JPS6036533A - Manufacture of porous anion exchange membrane - Google Patents

Abstract

PURPOSE:To readily obtain the titled membrane of high-dialysis performance, having quaternary ammonium salt group as the anion exchange group, by the reaction, in a water-soluble organic solvent, between active chlorine group-contg. resin and amine followed by making the resultant solution into membrance through dry-wet process. CONSTITUTION:The objective ion exchange membrane having quaternary ammonium salt group as the anion exchange group, can be obtained, by adding (A) an active chlorine group-contg. resin (pref. vinyl chloride resin) and (B) an amine (pref. trimethylamine) to an organic solvent such as dimethylacetamide preferably in such amounts as to be 5-10wt% and 20-30wt%, respectively, to carry out a reaction followed by making the resultant solution into porous membrane in the form of flat film, hollow fiber, etc. USE:For electrodialysis, diffusion dialysis, etc.

Description

[Detailed Description of the Invention] The present invention relates to a method for producing a porous (α15.! ion exchanger).
Anion exchange t+-;L! A method of manufacturing porous ion exchange (Q 71) with a quaternary ammonium salt 2 as follows.

1 life ion parent membrane C, it allows anion to pass through more selectively + 1 one thing, so using this property, electricity y-me 4fr, expansion f7k dialysis? Urui is industrially useful for salt electrolysis, etc., and is rated +{2+. 7. 7. 7 hours of electricity will make you realize how effective it is. :: A') l. So, the medium H・I} and the ion i excellent precipitation degree 61 and 1 degree Z, that is,
Required for anion exchange. In general, it is known that this dialysis rate can be improved by making the membrane thinner, but if the thickness is made extremely Lσ, it is inevitable that Difficult to handle Ii′” due to decreased membrane strength.
“1゜(IF), and practicality will be lost.

In order to eliminate these drawbacks, Book 11
Purification 1 - Purification (I upper part 9) Chemical resistance and support f1 for reinforcing the fluoropolymer porous membrane
・I have carefully considered the method of anion exchange 1i1; 1:. 1' Since the adhesion between $1 is sufficient and 1f is higher than 1F, the anion・'2! [During the handling of the I membrane, I noticed that both of the 'J'l AFs were not working properly. The ZX point between is Mira In,
In order to solve this problem, the applicant further developed a method for treating polymers such as porous vinyl-based (material) membranes with plasma. When used as a support on the 7th column, Kei Kono et al.
Between j"i: l71 &ij!' ii! L 'j"J
Luko (!: 'l: Ahead 1c Heading L T.H (
(Refer to Special 1″IQ No. 1983, No. 57230.503).

In this way? 4, i Ranoshiru 1 Rattan/If- Anion exchanger containing an ion-exchangeable group f1λ having a quaternary ammonium salt i1L as an exchangeable group f I' + m k An anion exchange In'< V :l: . , the effect is J. ．． The process of forming the L layer:,;,E layer is required when the target is sufficiently grown.
), so the 9th L'if l
I can't see the demand for l+, 5.

Therefore, the inventor of the present invention simplified the manufacturing process by one step by directly performing ion cross-fertilization 31,(;・j-t people with E-1 fat-breakable material). 4, same 1i', 6. Porous j14 simple substance-c anion father 1 without providing an expense layer
・7; By forming j・I, dialysis 141, as a result of decaying aJ in order to obtain qy with excellent performance,
41. Chlor's ``rZ-Ij': 1fJ and amine were dissolved in an aqueous solvent, and then the solution was dissolved in a 1λgl. From this, we have discovered a plan to create a porous ion exchange membrane containing quaternary ammonium jr.:F groups as λ ion exchange groups. Invention 1: Anion exchange performed in this manner 1
1D2 t: Inspired by the rebuilding method.

Active chlorine, I, (containing fat is salt I, 1' vinyl/
I-1, which is obtained by combining single gases of L (1 (1) vinyl chloride thread tree BFt when combined, Iff.
Chloromethane group-containing styrenic resins such as f7 are used. It's 1, Ryomin Toji ζC1 I♀l'di (
f> can be used, but aliphatic amines such as ethylenediamine, methylamine, and 1.limethylamine are particularly suitable.

Kono L et al.'s active 1, 7-11 group-containing resin and amine are water-soluble, bottle-soluble compounds. Approximately 3 to 20 liters each, preferably approximately 5 to 10 liters! % and approx. 15 to 35 %, and 5 to 30 % and about 20 to 30 fl % of addition 1
1 and subjected to reaction. As a water-soluble solvent,
Any substance can be used as long as it dissolves the active chlorine group-containing toner amine, but dimethylborumamide, dimethylacetamide, and the like are preferably used. The reaction is carried out at a temperature of approximately 20 to 1.00°C, preferably at a temperature of approximately 50 to 1.00°C.
The process is carried out at a temperature of 80 DEG C. for about 12 to 15 hours, and the active chlorine groups of the resin are equalized to quaternary ammonium.

The reaction solution is made into a porous film in the shape of a flat film, hollow fiber, or any other shape by using a dry-wet method using a cooling raft, a water-based membrane, or a solid agent.

A porous bamboo anion exchange membrane containing a quaternary ammonium salt; j, I: as an anion-exchangeable group is an active polymer, j, (containing resin and amine). It is easy to manufacture, and it does not have a twisted wave layer. So,
It is also said to have excellent dialysis performance ;:)/J Kak
4 cheat.

Next, the invention will be explained using a real example.

Modification 4 Example 1 Polychloride (Nippon Zeon product E-103P)
74
The solution was heated to 80° C. for 5 hours, and then cooled to room temperature. It was signed.

The porous anion exchange membrane thus obtained was attached to a two-chamber dialysis cell, and 2 N H , SO a 'l
'i and IN-FθSO4 aqueous solution.
Vi test M hair, conduct, sulfuric acid dialysis uncertainty and the success of both υ1
The speed ratio and 11 were measured.

Actual bending; Example 2 In Example 1, the reaction [1,9.
! ! I got Jku9.

Example 3 In Example IVC, trimethylamine 'a'' 3(l
The percentage of iri fan% is included.
Ami Fl'i'; lfζ゛ was washed away.

Example 4 In Example 1v, 1 beer in 10 tlj
%nori? Cimethynolease 1/amiF contained in IJ combination
I'+7 e(l lr: Used 1, ta.

The dialysis trial results for each of the above examples are shown in the table below.

Claims (1)

[Claims] 1. Live juice containing chlorine groups (liquid fat and amines are dissolved in water). ．j
Anionic interaction characterized by
II's I'GJ ;'+5E method of ion exchange. 2 Active chloro group-containing tree)]; The characteristic n1'' Ml is a resin yarn containing active chlorine groups;
Porous anion exchange well: 1 production method.