modified polymer of the present invention can be used for various molded products, such as various parts in the electrical and electronic fields, transparent conductive films for liquid crystal displays, housings, automobile parts, interior materials for aircraft, gears, dental materials, etc. It can be used in a wide range of fields, such as steam sterilization containers. It is possible to significantly improve problems such as "easy to adhere" and "difficult to adhere". In particular, the resin of the present invention can be said to be a suitable material as it has both sufficient durability and hydrophilicity as a membrane material for forming separation membranes such as reverse osmosis membranes, ultrafiltration membranes, and membrane filters.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 15 g of polyether sulfone (degree of polymerization: 80) having a repeating unit represented by the following formula (I) with a chlorine group at the end was dissolved in dimethyl sulfoxide (DMS).
(abbreviated as O) dissolved in 70 mZ, vinylpyrrolidone 15
g was added thereto, and while stirring, N2 gas was blown in for 10 minutes.

After raising the temperature of this solution to 70°C, 0.38 g of azobisisobutyronitrile was added and stirred for 4 hours. Return to room temperature
．． After adding 2 g of hydroquinone, 50 g of solution was taken. In this solution, polyether sulfone having a repeating unit represented by formula (I) (degree of polymerization about 80) Log,
A solution consisting of 30 g of DNSo and 10 g of 77 tons was mixed and stirred day and night to obtain a homogeneous solution. After filtering and degassing this solution, polyester nonwoven fabric (MP-80K,
(manufactured by Nippon Vilene Co., Ltd.) to a thickness of 150p, exposed to a certain atmosphere for a certain period of time, and then immersed in water at 10°C to obtain an asymmetric separation membrane. Furthermore, after hot water washing at 90°C for 15 minutes, the pure water permeability coefficient (Lp).

The rate of decrease over time in LP (β) and the rate of elimination of bovine serum albumin (R) were measured.

The definition of each parameter is as follows.

(However, the value after 1 hour of filtration is taken as 1, and the L2 after 1.3 hours is taken as 3.), and the concentration of Alfumin in the plate after 1 hour of filtration is LP' = 8.0 m3/m''. day/kg/c
m”, β-5.0% and R=100%.

In addition, this separation membrane is dried and the membrane material polymer is dissolved in DMSO.
-d6 (deuterated DMSO) dissolved and 1HNMR
(I00MHz) revealed that the polyvinylpyrrolidone component was present in an amount of 15 mol% (7.8% by weight) in monomer units.

Comparative Example 1 The polyether sulfone used in Example 1 (polymerization degree of about 80
) A separation membrane was formed in the same manner as in Example 1 from only the solution of . This separation membrane has LP' = 9.6 m 3 / m
2・day・kg/cm2, but it is β-20% and the pure water permeation rate is significantly reduced.

Example 2 A reaction mixture containing modified polyether sulfone obtained in the same manner as in Example 1 was diluted with DMSO and dropped into water to precipitate the polymer. The polymer was collected by filtration, washed with water and vacuum dried at 60°C, and then 20g of it was collected.
was dissolved in 80 g of DMSo and cast onto a smooth glass plate to a thickness of 400 mm.

A transparent uniform film (thickness: 504 mm) was obtained by gradually evaporating DMSO at 80"C. This was peeled off from the glass plate and immersed in a 50% ethanol aqueous solution to completely remove the solvent. It was dried again and the surface When the contact angle with water was measured, it showed extremely good wettability of 47°.The glass transition point (Tg) of this film was measured using a differential scanning calorimeter (MODEL DSC-2 manufactured by PerkinElmer).
When measured by , it showed a high Tg of 218°C.

Comparative Example 2 The polyether sulfone used in Example 1 (polymerization degree of about 80
) was prepared in the same manner as in Example 2, and the contact angle was measured. The contact angle of this film is 78
°, and the surface was extremely difficult to wet.

Example 3 The polymerization of Example 1 was carried out on a 10-fold scale, and the polymer was recovered from the reaction mixture in the same manner as in Example 2.
After washing with 0% acetone aqueous solution and drying, polymer 1
Obtained 50g. Polyether sulfone (abbreviated as PI!S) 100g of this modified polymer was used in Example 1.
0 g, 600 g of DMSo, and 200 g of polyethylene glycol (abbreviated as PEG, molecular weight: 200) were dissolved to obtain a uniform film-forming solution (dope). After filtering and defoaming, this dope is extruded from an annular nozzle for manufacturing hollow fibers, and DMSO/water = 1:1 (weight ratio) is sent inside the hollow fibers to coagulate it, and water is supplied from the outside as a coagulation liquid. It solidified. The inner diameter of the obtained hollow fiber was 800 tm, the membrane thickness was 250-, and LP' = 15 m''/m''・day・kg
/cm”.

R=70%. Also 200 ppm of cytochrome C
This hollow fiber was immersed in the solution and left at room temperature for 17 hours.

When the adsorption amount to the hollow fiber was determined from the concentration change, 1. O
It showed an extremely low adsorption amount of pg/mg dry hollow fiber.

Comparative Example 3 Hollow fibers were obtained in the same manner as in Example 3, using only 200 g of PES used in Example 1 without using the modified polymer of Example 3 at all. LP' of the obtained hollow fiber = 12.5 m
”/mz・day1<g/cm2.R=95%,
The adsorption amount of cytochrome C measured in the same manner as in Example 3 was a high value of 26 pg/mg dry hollow fiber.

Example 4 DM 2 g of the modified polymer of Example 3 in a pear-shaped flask.
Dissolve in 98g of So and add PEG (
When 45 g of 200 (molecular weight) was added, the solution became opaque. When left for 10 days, it was separated into a transparent supernatant and a transparent thick layer. The thick layer was taken out, coagulated with ethanol, crushed into small pieces, thoroughly washed with ethanol, and then dried under vacuum to obtain 082 g of solid content. The polymer obtained by this fractional precipitation was subjected to gel permeation chromatography (G
PC) and 'II-NMR, the following results were obtained.

MW=70000. Mn=50,000. Mw/
Mn=1.4.

Polyvinylpyrrolidone (PVP) component: 34% by weight,
Analysis of the original modified polymer used for fractional precipitation revealed that M
w=41.000. Mn=23.000. Mw/M
n-1,8, and the PVP component was 16% by weight.

In addition, instead of this modified polymer, PES, which is the raw material for the modified polymer, is used as a PvP homopolymer (molecular weight 40,000
) and 84:16 (weight ratio) was used for the same fractional precipitation operation, but the solution did not become opaque and no thick layer was obtained.

From the above facts, the polymer obtained by fractional precipitation is PES
It was found that this was a modified PES in which the component and the pvp component were chemically bonded.

Claims (1)

[Claims] 1. A polymer component of a compound having a vinyl group, which is produced by reacting a hydrophobic aromatic polymer having a halogen end in the presence of a compound having a vinyl group and a radical polymerization initiator. A modified polymer having a content of 10% by weight or more. 2. A method for producing an aromatic polymer, which comprises reacting a hydrophobic aromatic polymer having a halogen end in the presence of a compound having a vinyl group and a radical polymerization initiator. 3. A homopolymer in which the hydrophobic aromatic polymer has a repeating unit represented by the following formula (I), or a homopolymer having a repeating unit represented by the formula (I) and a repeating unit represented by the following formulas (II) to (IV). 3. The method according to claim 2, wherein the copolymer is a copolymer having at least one type of repeating unit selected from repeating units. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) ▲Mathematical formulas , chemical formula, table, etc. ▼...(IV) 4. The compound according to claim 2, wherein the vinyl group-containing compound is one or more monomers of the compound represented by the following formula (V). Production method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(V) (Here, R_1 is hydrogen or methyl group. Also, R_2
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_3 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (M is hydrogen, or an alkali metal or basic substance that ionically bonds with carboxylate ions), ▲Mathematical formulas, chemical formulas, tables, etc.▼ (R_4 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms) ), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_5 and R_6 are each hydrogen or an aliphatic hydrocarbon group having 1 to 20 carbon atoms), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (n is an integer from 0 (valence bond) to 10, M is hydrogen, or an alkali metal or basic substance that ionically bonds with the sulfonate ion), ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ (R_7, R_8 and R_9 each have 1 to 20 carbon atoms.
(R_1_0 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and n is an aliphatic hydrocarbon group having 1 to 20 carbon atoms. An integer from 4 to 6, is a hydrocarbon group, and X^■ is a halogen ion). } 5. A polymer composition comprising a mixture of the modified polymer according to claim 1 and a hydrophobic polymer.