JPH0678510B2 - Hollow fiber binding adhesive - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hollow fiber binding adhesive. More specifically, the present invention relates to a hollow fiber binding adhesive for adhering ends of a permselective hollow fiber membrane used for separating and collecting components of a gas or liquid mixture.

[Conventional technology]

The separation process of recovering a specific component from a mixture of gas, liquid, etc. using a separation membrane has been widely noticed by the industrial world as an energy-saving separation method, and development of a fluid separation device used in such a separation process is expected. .

Among the fluid separation devices, the hollow fiber membrane has not only the advantage that the packing density of the membrane is high and the effective membrane area is large as compared with the film-shaped flat membrane, but it is also excellent in pressure resistance and self-supporting property. Therefore, it is industrially very useful and can be widely used.

Since the hollow fiber-containing fluid separation device can be packed to have a high membrane surface area per unit volume, many fluid separation operations can be performed.
For example in gas-gas, gas-liquid, liquid-gas and liquid-liquid separations, the device can be made quite compact.

In these fluid separation devices, at least one end of each hollow fiber is embedded and fixed in an adhesive agent, and the fluid on the primary side and the permeate fluid on the secondary side are sealed. In the fluid separation device using the hollow fibers, the performance of the adhesive as the hollow fiber binding agent has an important influence on the performance of the selective hollow fiber membrane.

Conventionally, a wide variety of resins have been proposed as such adhesives. For example, JP-A-56-111007 discloses a polyglycidyl resin and an imidazole curing agent, and JP-A-58-61.
No. 162 describes a composition of bisphenol A glycidyl resin and a specific curing agent.

[Problems to be solved by the invention]

The hollow fiber binding adhesive of such a fluid separation device is generally used for fluid separation of a chemical plant containing a deteriorating substance, particularly for a liquid containing an organic compound, deterioration due to long-term operation, swelling, It is required that the mechanical strength does not decrease due to cracks or the like and the adhesiveness between the hollow fiber and the hollow fiber binding adhesive does not decrease.

Conventionally proposed resins have drawbacks such as swelling, deterioration, erosion, deterioration of mechanical strength due to cracks, adhesion to hollow fibers, etc. for applications such as separation of organic solvents. However, there is a problem that it can be applied only to limited uses.

[Means for solving problems]

The present inventors have diligently studied an adhesive for forming the end portion of the hollow fiber in manufacturing the hollow fiber module of the fluid separation device. As a result, a polyfunctional compound obtained by reacting diaminodiphenylmethane with a glycidyl compound is obtained. It was found that epoxy resin containing epoxy compound is remarkably excellent in chemical resistance, heat resistance and mechanical strength, and is useful for obtaining a fluid separation module having good hollow fiber binding moldability and durability. Has reached the present invention.

That is, the gist of the present invention is characterized by containing at least one polyfunctional epoxy compound represented by the following general formula (I), (II) or (III), a curing agent, and, if necessary, a curing accelerator. Hollow fiber binding adhesive, (In the formula, R _{1 to} R ⁴ are H or Represents three or more of R ^{1 to} R ⁴ Is. ) (In the formula, R ^{1 to} R ⁴ are H or Represents However, at least ^one of R ¹ and R ² and R ³ ,
One of R ⁴ Is. ) (In the formula, R ^{1 to} R ³ are H or And at least two of R ^{1 to} R ³ are Is. The polyfunctional epoxy compound represented by the general formula (I) used in the present invention is a trifunctional or tetrafunctional epoxy compound which is usually obtained by reacting diaminodiphenylmethane with epihalohydrin. Specific examples thereof include triglycidylated diaminodiphenylmethane and tetraglycidylated diaminodiphenylmethane, but a mixture of both may be used.

The polyfunctional epoxy compound represented by the general formula (II) used in the present invention is usually obtained by reacting xylylenediamine with epihalohydrin. Specific examples of the polyfunctional epoxy compound include diglycidylated xylene diamine, triglycidylated xylene diamine, tetraglycidylated xylene diamine, and the like, with preference given to tri- or tetraglycidylated xylene diamine. It may also be a mixture of two or more of di, tri and tetraglycidylated xylenediamine.

The polyfunctional epoxy compound represented by the general formula (III) used in the present invention is usually obtained by reacting cyanuric acid with epihalohydrin. Specific examples of the polyfunctional epoxy compound include diglycidyl isocyanurate and triglycidyl isocyanurate, but triglycidyl isocyanurate is preferable. Further, it may be a mixture of di, tri, and glycidyl isocyanurate.

The polyfunctional epoxy compound represented by the formula (I), (II) or (III) may be used alone, but it is usually used as a mixture with another polyfunctional epoxy compound. In this case, the amount of the polyfunctional epoxy compound of the formula (I), (II) or (III) can be arbitrarily selected depending on the structure of the other polyfunctional epoxy compound to be added, but it is usually based on the whole polyfunctional epoxy compound. It is 10 mol% or more, preferably 25 mol% or more. When the proportion of the polyfunctional epoxy compound of the formula (I), (II) or (III) of the present invention is extremely low, the properties as a hollow fiber binding adhesive such as heat resistance, solvent resistance and mechanical strength are improved. It is not preferable to decrease.

Other multifunctional epoxy compounds that may be useful in combination with the multifunctional epoxy compound of formula (I), (II) or (III) include, for example, epichlorohydrin and bisphenol A, resorcinol, catechol, hydroquinone, fluoro. Logricinol, 4,4'-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) ethane, bis (2-hydroxynaphthyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 4,4 ' -Dihydroxydiphenyl sulfone, ethylene glycol, propylene glycol, butanediol, pentanediol, isopentanediol, linoleic acid dimer, poly (oxypropylene) glycol, 2,4,4'-trihydroxybisphenyl, 2,2 ', 4,4'-tetrahydroxybisphenyl, bisresorcinol F, 2, 2 ', 4,4'-
Tetrahydroxybenzophenone, bisphenol hexafluoroacetone, aniline, p-aminophenol, isocyanuric acid, hydantoin, 1,1 ', 2,2'-
All poly, including glycidyl reaction products with any compound selected from tetra (p-hydroxyphenyl) ethane, phenol, formaldehyde novolac, o-cresol-formaldehyde novolac, cycloaliphatic alcohols and mixtures thereof. A glycidyl resin may be used.

Among these, preferred polyfunctional epoxy compounds include
Mention may be made of bisphenol A, phenol-formaldehyde novolac, or polyfunctional epoxy compounds obtained by the reaction of o-cresol-formaldehyde with epichlorohydrin.

Examples of the curing agent and curing accelerator used in the present invention include polyamine curing agents, oxidative curing agents and amine curing accelerators.

Examples of the polyamine curing agent and the amine curing accelerator include isopropylamine, polymethylenediamine, polyalkyletherdiamine, dialkylenetriamine (eg, diethylenetriamine), trialkylenetetramine (eg, trimethylenetetramine), diethylaminopropylene, N-aminoethyl. Ethanolamine,
N, N-benzyldimethylamine, 1,3-bis (dimethylamino) -2-propanol, menthanediamine, aminoethylpiperazine, 1,3-diaminocyclohexane, bis (p-aminocyclohexyl) methane, m-phenylenediamine, m-xylylenediamine, 4-, 4'-diaminodiphenylmethane, diaminodiphenyl sulfone,
Isophorone diamine, piperazine, N-methylpiperazine, piperidine, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), tri-2-ethylhexanoate salt of DMP-30, modified aliphatic polyamines such as Halohydrin ether of glycol polyamine adduct (adduct), dimethamine adduct of allocymen diepoxide,
Aminoalkoxysilane adduct of propylene oxide,
Examples of the hydroxypolyamine and other oxidative curing agents include boron trifluoride, aluminum chloride, boron trifluoride monoethylamine, maleic anhydride, phthalic anhydride, chlorendic anhydride, pyromellitic dianhydride, and benzophenone tetra. Carboxylic dianhydride, dodecenyl succinic anhydride, methyl nadic acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and others, amides such as phosphorus amide [eg p-phenylene bis (anilinophenylphosphine oxide)], urea (Including substituted urea and urea-formaldehyde), N, N-diallyl melamine, triallyl cyanurate, hydrazide, amino acetals such as bis (2-dimethylaminoethoxy) methane, bis (1-dimethylamino-2-propoxy) methane. , 1,6-bis (2- Methylaminoethoxy) hexane, alpha,. Alpha .'- bis (2-dimethylaminoethoxy) -
p-xylene, bis (3-dimethylamino-1-propoxy) methane, 2,6-bis (2-dimethylaminoethoxy) pyridine, 2,6-bis (1-dimethylamino-2-)
Propoxy) pyridine, 2,6-bis (3-dimethylamino-1-propoxy) pyridine, bis (2-dimethylaminoethoxy) methane, bis (2-N-morpholinoethoxy) methane, 1,1-bis (2- Dimethylaminoethoxy) propane, 2,2-bis (2-dimethylaminoethoxy) propane, α, α′-bis (2-dimethylaminoethoxy) toluene, 1,1-bis (2-dimethylaminoethoxy) butane, 1 1,1-bis (2-dimethylaminoethoxy) ethane, 1,1,2,2-tetrakis (2-dimethylaminoethoxy) ethane and the like.

Particularly preferable as the curing agent is an alicyclic or aromatic diamine. These diamines include 4,4'-
Preferable examples include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine and the like.

The amount of the curing agent used is usually an epoxy equivalent, and when a curing accelerator is used, the amount of the curing accelerator used is usually 0.01 to several parts by weight with respect to 100 parts by weight of the epoxy compound.

To bind hollow fibers using the adhesive of the present invention, a composition obtained by uniformly mixing the polyfunctional epoxy compound of the formula (I), (II) or (III), a curing agent and, if necessary, a curing accelerator. The hollow fibers can be bound by injecting into a casting mold in which a bundle of a large number of hollow fibers is inserted, and gradually heating and curing.

The curing temperature is appropriately determined depending on the shape, size, etc. of the composition, but the final curing temperature is preferably 80 ° C or higher, and particularly preferably 150 ° C or higher for 0.1 to 24 hours. It is possible to obtain an adhesive for bundling hollow fibers, which has properties and chemical resistance.

By using the hollow fiber binding adhesive of the present invention, the hollow fiber module of the fluid separation device can be easily industrially molded by a stationary method, a centrifugal molding method or the like.

Examples of the hollow fiber membrane applicable to the present invention include natural and synthetic polymers such as polysulfone, polyether sulfone, polyamide, polyamideimide, polyimide, polyphenylene oxide, cellulose acetate, polyacrylonitrile, polystyrene, polyester, or their copolymers. A polymer or derivative formed into a hollow fiber membrane by a wet or cyclic spinning method is preferably used. In addition to this, a composite hollow fiber separation membrane in which a polymer compound is laminated on these hollow fiber membranes can be used, but is not limited thereto.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto without departing from the gist thereof.

Example-1 A hollow fiber separation membrane made of polyimide (1000 pieces) is bound,
18 g of diglycidyl ether bisphenol A, 12 g of tetraglycidyl diaminodiphenylmethane, 21 g of diaminodiphenyl sulfone and 16 g of isophoronediamine are poured into a casting mold to bond the hollow fiber ends and left at 20 ° C for 10 hours. Then, curing was performed under conditions of 100 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 5 hours. After cutting one side and opening the hollow fiber, the hollow fiber module was sealed in a pressure vessel. Through this fluid separator, a mixed solution of water / ethanol = 5/95 (weight ratio) was circulated under the condition of 95 ° C (pressure 5kg / cm ² G), the secondary side was set to 30 Torr, and the pervaporation method was used. A dehydration test of ethanol was conducted.

The water / ethanol separation ratio was 850, and there was no change over time in the performance for one month.

No change in the appearance of the epoxy resin (crack, erosion) was observed after the test, and the adhesiveness between the hollow fiber and the adhesive was good.

Example-2 Using the hollow fiber module produced in Example-1, water /
Add a mixture of isopropyl alcohol = 1/88 (weight ratio) to 75
It was circulated under the condition of ° C and the secondary side was set to 30 torr, and a dehydration test of isopropyl alcohol was conducted by a paper vaporization method.

The water / isopropyl alcohol separation ratio is 3500, which is 1
No change in performance was observed over the months.

No change in the appearance (crack, erosion, swelling) of the epoxy resin used for binding the hollow fibers after the test was observed, and the adhesion between the hollow fibers and the adhesive was good.

Example-3 The hollow fiber module produced in Example-1 was treated in an acetone bath at 90 ° C. for 9 hours, and then a mixture of water acetone = 3/97 (weight ratio) was treated at 90 ° C. (pressure 5 kg / cm ² -G) was circulated and the secondary side was set to 30 torr, and a dehydration test of acetone was conducted by a pervaporation method.

The water / acetone separation ratio was 80, and there was no change over time in the performance for one month.

No change in the appearance (crack, erosion, swelling) of the epoxy resin used for binding the hollow fibers after the test was observed, and the adhesion between the hollow fibers and the adhesive was good.

Example-4 A cylinder having a height of 1 cm and a diameter of 3 cm was formed without using a hollow fiber by using the same adhesive composition as in Example-1, and after standing at 20 ° C for 10 hours, 100 ° C-1 hour, Further 150 ℃ -1 hour, further 18
Post cure was performed under the condition of 0 ° C. for 5 hours.

Immerse this molded product in acetone solution, first at 90 ° C for 10 hours,
Then, it was left at room temperature for 14 hours, and this was repeated for 60 days to evaluate the solvent resistance and durability of the adhesive. No changes in appearance such as cracks, erosion and swelling were observed.

Example-5 A hollow fiber separation membrane made of polyimide (1000 pieces) was bound,
A composition in which 50 g of an epoxy compound in which diglycidyl ether bisphenol A and tetraglycidylated xylenediamine are mixed in a 1.4 / 1 molar ratio and 21 g of a curing agent in which diaminodiphenylmethane and isophoronediamine are mixed in a 1/1 molar ratio are uniformly mixed. Is poured into a casting mold and the ends of the hollow fibers are bonded, left at 20 ° C for 10 hours, then at 90 ° C for 3 hours, then at 177 ° C.
Curing was carried out under the condition of 5 hours. The heat distortion temperature (HDT) of this product was 168 ° C. After cutting one side and opening the hollow fiber, the hollow fiber module was sealed in a pressure vessel.

A pervaporation method was performed by passing a mixed liquid of water / ethanol = 5/95 (weight ratio) through this fluid separator under the conditions of 95 ° C (pressure 5 kg / cm ² -G) and setting the secondary side to 30 Torr. The dehydration test of ethanol was performed by.

The water / ethanol separation ratio was 850, and there was no change over time in the performance for one month.

No change in the appearance of the epoxy resin (crack, erosion) was observed after the test, and the adhesiveness between the hollow fiber and the adhesive was good.

Example-6 Using the hollow fiber module produced in Example-5, water /
Add a mixture of isopropyl alcohol = 12/88 (weight ratio) to 7
A dehydration test of isopropyl alcohol was conducted by a pervaporation method with circulation at 5 ° C. and a secondary side of 30 Torr.

The water / isopropyl alcohol separation ratio is 3,500,
There was no change over time in the performance for one month.

No change in the appearance (crack, erosion, swelling) of the epoxy resin used for binding the hollow fibers after the test was observed, and the adhesion between the hollow fibers and the adhesive was good.

Example-7 The hollow fiber module produced in Example-5 was treated in an acetone bath at 90 ° C for 9 hours, and then a mixture of water / acetone = 3/97 (weight ratio) was added at 90 ° C (pressure 5 kg / cm). ^2- G) was circulated and the secondary side was set to 30 torr, and a dehydration test of acetone was conducted by a pervaporation method.

The water / acetone separation ratio was 80, and there was no change over time in the performance for one month.

No change in the appearance (crack, erosion, swelling) of the epoxy resin used for binding the hollow fibers after the test was observed, and the adhesion between the hollow fibers and the adhesive was good.

Example-8 A column having a height of 1 cm and a diameter of 3 cm was molded using the same adhesive composition as in Example-5 without inserting a hollow fiber, and after standing at 22 ° C for 75 hours, 100 ° C-3 hours, Post-cure was performed under the condition of 177 ° C. for 5 hours.

Immerse this molded product in acetone solution, first at 90 ° C for 10 hours,
Then leave it at room temperature for 14 hours, repeat this for 60 days,
The solvent resistance and durability of the adhesive were evaluated.

No changes in appearance such as cracks, erosion and swelling were observed.

Example-9 A hollow fiber separation membrane made of polyimide (1000 pieces) was bound,
Triglycidyl isocyanurate 25 g, methyl nadic acid anhydride 39 g, and N, N-benzylmethylamine 0.25 g of a composition uniformly mixed were poured into a casting mold to bond the hollow fiber ends, and the mixture was stirred at room temperature for 15 After left for 130 hours-2 hours, then 150 degrees
It was cured under the conditions of -3 hours and 230 ° C-17 hours.

One side was cut, the hollow fiber was opened, and then the hollow fiber module was sealed in a pressure vessel.

A water / ethanol = 5/95 (weight ratio) mixture was passed through this fluid separator under conditions of 95 ° C (pressure 5 kg / cm ² -G) to a secondary side of 30 Torr, and ethanol was applied by pervaporation. The dehydration test was performed.

The water / ethanol separation ratio was 850, and there was no change over time in the performance for one month.

No change in the appearance of the epoxy resin (crack, erosion) was observed after the test, and the adhesion between the hollow fiber and the adhesive was good.

Example-10 Using the hollow fiber module manufactured by the same method as in Example-9, a mixed solution of water / isopropyl alcohol = 12/88 (weight ratio) was circulated under the condition of 75 ° C. Then, a dehydration test of isopropyl alcohol was conducted by a pervaporation method.

The water / isopropyl alcohol separation ratio is 3500, which is 1
No change in performance was observed over the months.

No change in the appearance (crack, erosion, swelling) of the epoxy resin used for binding the hollow fibers after the test was observed, and the adhesion between the hollow fibers and the adhesive was good.

Example-11 A hollow fiber module manufactured by the same method as in Example-9 was treated in an acetone bath at 90 ° C for 9 hours, and then water / acetone = 3 /
A 97 (weight ratio) mixed solution was passed under the conditions of 90 ° C. (pressure 5 kg / cm ² -G), the secondary side was set to 30 Torr, and a dehydration test of acetone was performed by a pervaporation method.

The water / acetone separation ratio was 80, and there was no change over time in the performance for one month.

No change in the appearance (crack, erosion, swelling) of the epoxy resin used for binding the hollow fibers after the test was observed, and the adhesiveness between the hollow system and the adhesive was good.

Example-12 A cylinder having a height of 1 cm and a diameter of 3 cm was molded using the same adhesive composition as in Example 9 without inserting a hollow fiber, and after standing at 22 ° C for 7 hours, 130 ° C-2 hours, and further. 150 ℃ -3 hours, 230
Post-cure was performed under the condition of -17 ° C.

Immerse this molded product in acetone solution, first at 90 ℃ -10 hours,
Then, it was left at room temperature for 14 hours, and this was repeated for 160 days to evaluate the solvent resistance and durability of the adhesive.

No changes in appearance such as cracks, erosion and swelling were observed.

Comparative Example-1 The following triglycidyl compound of meta-aminophenol 100
Parts by weight, 151 parts by weight of methyl nadic acid anhydride and 3 parts by weight of N, N-benzyldimethylamine are uniformly mixed to form a cylinder of 1 cm × 3 cmφ, 120 ° C.-3 hours, further 150 ° C.-8 hours, further
It was cured at 180 ° C. for 8 hours. This molded product was immersed under the same conditions as in Example-4. When observed one day later, the surface of the molded product was eroded and partly dropped off.

Comparative Example-2 100 parts by weight of dichlycidyl ether bisphenol A, 93 parts by weight of methyl nadic acid anhydride, and 3 parts by weight of N, N-benzyldimethylamine were uniformly mixed, and molded and cured under the same conditions as in Comparative Example-1, An immersion test was conducted. When observed 15 days later, cracking was observed and eroded holes were observed on part of the surface.

〔The invention's effect〕

This hollow fiber binding adhesive has no drawbacks such as erosion in high temperature organic solvents such as acetone, ethanol, hexane, isopropyl alcohol, and butyl acetate, generation of cracks, and deterioration of adhesion with hollow fibers due to swelling. Has excellent chemical resistance.

Moreover, since this adhesive has sufficient heat resistance and mechanical strength, it is particularly useful for separating organic solvents by the pervaporation method (pervaporation method), but it is also useful for gas separation containing chemically active substances. It can also be suitably used in applications such as ultrafiltration and reverse osmosis to remove solutes in organic solvents.

Claims (1)

[Claims] 1. The following general formula (I), (II) or (III)
An adhesive for bundling hollow fibers, comprising at least one polyfunctional epoxy compound represented by, a curing agent, and, if necessary, a curing accelerator. (In the formula, R ^{1 to} R ⁴ are H or Represents three or more of R ^{1 to} R ⁴ Is. ) (In the formula, R ^{1 to} R ⁴ are H or Represents However, at least ^one of R ¹ and R ² and R ³ and R
⁴ either Is. ) (In the formula, R ^{1 to} R ³ are H or And at least two of R ^{1 to} R ³ are Is. )