JPH02293025A - Membrane module and its production thereof - Google Patents

Abstract

PURPOSE:To obtain a porous membrane module having superior heat and chemical resistances by mixing two kinds of epoxy resins represented by specified structural formulae in a specified ratio in the number of epoxy groups and curing the mixture with an alicyclic amine to carry out potting. CONSTITUTION:A membrane module is obtd. with a potting agent contg. epoxy resin represented by formula (i) and epoxy resin represented by formula (ii) in 0.2 to 3 ratio in the number of epoxy groups and further contg. an alicyclic amine. In the formula (i), each of R<1> to R<4> is H or methyl, each of Ar<1> to Ar<4> is an arom. ring which may have two or less Cl or Br substituents and (k) is an integer of 0 to 5. In the formula (ii), each of R<5> to R<8> is H or methyl, each of Ar<5> and Ar<6> is an arom. ring which may have two or less Cl or Br substituents and each of (m) and (n) is an integer of 1 to 3.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a membrane module used for filtration of liquids and gases and a method for manufacturing the same.

(Prior Art) In recent years, membrane modules with fluid filtration capabilities have come to be widely used in the medical field, liquid and gas processing fields, etc.Recently, membrane modules with fluid filtration capabilities have been increasingly used in fields that require heat resistance and chemical resistance. The use of is also expanding.

For example, heat-resistant membranes include polyether sulfone,
Examples include membrane materials such as boribropylene.

However, hollow fiber membranes made of polyether sulfone have poor strength and elongation, so there is a risk of them breaking in intense liquid flow. Further, when the polypropylene hollow fiber membrane passes through hot water for a long period of time, it undergoes oxidative deterioration and becomes brittle.

On the other hand, porous membranes made of polyethylene have excellent hot water filtration properties and chemical resistance, but have a relatively low melting point.

Therefore, although urethane resin has poor heat resistance and chemical resistance, it has been used exclusively as a botting agent for polyethylene porous membranes because it generates little heat during curing. on the other hand,
Epoxy resins have excellent heat resistance and chemical resistance, but in the case of commonly used bisphenol resins, for example, the heat generation temperature during curing is higher than the melting point of polyethylene, so polyethylene porous membranes are It could not be used for potting. Therefore, it has been desired to develop a botting agent that can bott polyethylene porous membranes and has excellent heat resistance and chemical resistance.

[Problem to be solved by the invention]

An object of the present invention is to provide a resin for botting that has excellent heat resistance, chemical resistance, and impact resistance and can be applied to botting polyethylene porous membranes.

Another object of the present invention is to provide a membrane module, particularly a polyethylene porous membrane module, which has a botting portion with excellent heat resistance, chemical resistance, and impact resistance.

[Means to solve the problem]

That is, in the present invention, the end portion of the porous membrane housed in the module case is formed by (a) the following general formula (i) Rl (wherein R1 to R4 are each independently hydrogen, a methyl group, Ar'~Ar' is an aromatic ring which may each independently have up to two chlorine or bromine substituents, k is 0 to 5
indicates an integer. ) Epoxy resin A, (b)
General formula (ii) below? a 1000-CH2-CI-)7-0-C112-11;}I
-Cl+■ (In the formula, 85 to R8 are each independently hydrogen or methyl group, ^r5 to Ar' are each independently 2
m and n represent integers from 1 to 3; ), and (C) contains an alicyclic amine, and the ratio of the number of epoxy groups in epoxy resin A and epoxy resin B is 0.2.
This is a porous membrane module made by curing and potting the bottling agent No. 3 to 3.

(Function) The botting agent used in the present invention has (a) the general formula (
i) Epoxy resin A represented by (b) the general formula (
Epoxy resin B represented by 11) and (C) resin.
Contains a cyclic amine.

If a composition consisting only of epoxy resin A and a curing agent is used as a botting agent, the exothermic temperature during curing will be too high, and the temperature of the botting agent will be close to or higher than the melting point of the polyethylene porous membrane, which may cause botting. I can't.

In the epoxy resin A used as component (a), in the general formula (i), k is suitably an integer of O to 5. If it exceeds 5, the viscosity becomes too high.

In addition, epoxy resin B used as component (b) is
In the general formula (ii), m and n are suitably integers of 0 to 3. If it exceeds 3, the viscosity will become too high.

The mixing ratio of epoxy resin A and epoxy resin B is preferably used such that the ratio of the number of epoxy groups in epoxy resin A to the number of epoxy groups in epoxy resin B is 0.2 to 3.
0.3-2 is more preferable.

If it is less than 0.2, heat resistance and chemical resistance will deteriorate, which is not preferable. If it exceeds 3, the heat generation temperature during curing becomes too high, which is not appropriate.

Various amines, amides, acid anhydrides, etc. can be used as curing agents for the mixed epoxy resin containing the above components (a) and (b), but among these curing agents, alicyclic Amines exhibit the most excellent properties in terms of their curing behavior (curing time, exothermic temperature, etc.), especially when used as a potting agent for polyethylene porous membranes.

Alicyclic amines used as component (C) include menzendiamine, inphoronediamine, N-aminoethylbiverazine, and 3.9-bis(3-aminopropyl).
-2.4,8.10-tetraoxysub(5.5) undecane adduct, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, 4-amino(2,2 , 6,8-tetramethyl)piveridine, etc., and these may be used alone or in combination.

The amount of alicyclic amine (C) used is preferably such that the total number of epoxy groups in component (a) and component (b) is equal to the amount of epoxy groups in component (C}, and is 0.4 to 2.5. It is more preferable to use it as follows.

If there are fewer amino groups, the curing time at room temperature will be longer.
If there are too many amino groups, unreacted amines will remain, causing problems such as elution.

When preparing a potting agent containing components (a) to (C) used in the present invention, these components may be mixed in any order.

The botting agent containing components (a) to (C) used in the present invention has an initial viscosity of 2000 to 2 at (25°C).
0,000 cps, the curing time is within 20 hours, it can be cured at room temperature, the heat generation temperature is low, and it can also be used for botting polyethylene porous membranes with a low melting point.

Further, it is preferable to further perform post-curing after curing at room temperature because crosslinking progresses and heat resistance and chemical resistance are improved. When polyethylene is used as the porous membrane, the post-curing temperature must be below the melting point of polyethylene.

The module case can be made of various resins or metals, but in the case of resin, it is preferable to use polypropylene resin or polysulfone resin, which has good hot water resistance and chemical resistance. When polypropylene wood is used as a module case, it is desirable that the inner surface of the case be surface-treated to improve adhesion to the botting agent.

Surface treatments for polypropylene resin include plasma discharge treatment, corona discharge treatment, flame treatment, ultraviolet treatment, ozone treatment, chromium mixed acid treatment, n-hexane treatment, brusher coating, surface roughening, etc., and these treatments alone It is carried out with or in combination.

The porous membrane used in the present invention is preferably a membrane made of polyolefin, polysulfone, or the like from the viewpoint of heat resistance and chemical resistance. The form of the porous membrane may be a hollow fiber membrane or a sheet-like membrane such as a flat membrane.

Furthermore, various conventionally known methods can be used to make the membrane porous.

Various conventionally known botting methods can be employed to bott the end of the porous membrane into the module case using a botting agent.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 380 parts by weight of Ebicoat 828 (manufactured by Yuka Ciel Epoxy ■) as the epoxy resin A, 315 parts by weight of Evolite 3002 (manufactured by Kyoeisha Yushi Kagaku Kogyo ■) as the epoxy resin B, and Kayabond (:-950) as the alicyclic amine.
(manufactured by Nippon Kayaku ■) Using a botting agent consisting of 114 parts by weight, a polyethylene porous membrane (EHF410
(;, product name, made by Mitsubishi Rayon■) is bent at the center,
It was made into a U-shape, housed in a module case, and a botting agent was poured into it for botting. The module case was made of polypropylene, and the inner surface of the potting part was flame treated.

Potting was carried out under centrifugal force, and the resin was kept at room temperature for 2 hours.
After being left for 4 hours, post-curing was performed at 60°C for 5 hours and then at 90°C for 5 hours. Afterwards, water pressure was applied to check for leaks. A water pressure of 1 kg/cm2 was applied for 3 minutes to check for leaks, and if there was no leakage, the water pressure was increased in steps of 1 kg/cIm2, and leak tests were carried out for each 3 minutes until the water pressure reached 5 kg/c.

If the adhesion is poor, water leaks from the adhesive interface between the module case and the botting agent, but no leakage was observed.

Further, the polyethylene porous membrane fixed in the potting agent was not melted, and potting was performed well as in the case of conventional potting with urethane resin.

In addition, with this module, 90℃ hot water can be heated at a differential pressure of 1kg/c.
After filtering with m2 for 200 hours, the module was dried and a similar leak test was performed, but no water leaks were found. .

Examples 2 to 8 U-shaped modules of polyethylene porous membranes were created in the same manner as in Example 1 using various potting agents consisting of epoxy resin A, epoxy resin B, and alicyclic amine shown in Table 1. . The module case is made of surface-treated polypropylene resin or polysulfone resin.

The heat resistance of the obtained hollow fiber membrane module was evaluated by hot water filtration or steam sterilization. Further, chemical resistance stability evaluation was performed by conducting a leakage test in the same manner as in Example 1 using various chemical solutions such as acid, alkali, and ethanol. Table 1 shows the manufacturing conditions and evaluation results of the hollow fiber membrane module.

Comparative Examples 1 to 5 Urethane resin was used as a botting agent (Comparative Examples 1 and 2), epoxy resin A was used alone (Comparative Example 3), epoxy resin B was used alone (Comparative Example 4
), using an aliphatic amine as a curing agent (Comparative Example 5)
) A hollow fiber membrane module was produced in exactly the same manner as in Example 1, except that the following was used. The manufacturing conditions and evaluation results of the membrane module are shown in Table 1.

Epicoat 828: Made by Yuka Ciel Epoxy ■, epoxy equivalent: 190 Epicoat 834: Made from Yuka Ciel Epoxy ■, epoxy equivalent: 250 Coronate 4403 + Epolite 3302, manufactured by Nippon Polyurethane ■: Epoxy equivalent: 3, manufactured by Kyoeisha Yushi Kagaku Kogyo ■
15 Kayabond C-950: Nippon Kayaku ■, amine equivalent 3
8 Kayabond G-900: Manufactured by Nippon Kayaku ■, 1 per amine
45 Nipporan 4221: Made by Nippon Polyurethane ■ Epicure T-1: Made by Yuka Shell Epoxy ■, amine equivalent 70
, aliphatic amine [Effects of the Invention] As is clear from the above description, according to the present invention, a porous membrane module having excellent heat resistance and chemical resistance, particularly a porous membrane module made of polyethylene, is provided. Its significance is great.

Patent applicant: Mitsubishi Rayon Co., Ltd.

Claims (4)

[Claims] (1) The end of the porous membrane stored in the module case is (a) The following general formula (i) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (i) (In the formula, R^1 ~ R^ 4 is each independently a hydrogen or methyl group, Ar^1 to Ar^4 are each independently an aromatic ring which may have up to two chlorine or bromine substituents, k
represents an integer from 0 to 5. ) Epoxy resin A represented by
, (b) General formula (ii) below ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (ii) (In the formula, R^5 to R^8 are each independently hydrogen or a methyl group, Ar^5 to Ar^ 6 is an aromatic ring which may each independently have up to two chlorine or bromine substituents, m
and n represents an integer of 1 to 3. ) and (c) an alicyclic amine, and the ratio of the number of epoxy groups in the epoxy resin A and the epoxy resin B is 0.
A porous membrane module potted by curing the potting agent according to No. 2 or 3. (2) The porous membrane module according to claim 1, wherein the module case is made of polysulfone resin or surface-treated polypropylene resin. (3) Claim 1, wherein the porous membrane is a polyethylene porous membrane.
Porous membrane module described (4) Claim that the ratio of the total number of epoxy groups in component (a) and component (b) to the number of amino groups in component (c) (▲There are mathematical formulas, chemical formulas, tables, etc.▼/-NH_2) is 0.25 to 4. Item 2. A method for producing a porous membrane module, comprising potting an end of the porous membrane in a module case using the potting agent according to item 1.