JP2631245B2 - Water resistant yarn bundle element - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to, for example, a "gas separation having selective permeability", which can selectively separate and purify moisture from a mixture of organic matter and water. The present invention relates to a yarn bundle element formed from "a yarn bundle composed of a large number of hollow fiber membranes". In the present invention, both end portions of the yarn bundle are fixed and bound to a plate with a resin plate obtained by heating and curing an epoxy resin composition including a heat-resistant epoxy resin and diaminonaphthalene, and have water resistance, heat resistance, The present invention provides a practical water-resistant yarn bundle element having durability and the like, and can be used by being incorporated in a gas separation membrane module having the above-mentioned applications such as separation and purification.

[Description of Prior Art]

Conventionally, both ends of the yarn bundle are fixed to form a "yarn bundle element composed of a yarn bundle of a hollow fiber membrane having selective permeability" built in a gas separation membrane joule for separation and purification of an organic substance mixture and the like. Various resin compositions have been conventionally proposed as resin plates to be formed.

For example, as the resin composition described above, JP-A-54-1110
No. 07 discloses a reaction product of a polyglycidyl resin and an imidazole curing agent, and the like.

However, a yarn bundle element formed of a resin plate formed from the above-mentioned known resin composition is required to perform a long-term separation operation when a liquid or a vapor (gas) containing an organic compound is to be subjected to membrane separation. , The resin plate deteriorates, swells, or cracks occur, and the mechanical strength of the resin plate decreases, or the binding adhesion (adhesion) with the hollow fiber decreases, There is a problem that the sealing performance of the yarn bundle is deteriorated.

In order to solve the above-mentioned problem, JP-A-1-2899881 discloses a reaction product (a polyfunctional epoxy compound) of diaminophenylmethane, diaminophenylene, or cyanuric acid with a glycidyl-based compound, a curing agent, It has been proposed to use a resin composition containing a curing accelerator as necessary as an adhesive for binding hollow fibers.

However, even with the above-mentioned resin composition, the mechanical strength of the formed resin plate could not be prevented from lowering.

[Problems to be solved]

An object of the present invention is to provide a yarn bundle element in which a gas-separating hollow fiber membrane having selective permeability is bound by a resin plate having substantially no decrease in mechanical strength while maintaining sufficient heat resistance and water resistance. It is to be.

[Means to solve the problem]

The present invention provides a resin formed by heating and curing an epoxy resin composition comprising a heat-resistant epoxy resin and diaminonaphthalene at both ends of a yarn bundle comprising a plurality of gas-permeable hollow fiber membranes having selective permeability. The present invention relates to a water-resistant yarn bundle element which is integrally fixed and bound by a plate.

1 in the epoxy resin composition used in the present invention.
As the heat-resistant epoxy resin as a component, for example, a polyfunctional epoxy resin such as a phenol novolak type epoxy resin and a glycidylamine type epoxy resin can be preferably exemplified.

Further, as the diaminonaphthalene as another component of the epoxy resin composition, 1,8-diaminonaphthalene,
Preferable examples include 2,4-diaminonaphthalene and 2,6-diaminonaphthalene, and 1,8-diaminonaphthalene is particularly preferred.

In the epoxy resin composition, diaminonaphthalene 10 to 50 parts by weight based on 100 parts by weight of the heat-resistant epoxy resin.
Parts by weight, especially the blending ratio to be about 15 to 45 parts by weight, the workability of molding the resin plate at the end of the yarn bundle, and
It is preferable in terms of heat resistance, water resistance, mechanical strength and the like of the formed resin plate.

The epoxy resin composition has a curing temperature of 60 to 160.
C, particularly preferably about 70 to 150 C,
The solution viscosity (rotational viscosity) around the curing temperature (curing temperature ± 10 ° C.) is preferably 0.01 to 10 poise, particularly about 0.1 to 5 poise, by centrifugal molding or standing the resin plate at the end of the yarn bundle. In molding or the like, it is preferable because the composition can quickly and easily penetrate and fill the gaps between the hollow fibers at the end of the yarn bundle, and the composition can be easily cured.

As the “gas separation hollow fiber membrane having selective permeability” used in the present invention, for example, water is selected as water vapor from the liquid or vapor such as a mixture of an organic substance and water on the permeation side of the gas separation hollow fiber membrane. Any gas-separating hollow fiber membrane that can be selectively permeated and dewatered may be used. For example, an asymmetric gas-separating hollow fiber membrane made of aromatic polyimide [a very thin dense layer (outer layer) and a considerably thick porous layer Hollow fiber membrane having a layer (supporting inner layer) (outer diameter: about 100 to 800 μm, thickness: about 100 to 100 μm)].

Examples of the aromatic polyimide include: (a) an aromatic tetracarboxylic acid component containing biphenyltetracarboxylic acid or its dianhydride as a main component (60 mol% or more); and (b) at least two aromatic tetracarboxylic acid components. An organic solvent-soluble aromatic polyimide obtained by polymerizing and imidizing an aromatic diamine component containing an aromatic diamine compound having a benzene ring as a main component (60 mol% or more) in an organic solvent [logarithm at 50 ° C.] Viscosity (concentration; 0.5g /
100 solvent, solvent; parachlorophenol) is 0.5 to 5, especially about 1 to 4 polyimide)], the heat resistance of the hollow fiber membrane, Suitable examples include water resistance.

Examples of the aromatic diamine compound having two or more benzene rings include 1,4-diaminodiphenyl ether, 1,4
-Diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 1,4-diaminodiphenylsulfone, bis (4-aminophenyl) benzene, bis (4-
Examples thereof include (aminophenoxy) benzene, bis (3-aminophenoxy) benzene, and 4,4′-bis (p-aminophenoxy) diphenyl ether.

Further, as the aromatic diamine component, an aromatic diamine compound having one benzene ring such as 2,5-aminobenzoic acid or diaminophenylene may be used in a small proportion at the above-mentioned “aromatic having 2 to 4 benzene rings”. Diamine compound "
It is also possible to use them together.

As the aromatic tetracarboxylic acid component, 3,3 ′,
4,4'- or 2,3,3 ', 4'-biphenyltetracarboxylic acid or its dianhydride can be used alone,
Along with the above-mentioned biphenyltetracarboxylic acids, pyromellitic acid or its dianhydride, benzophenonetetracarboxylic acid or its dianhydride, biphenylethertetracarboxylic acid or its dianhydride can be used in a small proportion.

In the present invention, the yarn bundle of the gas separation hollow fiber membrane described above is:
The length of the hollow fiber membrane is 10 to 200 cm, particularly about 20 to 150 cm, and the number of the hollow fiber membrane is 10 to 500,000, particularly 100 to 200,000, and further 1,000 to 100,000. Preferably, the outer diameter of the yarn bundle is about 1 to 50 cm, particularly about 3 to 30 cm.

In the yarn bundle element of the present invention, the thickness of the resin plate provided at the end of the yarn bundle is 5 to 20 cm, particularly 6 to 15 cm.
And the diameter of the resin plate is preferably about 1.001 to 1.05 times that of the external system of the yarn bundle.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples and the like.

Example 1 An asymmetric gas-separating hollow fiber membrane made of an aromatic polyimide obtained from biphenyltetracarboxylic dianhydride and diaminodiphenyl ether (length: 25 cm, outer diameter: 500
μm, film thickness: 100 μm) to form a yarn bundle, and insert both ends of the yarn bundle into an “injection mold” installed in a centrifugal molding machine. Then, while rotating the mold of the centrifugal molding machine at a high speed, 49.1 g of phenol novolak type epoxy resin (EP154, manufactured by Yuka Shell Co., Ltd.) and 10.9 g of 1,8-diaminonaphthalene
And a resin composition (viscosity at 90 ° C .: 1.5 poise)
The resin composition was poured into the casting mold to impregnate both ends of the yarn bundle with the resin composition. Further, the mold was heated at 90 ° C. for 4 hours and then at 180 ° C. for 4 hours to obtain the resin. The composition is cured to form resin plates at both ends of the yarn bundle. Finally, the cured portions (resin plates) of the resin composition at both ends of the yarn bundle are cut, and both ends of each hollow fiber are cut. Open the
A yarn bundle element was formed.

In the formation of the yarn bundle element, the resin composition was effectively filled in each gap of the gas separation hollow fiber membrane of the yarn bundle.

The yarn bundle element was housed in a pressure vessel and sealed to form a gas separation membrane module.

The permeation side (inside of the hollow fiber) of the gas separation hollow fiber was reduced to 100 torr by the above-mentioned gas separation membrane module, and ethanol /
Steam mixed with water (95 parts by volume of ethanol and 5 parts by volume of water) is supplied at a temperature of 150 ° C. and a pressure of ² kg / cm ² , and is subjected to steam dehydration by membrane separation. For 3 months to obtain ethanol with moisture removed.

In the dehydration operation of the separation of _{α (PH 2 O / PC 2} H 5 OH) represented by the ratio of the permeation rate PC ₂ H ₅ OH in the transmission rate PH ₂ O and ethanol vapor is 360, 3 months During this time, no decrease in gas separation performance was observed.

In the separation membrane module, after the dehydration operation described above, cracks, erosion, expansion, and the like of the resin plate of the incorporated yarn bundle element are not changed in appearance, and the resin plate between the hollow fibers of the yarn bundle is bonded by the resin plate. The properties were also good.

After the dehydration operation, the separation membrane module was subjected to a sealing test by measuring the amount of N ₂ gas permeated through the gas separation hollow fiber membrane. As a result, there was no problem.

Example 2 An epoxy resin composition was prepared by mixing 45 g of a glycidylamine-type polyfunctional epoxy resin (EP604, manufactured by Yuka Shell Co., Ltd.) and 15 g of 1,8-diaminonaphthalene (viscosity at 60 ° C .: 1 poise). ), A yarn bundle element was formed in the same manner as in Example 1.

In the formation of the yarn bundle element, the resin composition was effectively filled in each gap of the gas separation hollow fiber membrane of the yarn bundle.

The yarn bundle element was housed in a pressure vessel and sealed to form a gas separation membrane module.

Aside from supplying a mixed vapor of ethanol / water at 120 ° C. and 2 kg / cm ² to the gas separation membrane module in which the permeate side (inside of the hollow fiber) of the gas separation hollow fiber membrane was reduced to 60 torr,
A dehydration operation was performed in the same manner as in Example 1.

In the dehydration operation of the separation of _{α (PH 2 O / PC 2} H 5 OH) represented by the ratio of the permeation rate PC ₂ H ₅ OH in the transmission rate PH ₂ O and ethanol steam, it is an average of about 360 No decrease in gas separation performance was observed for three months.

In the separation membrane module, after the dehydration operation described above, cracks, erosion, expansion, and the like of the resin plate of the incorporated yarn bundle element are not changed in appearance, and the resin plate between the hollow fibers of the yarn bundle is bonded by the resin plate. The properties were also good.

After the dehydration operation, the separation membrane module was subjected to a sealing test by measuring the amount of N ₂ gas permeated through the gas separation hollow fiber membrane. As a result, there was no problem.

Reference Experimental Example 1 The epoxy resin composition used in Example 2 was poured into a cylindrical mold having a height (depth) of 3 cm and a diameter of 2 cm, and was injected at 60 ° C. for 5 hours and at 120 ° C. for 1 hour. Post-curing was performed at 140 ° C. for 1 hour, at 160 ° C. for 1 hour, and at 180 ° C. for 4 hours to form a column (cured product) having the above-mentioned size.

This cylindrical molded product was immersed in a 60% aqueous ethanol solution at 130 ° C. for 70 hours under N ₂ gas pressure to evaluate the solvent resistance and durability of the cured product.

After the test, the cylinder had no change in cracks, erosion, swelling, etc., and the weight increase was 1.96% by weight.

A test similar to the above-mentioned solvent resistance and durability test was conducted, except that pure water was used. As a result, no change was observed after the test, and the weight increase rate was 4.1% by weight.

In addition, the cylinder which is a cured product of the above-described epoxy resin composition has a compression elastic modulus of 293 kg / mm ² and a compression yield point strength of 20 kg / m.
m ² , compressive breaking strength: 28.1 kg / mm ² , flexural modulus: 343 kg / m
m ^2, bending strength: 8.0kg / mm ^2, (after immersion for 120 hours in water of the samples 130 ° C., measured at 170 ° C.) hot wet test at a high temperature and high moisture resistance test flexural modulus at: 112 kg / mm ² ,
Flexural strength of the hot wet property test: 3.3 kg / mm ² ,
And HDT (thermal denaturation temperature): 223 ° C.

The mechanical properties of the cylinder, which is a cured product of the epoxy resin composition, are excellent in bending properties, and particularly excellent in the hot wet test.

Also, the resistance to ethanol in the immersion test of immersion in a 60% by weight aqueous ethanol solution at 130 ° C. for 70 hours is extremely excellent.

That is, the resin plate forming the yarn bundle element of the present invention has excellent durability against high-temperature organic solvent vapor and water vapor and mechanical properties.

(Operation and effect of the present invention)

The yarn bundle element of the present invention has excellent heat resistance and is bound by a resin plate having extremely selected durability against high-temperature organic solvent vapor and water vapor. A module can be formed and used suitably for gas separation of a mixed vapor of organic vapor and water vapor.

Claims (1)

(57) [Claims] 1. A yarn bundle comprising a plurality of gas permeable hollow fiber membranes having selective permeability, both ends of which are made of a heat-resistant epoxy resin,
A water-resistant yarn bundle element, which is integrally fixed and bound by a resin plate formed by heating and curing an epoxy resin composition comprising diaminonaphthalene.