JP2841670B2 - Liquid separation material, liquid absorption separation material and liquid separation method using them - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a liquid separation material and a liquid absorption separation material using an alkylene oxide graft polyamide, and contains water, alcohol, chlorinated hydrocarbon and amines. It relates to a method for separating its contents from a liquid mixture.

[Conventional technology]

Conventionally, various polymer films have been proposed as functional films,
Membrane separation is used in place of distillation and rectification that require a large amount of energy in the conventional chemical industry, and application to liquid mixture separation in biotechnology and medical fields Applications of molecular membranes are becoming increasingly popular, and their applications are also expanding.

[Problems to be solved by the invention]

However, the permeation selectivity of polymer membranes is specific, and various membranes are used depending on the field of application, and various polymer membrane technologies are still in the development stage.

The inventors of the present invention have studied alkylene oxide graft polyamides for the purpose of modifying nylon, focusing on their functionality, and as a result, have found that they have liquid-liquid separation ability, and have reached the present invention.

Alkylene oxide graft polyamide, polyamide, ethylene oxide, 1,2-propylene oxide, can be obtained by a graft reaction with a _C2-4 1,2-alkylene oxide such as 1,2-butylene oxide, for example, It is already known in JP-A-47-897 and the like. These alkylene oxide-grafted polyamides are used for the purpose of modifying nylon as described above, and are mainly used to improve the hydrophilicity and antistatic properties of the polyamide, and mention the function of liquid separation of a liquid mixture. Nothing was done.

An object of the present invention is to provide a novel liquid-separating material and a liquid-absorbing separating material of a polyamide system by focusing on the functionality of the liquid-liquid separation of the alkylene oxide-grafted polyamide, and more particularly, water, alcohol, and chlorination. It is an object of the present invention to provide a liquid separation material that selectively separates a hydrocarbon and an amine from a liquid mixture containing the same and a liquid separation method using the liquid absorption separation material.

[Means for solving the problem]

According to the present invention, 1,2
-A liquid separating material comprising an alkylene oxide-grafted polyamide film obtained by grafting an alkylene oxide.

Further, according to the present invention, using a liquid separating material comprising an alkylene oxide graft polyamide film obtained by grafting 1,2-alkylene oxide to an unstretched polyamide film, water, alcohol, chlorinated hydrocarbon and A liquid separation method is provided, which comprises separating a compound containing a amine from a liquid mixture containing at least one of the amines.

Further, according to the present invention, there is provided a liquid absorption / separation material comprising an alkylene oxide-grafted polyamide and having excellent liquid absorption ability.

Furthermore, according to the present invention, using a liquid absorption separation material comprising an alkylene oxide graft polyamide,
A liquid absorption separation method is provided, wherein a compound contained in a liquid mixture containing at least one of water, alcohol, chlorinated hydrocarbon and amines is absorbed and separated.

 Hereinafter, the present invention will be described in more detail.

The alkylene oxide graft polyamide (hereinafter, simply referred to as a graft polyamide) used in the present invention is a polyamide and a _C2-4 1,2-- such as ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide. It can be obtained by reacting with an alkylene oxide.
As the polyamide, typical nylons such as nylon 6, nylon 66, nylon 610, nylon 11, and nylon 612 can be used.

The graft polyamide of the present invention has 1,2-
It may be obtained by using any known method for grafting an alkylene oxide. Usually, using the above-mentioned nylon powder or pellets, or film-like nylon and the above-mentioned alkylene oxide in a molar ratio of about 1: 0.5 to 10 without catalyst, in an autoclave under an inert gas atmosphere such as nitrogen, about 100 ° C. It can be obtained by holding for a predetermined time below to remove unreacted substances and homopolymers of alkylene oxide.

In this case, the graft polyamide obtained by the method described in JP-A-47-897 is water-soluble and is not preferred because it is limited in terms of conditions for use as a dispersant.

The graft ratio of the 1,2-alkylene oxide of the graft polyamide used in the present invention is not particularly limited, but usually, the liquid permeability increases with an increase in the graft ratio. Can be used. Generally, it is preferred to use a graft polyamide having a graft ratio of about 30% or more, preferably about 50% or more.

The graft polyamide obtained as described above is mainly one in which 1,2-alkylene oxide is reacted and polymerized on the amide group of the polyamide, and a polymer of the alkylene oxide is graft-bonded.

The liquid separation material of the present invention can be used as a liquid absorption separation material by filling it in a container as a membrane-like separation membrane or in the form of powder, granule, sheet, fiber or the like.

When used as a separation membrane, the liquid separation membrane is a thin film made of the above-mentioned graft polyamide, and the graft polyamide obtained by grafting onto a usual powdered or pelletized polyamide is used as a suitable solvent, for example, formic acid, sulfuric acid, trifluoroethanol. , Tetrafluoropropanol, hexafluoroisopropanol, etc., and a wet film forming method in which a thin film is formed from the solution, the solvent is removed and solidified to form a homogeneous film. Further, in this case, a film having a smooth surface, for example, a glass plate, a copper plate, and a metal roll or a belt is formed as a substrate used for producing a homogeneous film, and the film is peeled off from the substrate after the film is formed. By doing so, an extremely thin film can be obtained. Further, the graft polyamide may be melted to form a film by an inflation molding method or a T-die molding method.

The thin film-like homogeneous membrane can be used as it is as a liquid separation membrane, or can be used by laminating or bonding with another porous membrane. Further, a composite liquid separation membrane integrally formed on the surface of the porous membrane can be obtained by using a porous membrane as a base material for forming a homogeneous membrane.

In the present invention, a polyamide film is formed in advance by a known method, and a 1,2-alkylene oxide is directly grafted on the polyamide film. In the case of using a polyamide film-formed in advance by grafting, a graft polyamide film obtained by grafting a 1,2-alkylene oxide to an unstretched film, water, an alcohol such as methanol,
High permeability of chlorinated hydrocarbons and amines makes them more suitable for separating liquid mixtures containing them.

The liquid separation material of the present invention, the graft polyamide flat membrane,
Or it can be formed into a hollow fiber shape and made into various structures, normal filtration, microfiltration, separated by a normal pressure difference,
It can be used as a liquid filtration membrane for ultrafiltration, reverse osmosis, etc., ie, a liquid separation membrane.

In the present invention, the thickness of the homogeneous layer of the graft polyamide forming the liquid separation membrane is not particularly limited.
Used in a thickness of 0.1 to 500 μm.

The liquid separation membrane of the graft polyamide of the present invention selectively permeates water, alcohol, chlorinated hydrocarbons and amines, and in particular, water, methanol, methylene chloride, chloroform, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexa Methylenediamine, aniline, N-methylaniline, N-ethylaniline, o-methylaniline, m-methylaniline, o-chloroaniline, m-chloroaniline, pyridine are particularly high in permeability, It can be suitably used for purification, concentration and the like. For example, when a chlorinated hydrocarbon such as methylene chloride is used as a solvent for extraction or reaction, it can be effectively used for separating and removing them.

The liquid separation of the present invention can be applied to any of filtration separation by a pressure difference as described above, and particularly preferably, can be used for ultrafiltration, pervaporation, and the like. 150 ° C, particularly preferably 10-100 ° C
In under a pressure of about 0.1~100kg / cm ^2, particularly preferably about 0.5
It is preferably carried out under a pressure of 80 kg / cm ² .

The graft polyamide of the present invention can be effectively used for liquid separation by a membrane as described above, and also has an excellent ability to absorb water, alcohol, amines such as chlorinated hydrocarbons and aniline, and the like. It can also be applied as a material.

In this case, as described above, the graft polyamide of the present invention is preferably used as a liquid absorption / separation material in the form of powder, granule, sheet, fiber, or the like, and its shape, size, and the like are not particularly limited. Usually, a granule having an average particle size of 0.01 to 5 mm is used. In order to carry out absorption separation of a liquid content from a liquid mixture, as described above, a container such as a column is filled with the above-described morphological material and a predetermined liquid content such as water is absorbed while the liquid mixture is circulated. And may be separated. In addition, the above-mentioned morphological substance can be introduced and immersed in a liquid mixture or the like, and a predetermined liquid-containing substance can be absorbed and separated and removed.

The graft polyamide of the present invention has a peculiar phenomenon particularly in the absorption of water. For example, when water is absorbed using a graft polyamide having a graft ratio of 81.8%, the equilibrium water absorption (when the equilibrium at a predetermined temperature is reached) is obtained. Water absorption)
At 200 ° C, about 145% at 20 ° C, and about 112% at 100 ° C, the equilibrium water absorption is large at low temperatures, and decreases with increasing temperature.
Also, this phenomenon goes from 5 ℃ to 100 ℃ and from 100 ℃ to 5 ℃
Even if the temperature is repeatedly changed, the property does not change,
The graft polyamide liquid absorption / separation material of the present invention can repeat water absorption and water release with good reproducibility, and can be used repeatedly as a water absorption / separation material by absorbing and regenerating.

〔Example〕

Hereinafter, examples of the present invention will be described in detail. However, the present invention is not limited to the following examples.

In the present invention, the total polymerization rate (%), the graft polymerization rate (%), the homopolymerization rate (%), the weight increase rate (%), the graft rate (%), and the graft efficiency (%) are represented by the following formulas. Is a value calculated by However, in each of the following formulas, the amount of the charged polyamide is W _i , the amount of the alkylene oxide is Q, the weight of the solid after removing the unreacted alkylene oxide after the reaction is W _f , and the solid is washed with hot water to obtain the alkylene oxide. The weight of the hot water insoluble matter from which the homopolymer was removed was defined as Wf _' .

Example 1 unstretched film A ₀ of (liquid separation material production) Nylon 6 manufactured thickness 50 [mu] m (Ube Industries, Ltd., trade name: UBE1022B) 20g of ethylene oxide (Nippon Shokubai Kagaku Kogyo Co.) The mixture was charged in a stainless steel autoclave and reacted at 80 ° C. for a predetermined time in a non-catalyst, nitrogen gas atmosphere. After the reaction, unreacted ethylene oxide was removed by evaporation, and washing was performed for 4 hours in boiling water while replacing the boiling water by 1 hour. Then 50 ℃
For 72 hours to obtain a graft polyamide film.

As a result, to obtain a graft ratio as shown in Table 1 grafted polyamide film A ₁ to A _4.

For comparison, a graft reaction was performed in exactly the same manner using a nylon 6 biaxially stretched film B ₀ (manufactured by Kojin Co., Ltd., trade name: Boneal) instead of the unstretched film. Was. As a result, graft polyamide films B _{1 to} B ₄ (comparative examples) having a graft ratio as shown in Table ₁ were obtained.

Example 2 The graft ratio obtained in Example 1 was 116.7%, and the thickness was about 62 to 6%.
7 μm graft polyamide film A ₄ and graft ratio 9
8.6%, a graft polyamide film B ₄ having a thickness of about 29～34Myuemu, attached to RO-3 type reverse osmosis / ultrafiltration tester (manufactured by Bio-Engineering Co., Ltd.), each solvent 150ml addition, permeation area 31.2cm ^{2. The} amount of permeation after treatment at a pressure of 20 kg / cm ² at room temperature for 3 hours was measured.

 The results are shown in Table 2.

With polyamide unstretched film A ₀ which is not a comparative example grafted it was measured Torude amount in the same manner as in Example 2. As a result, in all cases, the amount of permeation was 0 ml.

Example 3 Nylon 6 powder having an average particle size of 0.2 mm (Ube Industries, Ltd.)
(Trade name: UBE1022B), and reacted for 6 hours in the same manner as in Example 1 to obtain a powdered graft polyamide having a graft ratio of 81.8%. The obtained powdered graft polyamide was filled in a spacer having a thickness of 2 mm, and was hot-pressed by sandwiching it between aluminum plates. Aluminum plate and spacer are coated with silicone KS700 (Shin-Etsu Chemical Co., Ltd.)
Hot pressing was performed at a temperature of 230 ° C. and a pressure of 100 kg / cm ² for 3 minutes (including 1 minute of residual heat time).

After hot pressing, the resultant was cooled at room temperature by sandwiching it between stainless steel plates having a thickness of 20 mm, and then vacuum dried at 50 ° C. for one day. A test piece was cut into 25 × 25 × 2 mm from the obtained molded piece and subjected to a water absorption test.

Two test pieces were immersed in water in an electronic thermostatic water bath ECW-6WEN type (manufactured by Tajiri Kikai Co., Ltd.) at 5 ° C., 20 ° C., and 100 ° C. or an oil bath. Water used was ion-exchanged water.
The change in weight was followed to calculate the water absorption. As a result, the equilibrium water absorption was 200% at 5 ° C, 145% at 20 ° C, 100% as described above.
It was 112% at ° C.

In addition, a water absorption cycle test was conducted in which the test pieces were alternately and repeatedly immersed in 5 ° C. water and 100 ° C. hot water, and the relationship between water absorption and time was shown in FIG. It can be seen from the change in water absorption shown in FIG. 1 that the graft polyamide apparently absorbs and releases water.

〔The invention's effect〕

The liquid separation material and the liquid absorption separation material of the present invention are excellent in absorption and permeability of water, alcohol, chlorinated hydrocarbons and amines, and are capable of permeating these components or other components from a liquid mixture containing them. They can be absorbed and separated, and chlorinated hydrocarbons are extremely useful industrially because they are used in large amounts as various solvents.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between water absorption and time in a water absorption cycle test in which the temperature of a graft polyamide liquid absorption / separation material of the present invention was changed.

Claims (4)

(57) [Claims] 1. A liquid separation material comprising an alkylene oxide-grafted polyamide film obtained by grafting a 1,2-alkylene oxide to an unstretched polyamide film. 2. Using a liquid separating material comprising an alkylene oxide-grafted polyamide film obtained by grafting a 1,2-alkylene oxide onto an unstretched polyamide film, water, alcohol, chlorinated hydrocarbon and amines A liquid separation method comprising separating a compound containing a compound from a liquid mixture containing at least one compound. 3. A liquid absorbing / separating material comprising an alkylene oxide-grafted polyamide and having excellent liquid absorbing ability. 4. A method for absorbing and separating a compound contained in a liquid mixture containing at least one of water, alcohol, chlorinated hydrocarbons and amines using a liquid absorption / separation material comprising an alkylene oxide graft polyamide. A liquid absorption separation method.