JPS62124128A - Production of crosslinked hydrophilic polystyrene - Google Patents

Abstract

PURPOSE:To obtain the titled polystyrene insoluble in organic solvent, having high heat-resistance, absorbing water, etc., and suitable for a water-ethanol separation membrane, by reacting a specific polyethylene oxide diamine derivative with a styrene-maleic anhydride copolymer. CONSTITUTION:(A) A polyethylene oxide diamine derivative produced by partially reacting 40-50% of the amino group of a polyethylene oxide diamine with an acid anhydride (e.g. succinic anhydride) or an epoxy compound (e.g. ethylene oxide having one epoxy group) is grafted to (B) a styrene-maleic anhydride copolymer in an organic solvent (e.g. chloroform). The time necessary for forming a three-dimensional network of polyethylene oxide amine with the reaction of the component B can be prolonged to a considerable extent to facilitate the molding and film-forming of the resin by preliminarily reacting the polyethylene oxide amine with an acid anhydride or epoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel crosslinked hydrophilic polystyrene. Since the hydrophilic polystyrene produced by the present invention is a crosslinked three-dimensional polystyrene, it is insoluble in all organic solvents and has heat resistance, and also absorbs water, alcohols, and water-alcohol moisture systems, and is generally It is used by forming it into a membrane. Applications include methods for producing graft polymers useful as water-ethanol separation membranes, reverse osmosis, capsules for sustained release of medical drugs, raw materials for contact lenses, materials for artificial organs, sustained release agents for chemicals, etc. It is something. Even if the starting material is a fragile film,
When polyethylene oxide diamine is grafted by the method of the present invention, the graft body of polyethylene oxide diamine with a molecular weight of about 300 to 500 is flexible and stretchable, and its tensile strength is more than twice that of before grafting. Become.

In other words, it plays the role of a plasticizer for polystyrene. In addition, since polyethylene oxide diamine with a large molecular weight of 4,000 to 6,000 is in a solid state, the hydrophilic group portion of the graft material aggregates microscopically during the molding process, separates from the hydrophobic polystyrene, and solidifies, resulting in a microphase. The film, which was found to form a separate structure by X-ray diffraction, strongly absorbed water, ethanol, and water-ethanol mixtures. In particular, in the case of a mixture of 40 parts water and 60 parts ethanol in a water-ethanol moisture solution, the absorption rate was the highest. The film is formed by pouring the reaction system together with the organic solvent onto a glass plate and drying it naturally. When this film is heated to 80 DEG C. to 150 DEG C., the acid anhydride reacts with the amine group, and the resulting amide changes into an imide form. There are many commercially available styrene-maleic anhydride copolymers, but those with a molecular weight of 100,000 or more are particularly suitable for use in film formation.

The feature of the present invention is that when a polyethylene quinododiamine solution is added directly to a styrene-maleic anhydride copolymer bath, it immediately gels even at room temperature, and the entire reaction system becomes solid and cannot be molded. On the other hand, polyethylene quinododiamine is reacted with an acid anhydride or an epoxy compound in advance, and the 6'! If it is reacted with a polystyrene solution at a temperature of 50 to 40 degrees, the remaining amino groups will completely react and a graft polymer will be obtained. , film formation is possible. The graft polymer ultimately becomes three-dimensional and becomes an insoluble and infusible polymer.

It is sufficient for all reactions to be left at room temperature or stirred with a magnetic stirrer. The solvent used in the reaction is styrene-maleic anhydride copolymer, polyethylene oxide diamine, various acid anhydrides,
Organic solvents that dissolve various epoxy compounds are desirable, but
An organic solvent may also be used. In addition to dissolving the entire compound, a low boiling point solvent is advantageous in terms of the molding process.

Examples of solvents that satisfy these conditions include chlorinated aliphatic compounds such as chloroform, dichloromethane, dichloroethane, and trichloroethane, as well as tetrahydrofuran, acetone, and methyl ethyl ketone. Polyethylene oxide diamine has a molecular weight of 300, 500, 700,
1000, 4000, 6000 or so are available. The reaction with acid anhydrides and epoxy compounds is very fast even at room temperature, and when about 40 of the total amino groups are reacted with the acid anhydride and then reacted with the styrene/% water maleic copolymer, nihapolyethylene oxide is produced. Since those with amine/group 'e remain at both ends, crosslinking occurs relatively quickly and the crosslinking density is high, but when reacted with a 50 amine group, the crosslinking reaction is very slow. Become.

The most effective acid anhydrides are usually phosphoric anhydride, maleic anhydride, phthalic anhydride, etc., and the epoxy compounds are preferably ethylene oxide, propylene oxide, epichlorohydrin, etc., which are epoxy-based.

The graft polymer classified in the present invention has high water absorption and alcohol absorption properties, and the squareness of its absorption is mainly proportional to the grafting ratio of polyethylene oxide diamine. Therefore, although it is advantageous to graft polyethylene oxide diamine with a high molecular weight, the strength is the same as that of the original polystere/copolymer and does not improve.

In the reaction between a styrene-maleic anhydride copolymer and a polyethylene oxide diamine derivative, the reaction process can be taken out sequentially and the reaction rate can be calculated from the reduction rate of the heater at 1760 m in the infrared absorption spectrum using a jet line. . Grafting can be easily and calculated by simply reacting the desired bamboo polyethylene oxide diamine with the number of moles of maleic acid in the copolymer at room temperature.

Next, the present invention will be explained in more detail using actual examples.

Example 1 Using chloroform as an organic solvent, 1 g of styrene
Maleic anhydride copolymer (molecular weight: 122,000, molar content of maleic anhydride: 11.7) was dissolved in a total of 20 ml of solvent, and 3 pieces of this were prepared.

Separately, in tetrahydrofuran of K 5 me, 0.0148 g of phthalic anhydride, 0.01 g of succinic anhydride,
Dissolved in 0.0098 g' of maleic anhydride and separately 0.69 polyethylene oxide diamine (946,000 molecules)
'< ] A solution of Otnl dissolved in chloroform is
Prepare phthalic anhydride, succinic anhydride,
One mouthful of anhydrous maleic acid solution was added and reacted at room temperature for 2 hours using a magnetic stirrer.

Through this reaction, 50% of the amino groups in the polyethylene oxide diamine react to form an amide, which has lower reactivity than an amine. These three solutions were respectively added to the chloroform solution of the styrene-maleic anhydride copolymer prepared initially, and reacted at room temperature while stirring with a magnetic stirrer. All of the reactions in these three buildings were colorless, transparent, and homogeneous, and the viscosity of the entire system increased gradually, reaching 50 cpsK after 6 hours, and when stirred and pulled up with a glass rod, it became stringy.

If you remove the quadrupedal reaction, the chapter I Sara will reach 60C1)8, and 50
30 minutes after reaching Cp8, it was assimilated (three-dimensional f) and became unmoldable. Therefore, in order to obtain the original object, we repeated the process again under exactly the same conditions, and the viscosity was 50.
cps is reached, the reaction system is poured onto a glass plate with strings to form a film, air-dried, and the next day heated at 80°C for 1 hour to completely remove chloroform and completely remove unreacted residual amine groups. Made it react. The reaction was carried out sequentially by taking out a portion of the reaction system and measuring its infrared absorption spectrum.
The reaction rate was calculated from the rate of decrease in the absorption of water based on the detection line. According to this, the graft reaction was completed in 1 hour. In this case, in the grafting reaction using polyethylene oxide diamine not treated with Kuma anhydride, it became three-dimensional and assimilated within 5 minutes after addition.

The obtained film was subjected to IH-NMI (spectral analysis f3
．． 61) 1) m2, 13C-NMR spectrum analysis The absorption of ethylene oxide was observed at 0.73 ppm, and X#j! 20.6 and 22 for diffraction by
．． A peak was observed at 0 (2θ).

In thermal analysis using DSC, an endothermic peak was observed at 65.5°C, indicating that polyethylene diamine (molecular weight 6.000
) present in II-(,+3cmNMR,X@,
It showed the same value as the analysis value such as DSC.

The graft ratio of the film obtained in this experiment was calculated from 1R to 1H-N and an infrared absorption spectrum of 1760 m', and was 60, and it seems that there were no unreacted substances. In addition, the detection of X-ray diffraction and DSCK crystalline polyphthalene oxide indicates that during the process of solidification of this graft film and evaporation of the solvent, the highly hydrophilic part is microscopically compatible with the rough aqueous part. It is a microphase-separated film created by separation.

There was no noticeable difference in physical properties between films using three different acid anhydrides, probably because the amount of acid anhydride used was very small.

The obtained film contains 15wt of water and ethanol'! r
In the 25wt% ethanol-water mixed system, the absorption reached a peak at 80% ethanol and 20% water, and 75wt4 was absorbed. The tensile strength of the film was almost the same as that of an ungrafted styrene copolymer film, but it was very flexible in a water and ethanol mixture.

Example 2 Styrene-maleic anhydride copolymer (molecular weight 122.
000. 1 g of maleic anhydride (mol number 11.7%) was dissolved in 20 rnl of dichloroethane. Polyethylene oxide diamine (molecular weight 4030) 3,! i'e
Dissolve in 15ml dichloroethane and add 5ml to this solution.
Propylene oquinide dissolved in ml dichloroethane 0
．． 0432. ! 9 was added and reacted at room temperature for 3 hours. The reacted solution was added to the previously prepared dichloroethane solution of styrene-maleic anhydride copolymer at room temperature, and the mixture was stirred and reacted with a magnetinox stirrer. During the reaction process, the reaction rate of the reaction system was successively monitored using infrared absorption spectra.

Since this reaction was completed in one hour, the reaction system solution was immediately poured onto a glass plate to form a film, and at the same time, a portion was left to monitor the state of the reaction. Viscosity is 50C after 1 hour and 20 minutes
pS, and was removed after 1 hour and 30 minutes. Regarding physical properties
') f-C-NMR spectrum, X-ray spectrum, DS
Molecule i described in Example 1 with C thermal analysis spectrum
The same as the polyethylene diamine grafted product with a molecular weight of 4030, it is a crystalline solid with a melting point of 65.
I think this is because they have the same feature of indicating °C. The grafting rate reached 300 wt%. This film is hard and brittle, and is of little practical use in membrane form, but water 5 Q wt%
In the water-ethanol mixed solvent, the weight peaked at 60% ethanol and 40% water, and 170% by weight was absorbed. The membrane with such a high graft ratio absorbed a large amount of water, ethanol, etc., swelled, swelled greatly, and became soft.

Example 3 Thule: y-maleic anhydride copolymer (molecular 1t
109800, number of moles containing maleic anhydride 13.6%)
1 g was dissolved in 20 ml of chloroform.

Separately, to a solution of 0.311 g of polyethylene oxide diamine (molecular weight 525) dissolved in chloroform IQ ml, a solution of 0.059.9% of cono-phosphoric anhydride dissolved in 5 ml of tetrahydrofuran was added. The reaction mixture was allowed to react for 21 hours at room temperature with stirring using a mug stirrer. The amount of co-phosphoric anhydride is in this case the amount necessary and sufficient to react with half of the amine groups in the polyethylene oxydodiamine. After the reaction was completed, it was added to the previously prepared styrene-maleic anhydride copolymer solution and reacted at room temperature with stirring.As in the previous example, the reaction was successively tracked using infrared absorption spectroscopy and the reaction rate was calculated. In the case of polyethylenediamine having a small molecular weight, the reaction was rapid, and the reaction was completed after 30 minutes, and the viscosity reached a value close to 50 CpS, so a portion was poured onto a glass plate and formed into a film. The remaining reactants were used as they were for viscosity measurements and assimilation time measurements. The time until assimilation was 1 hour, and the viscosity was 60 Cpθ. The grafted polymer poured onto the glass was air-dried until the next day, and further 1. After heating the OOoC for 1 hour, cooling it and putting it in water, the membrane was peeled off.
In the case of a mixed solution of water and ethanol, the absorption rate was the highest at 45 wt% when 70% of ethanol was mixed with 30% of water. This film is extremely flexible, stretchy, transparent, and meets JIS K630 standards.
The tensile strength of the styrene-maleic anhydride copolymer before grafting was 23.5 megapascals in the tensile test according to method 1, which was 85 times stronger than the tensile strength of 12.7 megapascals in the same test for the styrene-maleic anhydride copolymer before grafting.

Procedural amendment (voluntary) 61 Kagiken No. 2 1985 1 6 Japanese Patent Office Commissioner Uga Michibe Yakyo 1, Indication of case Patent Application No. 263257 1985 2)
Title of the invention: Cross-linked, hydrophilic polystyrene production 3, patent related to the amended conceptual method case Applicant address: 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo Name (114) Director of the Agency of Industrial Science and Technology Tokaka Tatsu :8. Contents of the amendment (engraving of the specification originally attached to 11!1i1118)
As shown in the attached sheet. (No change in content)

Claims (3)

[Claims] (1) Add an acid anhydride or an epoxy compound to the amino group in polyethylene oxide diamine with a concentration of 40 to 50
A method for producing crosslinked, hydrophilic polystyrene synthesized by a graft reaction of a partially reacted polyethylene oxide diamine derivative with a styrene-maleic anhydride copolymer. (2) The acid anhydride described in claim 1 refers to an aliphatic or aromatic compound containing one acid anhydride structure, and the epoxy compound refers to an aliphatic compound containing one epoxy group. family,
It is an aromatic compound. A method for producing crosslinked, hydrophilic polystyrene according to claim 1 by reaction with these compounds. (3) The manufacturing method according to claims 1 and 2, in which the reaction is carried out by dissolving it in an organic solvent and carrying out the reaction at room temperature.