JPH02293024A - Membrane module and its production - Google Patents

Abstract

PURPOSE:To obtain a porous membrane module having superior heat and chemical resistances by curing bisphenol type epoxy resin and liq. polysulfide rubber or epoxy resin having polysulfide bonds with an alicyclic amine to carry out potting. CONSTITUTION:Bisphenol resin such as bisphenol A, F or S resin is mixed with liq. polysulfide rubber or epoxy resin having polysulfide bonds. The pref. epoxy equiv. of the bisphenol resin is 160 to 500. The resulting liq. mixture is cured by adding an alicyclic amine such as menthenediamine or isophoronediamine. A membrane module, especially a porous membrane module of polyethylene with potting parts having superior heat, chemical and shock resistances is obtd.

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 having fluid filtration capabilities have come into widespread use in the medical field, liquid and gas processing fields, and the like. Recently, its use in fields that require heat resistance and chemical resistance is expanding.

For example, heat-resistant membranes include polyether sulfone,
Examples include those whose membrane material is polypropylene or the like.

However, hollow fiber membranes made of polyether sulfone have poor elongation and are likely to break in intense liquid flow. Furthermore, hollow fiber membranes made of polypropylene undergo oxidative deterioration and become brittle when hot water passes through them for a long period of time.

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 potting agent for polyethylene porous membranes because it generates little heat during curing. on the other hand,
Although epoxy resins have excellent heat resistance and chemical resistance, for example, in the case of the commonly used bisphenol resin, the heat generation temperature during curing is higher than the melting point of polyethylene, so polyethylene porous film It could not be used for potting. Therefore, it has been desired to develop a potting agent that can pot polyethylene porous membranes and has excellent heat resistance and chemical resistance.

(Problems to be Solved by the Invention) An object of the present invention is to provide a potting resin that can be used for potting polyethylene porous membranes and has excellent heat resistance, chemical resistance, and impact resistance.

Another object of the present invention is to provide a membrane module, particularly a polyethylene porous membrane module, having a potting part 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 made of (a) a bisphenol type epoxy resin, (b) a polysulfide liquid rubber or an epoxy resin having a polysulfide bond, and (c) an alicyclic type epoxy resin. This is a porous membrane module potted by curing a potting agent containing an amine.

[Effect]

The potting agent used in the present invention contains (a) a bisphenol type epoxy resin, (b) a polysulfide liquid rubber or an epoxy resin having a polysulfide bond, and (c) an alicyclic amine.

If a composition consisting only of a bisphenol-type epoxy resin and a cyclic amine curing agent is used as a potting agent, the exothermic temperature at the time of curing the potting agent becomes too high, and the temperature at the time of curing the potting agent exceeds the melting point of the polyethylene porous membrane. Potting is not possible because the area is larger than the neighborhood. Further, the combination of a bisphenol type epoxy resin and a liquid rubber having a polysulfide bond is not preferable because it takes a long time to cure although the curing exothermic temperature is low.

The bisphenol-type epoxy resin used as component (a) is produced by reacting various bisphenols with shrimp chlorohydrin, and in the present invention, various bisphenol-type epoxy resins can be used without particular limitation.

A typical bisphenol is bisphenolacetone (bisphenol A), which is produced by condensation with acetone.
), bisphenol-formalin (bisphenol F) produced by condensation with formalin and bisphenol sulfone (bisphenol S) produced by condensation with sulfuric acid.
can be mentioned.

The bisphenol-type epoxy resin (a) referred to in the present invention has a special type of bisphenol-type resin. Hydrogenated bisphenol A and hexahydride bisphenol A) resins having excellent weather resistance are included, and of course halogenated bisphenol type epoxy resins such as brominated resins and fluorinated resins are also included.

The bisphenol type epoxy resin preferably has an epoxy equivalent of 160 to 500, more preferably 170 to 400. When it is less than 160, the heat resistance of the cured resin deteriorates, and when it exceeds 500, the viscosity of the resin increases too much.

The polysulfide liquid rubber used as component (b) has a polysulfide bond (+S+=,
n≧1), may have branches, and has two or more thiol groups at the end of the main chain or branch, for example, HS-(c2}14-0-C11■-0
-(:2H4-S one soup, 02114-0-GH2-0
Examples include those having a structural formula such as -C2H4-S}I. This liquid rubber has excellent gas and vapor barrier properties, oxidation resistance, weather resistance, and ozone resistance, and is highly resistant to various solvents, fuel oils, acids, and alkalis, and has excellent low-temperature properties. Furthermore, by using it in combination with an epoxy resin, it is possible to improve various properties required of a potting agent, such as flexibility, imparting 8I impact resistance, improving adhesiveness, and reducing shrinkage during curing.

In addition, the epoxy resin having a polysulfide bond used as another of the five components (b) refers to an epoxy resin having a polysulfide bond (GoS}=) (n≧1) in the main barrel, such as Clh-C: H-CHz-S-
Examples include those having a structural formula such as (c2114-0-Cll2-0-CJI4-S-S total\/ (where R represents an alkyl group having 1 to 10 carbon atoms). For example, mairi can be obtained by the reaction of bis(dichloroethyl) formal and sodium polysulfide, but in some cases, it may be partially cross-linked by adding a suitable cross-linking agent such as a polyfunctional alkyl halide. For example, shrimp chlorohydrin can be used to introduce an epoxy group to the terminal end.In addition, these resins mix well with bisphenol epoxy resin to form a uniform resin solution, and are compatible with bisphenol epoxy resin. In comparison, it has greater elongation and less heat generation and curing shrinkage during curing.

When polysulfide liquid rubber is used as component (b), the mixing ratio of bisphenol type epoxy resin (a) and borisulfite liquid rubber (b) is the ratio of the number of epoxy groups to the number of thiol groups -elf-(1:H2 ( It is preferable to use it so that \/ /511) is 1 to +00, more preferably 5 to 50. If it is less than 1, the heat generation temperature during curing is low, but it takes a long time to cure. 100.
If it exceeds 100%, the exothermic temperature during curing is high and curing shrinkage is large, making it difficult to use as a potting agent.

In addition, when an epoxy resin having a polysulfide bond is used as component (b), the mixing ratio of the bisphenol type epoxy resin (a) and the epoxy resin having a polysulfide bond (b) is the ratio of the number of epoxy groups: bisphenol type/ The ratio of borisulfide type is preferably 0.1 to 5, more preferably 0.2 to 4. If it is less than 0.1, the chemical resistance of the cured resin will deteriorate, and if it exceeds 5, the exothermic temperature during curing will be too high, and the cured product will be brittle.
Moreover, it has large curing shrinkage and is difficult to use as a potting agent.

As component (b), polysulfide liquid rubber or epoxy resin having a polysulfide bond may be used alone, but of course they can also be used in combination.

As a curing agent for the mixed epoxy resin containing the above components (a) and (b), various amines, amic acid anhydrides, etc. can be used, but among these curing agents, alicyclic amines exhibits the best properties in its curing behavior (curing time, exothermic temperature, etc.), especially when used as a potting agent for porous polyethylene membranes.

Alicyclic amines used as component (c) include menzendiamine, isophoronediamine, N-aminoethylbiverazine, and 3.9-bis(3-aminoprobyl).
-2.4,8.10-tetraoxyspi(5.5)
Undecane adduct, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, 4-amino(2,2,6.6-tetramethyl)viveridine, etc., and these may be used alone. Or used in combination.

The amount of alicyclic amine (c) to be used is determined by the total number of epoxy groups in component (a) and component (b) and the amount of alicyclic amine in component (c). CH
-fl:H■ The ratio of mino radicals (\/ /-NH2) is 0.25 ~
It is preferable to use it so that it becomes 4.0, and 0.4 to 2
．． It is more preferable to use it so that it becomes 5.

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) for use in the present invention, these components may be mixed in any order.

The potting agent containing components (a) to (c) used in the present invention has an initial viscosity of 2,000 to 2,000 at (25°C).
0,000 cps, 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 potting polyethylene porous membranes with a low melting point.

Further, after curing at room temperature, it is preferable to perform post-curing at a temperature below the melting point of polyethylene because crosslinking will proceed and heat resistance and chemical resistance will improve.

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 resin is used as a module case, it is desirable that the inner surface of the case be surface-treated to improve adhesion to the potting 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, primer application, and surface roughening. 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 potting methods can be used to pot the end of the porous membrane into the module case using a potting agent.

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

Example! Ebicoat 834 as a bisphenol type epoxy resin
133 parts by weight (manufactured by Yuka Shell Epoxy ■), 50 parts by weight of LP-2 (manufactured by Toray Thiokol ■) as a polysulfide liquid rubber, and Kayabond C- as an alicyclic amine.
A porous polyethylene membrane (EHF410
G. Product name: Mitsubishi Rayon ■) is bent at the center and U
It was shaped into a letter shape, placed in a module case, and potted with potting agent poured into it. The module case was made of polypropylene, and the inner surface of the bottoming 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 is applied for 3 minutes to check for leaks, and if there is no leakage, the water pressure is increased in 1 kg/cm2 increments.
carried out up to.

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 filtration at m2 for 200 hours, the module was dried and tested for leaks in the same manner, with no evidence of water leakage.

Examples 2 to 9 U-shaped modules of polyethylene porous membranes were created in the same manner as in Example 1 using various botting agents consisting of bisphenol-type epoxy resin, polysulfide liquid rubber, and alicyclic amine shown in Table 1. did. Surface-treated polypropylene resin or polysulfone resin was used for the module case.

The heat resistance of the obtained hollow fiber membrane module was evaluated by hot water filtration or steam sterilization. Furthermore, the chemical resistance stability was evaluated 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.

Examples 10 to 18 U-shaped polyethylene porous membranes were prepared in the same manner as in Example 1 using various botting agents consisting of bisphenol-type epoxy resins, epoxy liquid resins having polysulfide bonds, and alicyclic amines shown in Table 2. A module was created. The module case is made of surface-treated polypropylene resin or polysulfone resin.

The obtained hollow fiber membrane module was evaluated in the same manner as Examples 1 to 9. Table 2 shows the manufacturing conditions and evaluation results of the hollow membrane module.

Comparative Examples 1 to 5 Urethane resin was used as the main ingredient of the potting agent (Comparative Examples 1 and 2), bisphenol-type epoxy resin was used alone (Comparative Example 3), and aliphatic amine was used as the curing agent. A hollow fiber membrane module was created in exactly the same manner as in Example 1 or 10, except that (Comparative Examples 4 and 5) was used. The manufacturing conditions and evaluation results of the membrane module are shown in Tables 1 and 2.

Epicoat 834: Made by Yuka Shell Epoxy ■, epoxy equivalent 250 Ebikoat 282: Made by Yuka Shell Epoxy ■, epoxy equivalent 190 Coronate 4403: Made by Nippon Polyurethane ■ LP-2
, L P-32: Made by Toray Thiokol Liv4 Flep 50: Made by Toray Thiokol ■, epoxy equivalent 330 Flep 1O: Made by Toray Thiokol ■, epoxy equivalent 3
60 Kayabond C-950: Nippon Kayaku ■, amine equivalent 3
8 Power Yahondo C-900: Nippon Kayaku ■, amine equivalent 45 Nipporan 4221: Nippon Polyurethane ■ Epicure T-1 = 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.

Claims (4)

[Claims] (1) The end of the porous membrane housed in the module case contains (a) a bisphenol-type epoxy resin, (b) a polysulfide liquid rubber or an epoxy resin having a polysulfide bond, and (c) an alicyclic amine. A porous membrane module that is potted by curing a potting agent. (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.
The 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.