JPH0226623A - Water-resisting fiber bundle element - Google Patents

Abstract

PURPOSE:To provide sufficiently high water-resisting properties at high temperatures by bonding integrally both opposite end portions of a fiber bundle comprising a number of hollow fibers having permselectivity to a resin plate formed by hardening epoxy resin compositions by heat. CONSTITUTION:Both opposite end portions of fiber bundle 1 comprising a number of hollow fibers having permselectivity are integrally bonded to resin plates 2, 2' respectively which are formed by hardening by heat epoxy resin compositions composed mainly of 100 pts.wt. of phenol novolac type epoxy resin and 0.6-2.0 pts.wt. of imidazole compounds such as 2-methyl imidazole, etc. Even though exposed to water at high temperatures for a long time, the resin plate exhibits sufficiently high water-resisting properties, so that it can be used in separation of gases such as dehydration of organic vapors such as methanol containing moisture, etc., for a long time.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a method for using a large number of hollow fibers having sufficient permselectivity to permeate, separate, and remove moisture from a mixed vapor of organic matter containing moisture. This relates to a water-resistant thread bundle element in which a thread bundle consisting of the above is fixed together with a resin plate heat-cured with a specific water-resistant epoxy resin composition.

Even when the yarn bundle element of the present invention is used to separate a mixture containing moisture, the resin plate of the yarn bundle element has excellent water resistance and does not easily deteriorate due to moisture. .

[Description of prior art]

In recent years, membrane separation processes have been proposed that use permselective separation membranes to dehydrate organic solvents containing water and purify and recover highly pure organic solvents.

The types of separation membrane modules used in this process include plate and frame types, tubular types, and hollow fiber bundle types, but the hollow fiber bundle type has the largest membrane area per unit volume and is therefore advantageous. Needless to say, in manufacturing a hollow fiber type separation membrane module, it is necessary to secure and bind both ends of the fiber bundle with a cured plate (resin plate) of casting resin, and the formation of this resin plate, There were also quite a few problems with performance.

Generally, in the method of gas separation (steam separation) of the vapor of a mixture of water and organic matter, the temperature of the vapor gas needs to be higher than the boiling point, so gas separation is usually performed at a high temperature of 100°C or higher. However, unsaturated polyester resin, polyurethane resin, etc. are generally known as casting resins, but because they have poor heat resistance and solvent resistance, they may deteriorate due to hydrolysis at high temperatures, cause cracks, etc. Because the resin swells, it cannot be used for fixing both ends of a hollow fiber bundle for gas separation.

Recently, a modified epoxy resin obtained by reacting a liquid polybutadiene having a reactive functional group (for example, a carboxyl group) with a phenol novolac type epoxy resin has been used as a resin composition to be formed at both ends of the yarn bundle element. It was disclosed in JP-A-62-1999 that an epoxy resin composition consisting of a resin, a heat-curable curing agent, and a curing accelerator can be used.
Although disclosed in Japanese Patent No. 74434, this known yarn bundle element also did not necessarily have sufficient water resistance, and was not practical for membrane separation of water-containing organic matter vapor.

[Problem to be solved]

That is, an object of the present invention is to provide a hollow fiber 1 having selective permeability to water, for example, in the vapor of an organic material containing water.
A yarn bundle element in which both ends of a yarn bundle are fixed and bound with casting resin, and the resin plate has sufficient water resistance even when exposed to moisture at high temperatures for a long time. It's an expensive resin board.

Another object of the present invention is to provide a yarn bundle element that can be used for a long period of time for gas separation such as dehydration of organic vapor containing water.

[Means for solving problems]

That is, in this invention, both ends of a fiber bundle consisting of a large number of hollow fibers having permselectivity are coated with 100 parts by weight of a phenol novolak type epoxy resin and 0.6 to 0.6 parts by weight of an imidazole compound.
The present invention relates to a water-resistant yarn bundle element characterized in that the element is integrally fixed and bound with a resin plate formed by heating and curing an epoxy resin composition containing 2.0 parts by weight as a main component.

Hereinafter, the present invention will be explained in more detail with reference to the drawings.

FIG. 1 is a perspective view showing an example of a water-resistant yarn bundle element according to the present invention, and FIG. 2 is a separation membrane module incorporating the yarn bundle element of FIG. 1 used for dehydration of organic vapor. It is a sectional view showing an example.

As shown in FIG. 1, the yarn bundle element used in the yarn bundle element of the present invention is capable of selectively transmitting moisture from a mixed vapor of organic matter such as an organic solvent containing moisture, A fiber bundle 1 in which a large number of hollow fiber separation membranes (hollow fiber membranes) formed of asymmetric separation membranes, porous membranes, composite separation membranes, etc. are bundled and cut, and a fiber bundle L thereof. It may be a thermosetting resin plate 2 for fixing and bundling provided at both ends, or a yarn bundle element 3 having a 2° angle.

The fiber bundle has, for example, (1) a length of each hollow fiber of 10 to 5;
00cI11, especially about 20 to 300c11, (
2) The outer diameter of each hollow fiber is 100 to 1500 μm, especially 20
0 to 1000 μm, and (3) a large number of hollow fiber separation membranes (for example, 10 to 500,000, In particular, a yarn bundle bundle in which 100 to 200,000 yarns are bundled with an appropriate bundler and then cut to form a flat opening surface at both ends of the yarn bundle,
Moreover, the diameter (apparent diameter) of the yarn bundle is 0.5 to 10
0 cm, especially about 1.0 to 60 cm is preferable.

The hollow fibers may be any hollow fiber separation membrane made of cellulose acetate, polyamide, polysulfone, polyimide, etc. Hollow fiber separation membranes are most suitable.

Examples of the polyimide include 2.3.3', 4'
or 3.3', 4.4°-biphenyltetracarboxylic acid or its acid dianhydride, 2.3.3'', 4'- or 3,3
',4.4'-A tetracarboxylic acid component whose main component is an aromatic tetracarboxylic acid such as 4'-benzophenonetetracarboxylic acid or its acid dianhydride, or pyromellitic acid or its acid dianhydride, and 4.4 "-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
4.4'-diaminodiphenylmethane, 3.4'-diaminodiphenylmethane, 2.2-bis(4-aminophenyl)propane, 1.4-bis(4-aminophenoxy)benzene, bis(aminophenoxy-phenyl)methane, Bis(aminophenoxy-phenyl)sulfone, 0
-) An aromatic polyimide obtained by polymerizing and imidizing a diamine component whose main component is an aromatic diamine compound such as lysine or 0-tolidine sulfone in approximately equimolar amounts in an organic solvent.

In addition to the above-mentioned aromatic diamine, the diamine component includes, for example, 0-lm- or P-phenylenediamine, 2,4-diaminotoluene, 3,5-diaminobenzoic acid, etc. having one benzene ring. The aromatic diamine may be contained in a proportion of about 20 mol % or less based on the total diamine components.

In this invention, the hollow fibers include a tetraralboxylic acid component whose main component is biphenyltetracarboxylic dianhydride, 3.4°-diaminodiphenyl ether, 4.
Producing a solution of aromatic polyimide obtained by polymerization and imidization from a diamine component whose main component is at least one aromatic diamine selected from the group consisting of 4'-diaminodiphenyl ether and 4.4''-diaminodiphenylmethane. An asymmetric hollow fiber separation membrane made of aromatic polyimide manufactured by a wet membrane forming method using a coagulating liquid and used as a dope for the membrane is preferable in terms of separation performance, heat resistance, durability, and the like.

In the yarn bundle element of the present invention, for example, the yarn bundle of the hollow fibers described above is placed in a mold of a centrifugal molding machine, and then the mold in which the yarn bundle is installed is rotated to form the yarn bundle. While supplying a specific epoxy resin composition to the tip of the yarn bundle, and applying centrifugal force due to the rotation of the mold to the epoxy resin composition at the tip of the yarn bundle in the mold, Any material may be used as long as it is manufactured by heating to a temperature of 50 to 100[deg.] C. and thermosetting to form resin plates at both ends of the yarn bundle.

In addition, in the above-mentioned centrifugal molding, the temperature of 110° C. is further higher by about 20 to 130°C than the temperature during centrifugal molding.
Temperature range of 0-250°C, more preferably 120-250°C
From the viewpoint of durability and mechanical properties of the resin plate, it is appropriate to further post-cure the resin plate of the yarn bundle element in the temperature range 1 of 200”C.

The epoxy resin composition used in this invention includes 100 parts by weight of a phenol novolac type epoxy resin and 0.6 to 2.0 parts by weight, preferably 0.8 to 2.0 parts by weight of an imidazole compound.
This is an epoxy resin composition containing 1.6 parts by weight as a main component.

The phenol novolac type epoxy resin may be any phenol novolac type epoxy resin produced by epoxidizing a phenol resin with epichlorohydrin or the like, and the average molecular weight of the epoxy resin is 300 to 3.
000, and the epoxy equivalent is preferably about 160 to 200.

As the above-mentioned phenol novolac type epoxy resin,
For example, DOW Chemical Company's DEN 431. and D.I.
! N438, and examples include Epicote 152 and Epicote 154 manufactured by Yuka Shell Epoxy ■.

Examples of the imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2ethyl-4
-methylimidazole, 2-undecylimidazole,
2-heptadecyl imidazole, 2-phenylimidazonyl, 1-benzyl-2-methylimidazole 1.1-
Examples include cyanethyl-2-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.

In the above-mentioned epoxy resin composition, if the blending ratio of the imidazole compound is too low, the curing reaction of the epoxy resin composition will be insufficient, making it impossible to obtain a strong resin board, and also if the blending ratio is too high. If it passes,
This is not appropriate because the heat generated during curing of the epoxy resin composition becomes too large, making it impossible to obtain a highly durable resin plate.

The yarn bundle element of the present invention has sufficient heat resistance, water resistance, mechanical strength, and solvent resistance. A separation membrane module in which the Shito element 3 (consisting of a yarn bundle 1 and resin plates 2 and 2'') of the present invention is built into a container 7 having a material extraction port 6, a permeate extraction port 5, etc. The separation membrane module can be used for long-term dehydration operations of various water-containing organic solvents.

The organic solvents to be dehydrated using the separation membrane module incorporating the yarn bundle element of this invention include methanol,
Ethanol, n-propertool, isopropertool, n
- aliphatic alcohols such as butanol, 5ec-butanol, tert-phthanol, ethylene glycol, alicyclic alcohols such as cyclohexanol, aromatic alcohols such as benzyl alcohol, organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, Examples include organic acid esters such as butyl acetate and ethyl acetate, ketones such as acetone and methyl ethyl ketone, cyclic ethers such as tetrahydrofuran and dioxane, organic amines such as butylamine and aniline, and mixtures of the above-mentioned compounds.

The present invention can be preferably used for dehydrating an aqueous solution containing alcohol among the above-mentioned organic substances, and particularly preferably for dehydrating an aqueous solution containing ethanol or isopropanol.

° [Example] Example 1 A tetracarboxylic acid component consisting only of 3.3', 4.4'-biphenyltetracarboxylic dianhydride and 4,4°-
Diaminodiphenyl ether 60 mol% and 4.4'-
A diamine component consisting of 40 mol% of diaminodiphenylmethane was added to about 150% of the diamine component in a p-chlorophenol melt.
Aromatic polyimide is produced by a wet spinning method in which a p-chlorophenol solution of aromatic polyimide obtained by polymerization and imidization at temperatures of A hollow fiber separation membrane was manufactured.

The hollow fiber separation membrane (length: 30 cii, outer diameter: 5
40 μm, inner diameter: 300 μm) and placed them in a mold inside a centrifugal molding machine, heated the mold inside the centrifugal molding machine to 85°C, and while applying centrifugal force by rotation, (a) Phenol novolac type epoxy resin (manufactured by Yuka Shell Epoxy ■, Epicoat 154 (viscosity at 52°C: 350-700 poise, epoxy equivalent: 176-1
81))) and (b) 1 part by weight of 2-ethyl-4-methylimidazole was supplied into a mold and centrifugally molded for 3 hours,
Resin plates were formed on both ends of the hollow fiber bundle to produce a fiber bundle element as shown in FIG. 1, and the fiber bundle element was further heated at 150° C. for 3 hours.
Post-curing of the resin plate was performed.

Using the yarn bundle element manufactured as described above,
The yarn bundle element is placed inside a container 71 having a raw material supply port 4, a non-permeate outlet 6, a permeate outlet 5, etc. as shown in FIG. 2, and the container is sealed. A separation membrane module was manufactured.

Then, while reducing the pressure inside each hollow fiber of the fiber bundle element 3 built into the separation membrane module to 5 amHg, water-ethanol mixed vapor heated to 150°C ( Concentration of ethanol;
80% by weight) is supplied at a pressure of 4 kg/aflG and allowed to flow along the outside of each hollow fiber of the fiber bundle element, causing permeation mainly consisting of water that permeates from the outside of each hollow fiber to the inside. The "vapor" is taken out from the permeate outlet 5, condensed and collected as a permeate by a trap containing dry ice and ethanol, and at the same time, the non-permeated vapor is taken out from the non-permeate outlet 6, and the same process is carried out as above. It was condensed and collected as a non-permeate by a trap.

The above-mentioned water-ethanol mixed vapor separation operation using the separation membrane module was carried out continuously for 1000 hours.
The composition and amount of the collected permeate and non-permeate were measured several times in between, and the water vapor permeation rate (PHZO: d/c+a −
sec - cmHg), and the permselectivity represented by the ratio of the water vapor permeation rate to the ethanol permeation rate (pnzo/PEtOH) was calculated.

As a result, the water vapor transmission rate was 0.7X10-”c4
/cdl -sec .emHg, and the r separation performance j represented by the permselectivity of 96 was maintained almost stably from the beginning of the separation operation to 1000 hours.

After performing the above-described separation operation, the separation membrane module used was disassembled, the yarn bundle element was taken out, and the appearance of the resin plate was inspected, but no abnormal changes were found.

On the other hand, the same epoxy resin composition used to form the resin plate of the yarn bundle element described above was poured into a test tube, and the test tube was heated and cured at 85°C for 3 hours and at 150°C for 3 hours. In this way, a resin rod for a sample having a diameter of 18 mm and a length of 30 mm was manufactured. The resin rod for this sample was immersed in a 60% by weight ethanol aqueous solution, and then the immersed ethanol aqueous solution was heated to a temperature of 130°C and maintained at that temperature for 70 hours, after which changes in its appearance (cracks and The occurrence of cracks) and changes in weight (degree of swelling of the resin rod) were investigated.

After the hot ethanol aqueous solution immersion test was completed, no change in the appearance of the sample resin rod was observed, and the weight of the sample resin rod increased by only 2.13% by weight. Ta.

Comparative Example 1 The epoxy resin was a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy ■, Epicoat 807 (viscosity at 25°C: 20-45 voids, epoxy equivalent: 160-175).
) except that a yarn bundle element was manufactured in the same manner as in Example 1, and then a separation membrane module was manufactured in the same manner as in Example 1.

The separation operation was carried out in the same manner as in the example except that the separation membrane module manufactured as described above was used. However, since the permselectivity was 10 or less from the beginning of the separation operation, the separation operation was After 100 hours from the start, the separation operation was stopped, the separation membrane module was disassembled, the yarn bundle element was taken out, and the appearance was observed. Many fine cracks and cracks had occurred.

On the other hand, as a result of conducting the same r-hot ethanol aqueous solution immersion test as in Example 1 except that the above-mentioned epoxy resin was used,
Many cranks were observed in the sample resin rod after immersion, and the weight of the sample resin rod increased by 3.91% by weight.

Comparative Example 2 As an epoxy resin composition, (a) liquid cis-polybutadiene having a carboxyl group and a phenol novolac type epoxy resin [manufactured by Yuka Shell Epoxy ■, Epicoat 154 (viscosity at 52°C = 350 to 700 poise, epoxy Equivalent: 176-18
100 parts by weight of a modified epoxy resin obtained by reacting 1)) with 1:10 (weight ratio), (b) 80 parts by weight of methylnadic anhydride as a curing agent, and (C) curing accelerator. A yarn bundle element was produced in the same manner as in Example 1, except that an epoxy resin composition consisting of 1 part by weight of 2-ethyl-4-methylimidazole was used as the agent, and further, the yarn bundle element was used. A separation membrane module was manufactured in the same manner as in Example 1 except for the above.

The separation operation was carried out in the same manner as in the example except that the separation membrane module manufactured as described above was used. However, since the permselectivity was below IO from the beginning of the separation operation, the separation operation After 100 hours from the start, the separation operation was stopped, the separation membrane module was disassembled, the yarn bundle element was taken out, and the appearance was observed. Many fine cracks and cracks had occurred.

On the other hand, except for using the above-mentioned epoxy resin, Example 1'
As a result of conducting the same r-heated ethanol aqueous solution immersion test, the sample resin rod had many cracks after immersion, and the weight of the sample resin rod had increased by 8.60% by weight. .

[Actions and effects of the present invention]

The yarn bundle element of this invention has particularly high water resistance because the resin plates at both ends of the yarn bundle are centrifugally formed using an epoxy resin composition with a special composition. The internally installed separation membrane module as shown in FIG. 2 can withstand long-term separation operations for water-containing organic substances, and has excellent durability to maintain separation performance.

[Brief explanation of the drawing]

FIG. 1 is a perspective view showing an example of a water-resistant yarn bundle element according to the present invention, and FIG. 2 is a separation membrane module incorporating the yarn bundle element of FIG. 1 used for dehydration of organic vapor. It is a sectional view showing an example. 1; Hollow fiber bundle, 2; Resin plate, 3; Yarn bundle element,
4; raw material supply port; 5; permeate outlet; 6; non-permeate outlet; 7; container. Patent applicant: Ube Industries, Ltd.

Claims (1)

[Claims] Both ends of a fiber bundle consisting of a large number of hollow fibers having selective permselectivity heat an epoxy resin composition whose main components are 100 parts by weight of a phenol novolac type epoxy resin and 0.6 to 2.0 parts by weight of an imidazole compound. A water-resistant yarn bundle element characterized by being integrally fixed and bound by hardened resin plates.