WO2015093080A1 - 半透膜の製造方法、および半透膜 - Google Patents
半透膜の製造方法、および半透膜 Download PDFInfo
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- WO2015093080A1 WO2015093080A1 PCT/JP2014/065456 JP2014065456W WO2015093080A1 WO 2015093080 A1 WO2015093080 A1 WO 2015093080A1 JP 2014065456 W JP2014065456 W JP 2014065456W WO 2015093080 A1 WO2015093080 A1 WO 2015093080A1
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- semipermeable membrane
- film
- salt
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
- B01D61/0022—Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
- B01D67/00113—Pretreatment of the casting solutions, e.g. thermal treatment or ageing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
- B01D71/641—Polyamide-imides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2323/16—Swelling agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01D2323/2181—Inorganic additives
- B01D2323/21817—Salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21827—Salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
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- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21827—Salts
- B01D2323/21828—Ammonium Salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2323/30—Cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2323/36—Introduction of specific chemical groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2323/64—Use of a temporary support
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01D2325/36—Hydrophilic membranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
Definitions
- the present invention relates to a method for producing a semipermeable membrane having both good semipermeable properties and sufficient strength, and a semipermeable membrane.
- composite membranes and asymmetric membranes are mainly used as reverse osmosis membranes or forward osmosis membranes.
- These membranes have two layers, a separation functional layer and a support layer.
- the separation functional layer has a substantial separation function.
- the support layer has a high physical strength, so that the entire membrane is given sufficient strength to be subjected to a pressurized water permeability test.
- the support layer has at least one or both of a porous membrane and a substrate.
- the separation functional layer is formed so as to cover the support layer.
- Many of the composite membranes used industrially are formed by utilizing interfacial polycondensation on a porous membrane.
- Patent Document 1 describes a membrane having a separation functional layer formed of polyamide.
- the asymmetric membrane is different from the composite membrane in that it is composed of a single material, but is substantially different from the composite membrane in that it has a dense layer substantially corresponding to a separation functional layer and a support layer having high mechanical strength.
- Patent Literature 2 describes a membrane using a cellulose acetate material.
- the support layer in these composite membranes and asymmetric membranes usually has a thickness of several tens of ⁇ m or more. As described above, the support layer is used to physically support a thin separation functional layer having low mechanical strength. However, by providing a support layer, (1) the water permeability obtained by the whole membrane is lower than the original water permeability of the separation functional layer, and (2) the salt content stays inside the support layer. Problems are known to occur.
- Patent Document 3 reports a composite membrane in which a separation functional layer is formed on a substrate having a large porosity and a small K value.
- Patent Document 4 describes a cellulose acetate thin film having a thickness of 1 ⁇ m or less.
- An object of the present invention is to provide a method for producing a semipermeable membrane that has both good semipermeable properties and sufficient strength, and a semipermeable membrane.
- Substance (D) from hydroxyl group and its salt, amino group and its salt, carboxyl group, its salt and its anhydride, sulfo group, its salt and its anhydride, and phosphate group, its salt and its anhydride
- One or more low molecular weight compounds selected from the group consisting of a low molecular weight compound containing at least one hydrophilic group selected from the group consisting of
- a semipermeable membrane having both good semipermeable property and sufficient strength can be produced.
- the semipermeable membrane of the present invention (hereinafter, sometimes simply referred to as “membrane”) has a repeating unit structure containing one or more structural sites selected from the group consisting of an amide group, an imide group, a sulfonyl group, and a heterocyclic ring. Is used as the main component of the membrane. Since these have a hydrogen bonding site in their repeating unit structure, they form a strong intermolecular hydrogen bond in the film. As a result, a film having high mechanical strength can be obtained.
- the main component of the film is preferably polyamide, polyamideimide, or polybenzimidazole, and particularly preferably polyamide having a planar amide bond.
- this semipermeable membrane is an ultra-thin film having a thickness of about 1 ⁇ m, there is no support by a support layer or a base material, and even if it is subjected to a pressurized water permeability test, the supply liquid leaks as it is, etc. Defects are less likely to occur. More specifically, the membrane has an effect that defects are hardly generated even after a pressurized water permeability test of about 1 to 3 MPa.
- the thickness of the film is set depending on the purpose of use, but is preferably less than 20 ⁇ m. Further, the thickness of the film may be 5 ⁇ m or less, or 1 ⁇ m or less. When the thickness of the film is less than 20 ⁇ m, high semi-permeability is obtained.
- the thickness of the film is preferably 0.1 ⁇ m or more.
- the thickness of the film may be 0.5 ⁇ m or more, or 0.8 ⁇ m or more. A particularly high strength is obtained when the thickness of the film is 0.1 ⁇ m or more.
- the form of the film is not particularly limited, and may be appropriately selected as necessary.
- a sufficient strength can be secured even with a self-supporting membrane having a thickness of about 1 ⁇ m, and a composite membrane can be used to ensure the necessary semi-permeability. You may ensure more sufficient intensity
- it may be a flat membrane or a hollow fiber membrane, and flexibly select the form of the membrane according to the desired semi-permeability and strength.
- the present invention has the advantage that it can.
- “semi-permeable” means having water permeability and solute removal performance.
- the membrane has the following paragraphs [0076], [0077] and [0078] when measured at a pressure of 1 MPa, a sodium chloride concentration of the soot supply liquid: 500 ppm, a soot temperature of 25 ° C., and a pH of 6.5.
- the (A / B) value which is the ratio of the A and B values calculated based on the formula for deriving the pure water permeability coefficient A and the salt permeability coefficient B described in the above, is preferably 0.1 or more. It is more preferably 3 or more, and further preferably 0.6 or more.
- the (A / B) value may be 1.5 or less, or 1.2 or less, 1.1 or less, or 1.0 or less.
- a film having (A / B) of about 0.3 to 1.5 can be obtained.
- each condition of the production method may be selected in order to develop suitable semi-permeability.
- the semipermeable membrane of the present invention can have more excellent semipermeable properties when it contains cross-linked ⁇ , cross-linked ⁇ , and substance (D).
- a semipermeable membrane having A / B which is an index indicating semipermeable property, is generally 5 or more and 20 or less.
- a / B increases or decreases by about 0.1 to 0.5 depending on the presence or absence of crosslinking ⁇ .
- a / B increases or decreases by about 0.1 to 0.5 with or without cross-linking ⁇ .
- a / B increases or decreases by about 0.3 to 1 depending on the presence or absence of cross-linking ⁇ and substance (D).
- the semi-permeable improvement effect of the bridge ⁇ , the bridge ⁇ , and the substance (D) is about 2 at the maximum when the numerical values are added.
- the semi-permeability improvement effect when these are combined reaches about 5 to 20 with a change in A / B. This effect was completely unexpected at first, and the inventors found it uniquely.
- the bridge ⁇ is a covalent bridge through a nitrogen atom in the main chain skeleton of the substance (A).
- the crosslinking ⁇ can be formed by various methods such as heat treatment, electron beam irradiation, ultraviolet irradiation, and plasma treatment, and may be formed by using a chemical reaction between the substance (A) and various crosslinking agents.
- the cross-linking agent various compounds capable of forming a covalent bond by a chemical reaction with the nitrogen atom in the substance (A) can be used, and the type is not particularly limited. Examples thereof include polyfunctional halides and melamine compounds.
- the crosslinking agent may be mixed in advance in the film forming solution.
- cross-linking ⁇ By forming the cross-linking ⁇ , effects such as improvement of semi-permeability and improvement of mechanical strength can be obtained.
- the formation of cross-linked ⁇ can be detected by measurements such as FT-IR (Fourier transform infrared spectroscopy), NMR (nuclear magnetic resonance), and X-ray analysis. It can be confirmed whether or not the film is dissolved by immersing it in a good solvent of A) and heating it appropriately.
- the covalent bond crosslink ⁇ is present, the film is insolubilized, and therefore the presence / absence of the crosslink ⁇ can be confirmed by solubility / insolubility.
- the bridge ⁇ is formed between an oxygen atom, a nitrogen atom or a hydrophilic group in the hydrogen bonding atomic group in the main chain skeleton of the substance (A) and a cation derived from the substance (C).
- the bridge ⁇ is formed by dissolving a salt in a solution containing the substance (A).
- the hydrogen bonding atomic group indicates, for example, an amide bond in the main chain in the case of polyamide, and an imidazole ring structure in the case of polybenzimidazole.
- the bridge ⁇ is formed by an electrostatic interaction between an anionic atom and a salt-derived cation.
- crosslinking ⁇ effects such as improvement of semi-permeability and mechanical strength can be obtained.
- Formation of the crosslinked ⁇ can be detected by measurement such as FT-IR, NMR, X-ray analysis, or elemental analysis of the components of the semipermeable membrane.
- various methods such as ICP emission spectroscopy, ESCA, EPMA, SIMS, and the like can be selected, whereby the cations derived from the substance (C) in the semipermeable membrane can be quantified.
- the amount of the substance (C) contained in the film can be clarified by thermally decomposing the film with sulfuric acid, nitric acid, or a mixed solution thereof, then forming a solution, and performing ICP emission spectroscopic analysis. it can.
- the cation derived from the substance (C) is preferably contained in an amount of 0.1% or more, more preferably 1% or more, based on the weight of the membrane.
- the semipermeable membrane of the present invention is characterized by containing a substance (D).
- the substance (D) is used for the purpose of improving the semipermeable property of the semipermeable membrane.
- the substance (D) is a poor solvent for the substance (A). Therefore, the substance (A) and the substance (D) are not compatible by simply mixing them, and the effect of improving the semi-permeability by the substance (D) cannot be obtained.
- the substance (C) is used in order to make these compatible. By the addition of this, the above-mentioned cross-linking ⁇ is formed. However, hydrogen bonds that are intermolecular interactions between the substances (A) are attenuated.
- the substance (D) When the substance (D) is added to the solution containing the substances (A) and (C) in this state, the substance (D) is surprisingly dissolved in the solution. This is because the mobility of the substance (A) is improved because the hydrogen bond is attenuated, and the free volume is improved, so that a gap is generated between the molecules of the substance (A), and the substance (D) is present in the gap. It is thought that compatibilization became possible by insertion. That is, in order for a semipermeable membrane to contain a substance (D), it is that bridge
- the “inside of the membrane” in the present invention is not the surface of the membrane or the pores (defects) on the order of micrometers, but the space between the polymer chains of the substance (A) and refers to the space on the order of nanometers. Further, the space serves as a water permeation path and determines the semi-permeability of the semi-permeable membrane of the present invention. The space is good from a semi-permeable point of view when there are more smaller spaces. Although details will be described later, the inventors think that the cross-linking ⁇ generally has an effect of reducing the size of the space, and the cross-linking ⁇ has an effect of increasing the space. It is considered that the substance (D) exists in the space.
- the substance (D) may be removed to some extent in a desolvation step described later and a washing step with hot water.
- the substance (D) finally present in the film can be confirmed by the presence or absence of a peak derived from the substance (D) by analyzing the film by a technique such as FT-IR, solid state NMR, DSC or the like. Furthermore, it is possible to quantify from the peak intensity.
- the carbon derived from the substance (D) in the present invention preferably accounts for 1% or more, more preferably 5% or more, based on the total carbon contained in the film.
- Examples of the method for producing the membrane include a production method comprising a step of forming a liquid film with a film-forming solution containing substances (A) to (C) described later, and a desolvation step of removing the solvent from the liquid film. It is done.
- a production method comprising a step of forming a liquid film with a film-forming solution containing substances (A) to (C) described later, and a desolvation step of removing the solvent from the liquid film. It is done.
- a more specific manufacturing method will be described.
- the film manufacturing method of this embodiment comprises preparing a film forming solution containing the following substances (A) to (C).
- Film-forming solution ⁇ Substance (A)>
- the inventors consider that the solution used for film formation (hereinafter referred to as “film formation solution”) preferably has a high viscosity. Therefore, the polymer concentration of the film forming solution and the molecular weight of the polymer contained in the film forming solution are preferably high as long as the solubility in the substance (B) is not impaired and the ease of filtration can be secured.
- the polymer contained in the film forming solution is preferably a polymer capable of forming hydrogen bonds in the film forming solution.
- a polymer capable of forming hydrogen bonds can improve the viscosity of the film-forming solution by a network formed by hydrogen bonds. Furthermore, even if the polymer capable of forming a hydrogen bond is not an ultra-high molecular weight polymer, it can achieve a solution viscosity sufficient to carry out the film forming step, which is preferable from the viewpoint of reducing the labor of synthesis. It is.
- a polymer capable of forming hydrogen bonds is also preferable from the viewpoint of economy because the concentration in the film-forming solution may be relatively low.
- a film formed of a polymer capable of forming a hydrogen bond can achieve high mechanical strength, and thus is preferable as a self-supporting film that does not include a support layer.
- the film-forming solution has a repeating unit structure containing one or more structural sites selected from an amide group, an imide group, a sulfonyl group, and a heterocyclic ring as the substance (A). It is preferable to provide. A more specific form of the substance (A) is shown below.
- polyamide, polyimide, polyamideimide, polybenzimidazole, polysulfone, polyethersulfone and the like are suitable. More specifically, the substance (A) is preferably polyamide, polybenzimidazole, or polyamideimide having a relatively rigid structure, and polyamide is particularly preferable because the hydrogen bond network is particularly strong. Further, the substance (A) may be one or more kinds of aromatic polyamides, and may be a meta-substituted aromatic polyamide. Further, the substance (A) may be a meta-substituted aromatic polyamide having a repeating unit containing an ether bond.
- the substance (A) may contain at least one of a hydrophilic group and a halogen atom.
- a hydrophilic group and a halogen atom can be contained as a substituent in the repeating unit of the substance (A). These substituents may be included in a part of the repeating unit structure or may be included in all repeating units.
- the ratio of the “repeating unit structure into which the substituent is introduced” to the ratio of “the repeating unit structure into which the substituent is introduced” to the ratio of the “repeating unit structure into which the substituent is introduced” is 1 to 100 in all the repeating unit structures. Preferably it is ⁇ 100 to 100.
- the hydrophilic group and the halogen atom should just be introduce
- hydrophilic group examples include a carboxyl group, a sulfo group, a phosphate group, an amino group, a hydroxyl group, and salts thereof.
- the hydrophilic group may be contained in the repeating unit structure of the substance (A).
- the polymer corresponding to the substance (A) may contain only one type of hydrophilic group, or one polymer may contain two or more types of hydrophilic groups.
- the halogen atom can further strengthen the interaction with the cation derived from the substance (C) described later.
- the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
- the hydrophilic group and the halogen group are preferably introduced as substituents of the polymer chain.
- the polymer corresponding to the substance (A) may contain only one type of halogen atom, or one polymer may contain two or more types of halogen atoms.
- hydrophilic group and the halogen atom can be combined according to the properties of the desired semipermeable membrane.
- the polymer used for the substance (A) may have a polarizable atomic group in combination with the above structure.
- the polar atomic group include a hydroxy group, an N-hydroxy group, a thiol group, a carboxyl group, a sulfo group, a phosphoric acid group, an amino group, a nitro group, a nitroso group, a halogen group, a diazo group, an azide group, and a cyano group.
- a part or all of the atomic group containing a hydrogen atom may be substituted with any alkyl group.
- the polymer which has the said atomic group may contain only 1 type in the said atomic group, and may be provided with the said several atomic group. The inclusion of these polarizable atomic groups is not an essential requirement for the substance (A).
- the polymer corresponding to the substance (A) may have any primary structure such as linear, branched, star, block polymer, gradient polymer, solar type.
- the film-forming solution may contain one or more polymers selected from polyamide and polybenzimidazole and having a hydrophilic group in the repeating unit structure.
- the film-forming solution may contain a meta-substituted aromatic polyamide having a repeating unit containing an ether bond and a hydrophilic group.
- the type of the substance (A) is not limited to the above examples.
- the substance (A) has solubility in the substance (B), can give a solution viscosity sufficient for carrying out the liquid film forming step to the film forming solution, and further has a hydrogen bond forming ability.
- the substance (A) is selected according to the strength, performance, etc. of the target semipermeable membrane.
- the film forming solution may contain only one type of polymer as the substance (A), or may contain two or more types of polymers.
- the substance (B) is a good solvent for the substance (A).
- various general-purpose organic solvents are mainly used. In the solution preparation step, only a single solvent may be used as the substance (B), or a mixed solvent composed of two or more types may be used.
- the substance (B) can be selected as long as the solubility of the substance (A) is not impaired.
- the substance (A) N-methyl-2-pyrrolidone, which is a good solvent for these substances, dimethyl sulfoxide, dimethylformamide is used as the substance (B).
- Amides such as, or sulfoxide solvents are preferred.
- Substance (C) is a salt.
- the inventors consider the reason why the water permeability of the membrane is improved as follows. Generally, when a membrane is formed by heating and drying a membrane-forming solution, the interaction between polymer chains works very strongly, so it is difficult to form pores that are water flow paths, and the water permeability of the membrane is reduced. Lower.
- the substance (C) can weaken the intermolecular interaction between the substances (A) by interacting with the substance (A). By forming a film in such a state that the intermolecular interaction is weakened, more pores are formed.
- mechanical strength can be realized by the substance (A)
- water permeability can be realized by the substance (C)
- a film having water permeability can be realized by the action of the substance (C).
- the substance (C) for example, various metal salts, ammonium salts, acetates and the like are preferably used.
- the metal salt include halides such as lithium, sodium, potassium, copper, calcium, barium, magnesium, mercury, and silver. Since trivalent or higher valent metal salts are easily oxidized, it is preferable to use divalent or lower valent metal salts for convenience in storage and handling.
- the substance (C) is particularly preferably a divalent metal salt.
- the film-forming solution may contain only one type of salt as the substance (C), or may contain two or more types of salt.
- the substance (C) an inorganic salt having not only the above-described effect but also an effect as a dissolution aid for the substance (A) can be selected.
- the content of the substance (C) in the film-forming solution (ratio of the weight of the substance (C) to the total weight of the film-forming solution) is 0.1% by weight or more with respect to the total weight of the film-forming solution. It is preferably 1% by weight or more. When the content of the substance (C) in the film-forming solution is 0.1% by weight or more, the effect of improving the semi-permeability of the film is particularly high. In addition, the content of the substance (C) in the film forming solution is preferably 20% by weight or less, and more preferably 10% by weight or less. When the content ratio of the substance (C) is 20% by weight or less, the substance (C) is easily dissolved in the film forming solution and hardly precipitated.
- the film forming solution may further contain a substance (D).
- the substance (D) is at least one compound selected from the group consisting of the following substances (a) and (b).
- the substance (D) is a hydrophilic substance, when the substance (D) is contained in the film forming solution, more pores serving as water channels are more easily formed, and water permeability is improved. An effect is obtained.
- the substance (D) is soluble in the film-forming solution containing the substances (A) to (C). This is because the substance (D) is soluble in the substance (B).
- the substance (D) can be present in the space generated by the effect of the substance (C) in the film forming solution and the obtained film by dissolving in the substance (B).
- the substance (D) can be compatible with the substance (A). That is, the substance (C) can act as a compatibilizer when a substance that is not compatible with the substance (A) is used as the substance (D).
- the solubility of the substance (D) is improved when the substance (C) is used in combination. That is, the substance (C) is preferably used when many substances (D) are added.
- the substance (D) includes compounds having two or more hydrophilic groups such as various diols, triols, and metal salts thereof; and two or more acidic compounds such as dicarboxylic acid and disulfonic acid. Examples thereof include organic acids having a group, salts thereof and anhydrides thereof.
- the polymer compound that can be used as the substance (D) include hydrophilic or water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, polyvinyl sulfonic acid, polybenzoic acid, and polystyrene sulfonic acid, and metal salts thereof.
- the substance (D) may be a low molecular compound.
- the substance (D) which is a low molecular compound may have 1 to 3 hydrophilic groups, a salt thereof or an anhydride thereof.
- the “low molecular compound” means a compound having no repetitive structure, particularly a compound having a molecular weight of less than 100.
- the substance (D) may be a polymer.
- the “polymer” is a compound having a repeating structure, particularly a compound having a molecular weight of 100 or more or a compound having a number average degree of polymerization of 500 or less.
- the substance (D) may be a diol or triol or a dicarboxylic acid anhydride.
- the addition amount of the substance (D) in the film forming solution is not limited to a specific numerical value, and depends on the kind and amount of the substance (A), the kind and amount of the substance (C), the target water permeability, and the like. Is set. However, when the substance (D) is a poor solvent for the substance (A) or is not compatible with the substance (A), the amount of the substance (D) added is set so that the substance (A) is insoluble and does not precipitate. Is done.
- the content of the substance (D) (the ratio of the weight of the substance (D) to the total weight of the film-forming solution) is 0.001% by weight to 40% by weight, or 1% by weight or more. It is preferably 20% by weight or less.
- the content of the substance D is 0.001% by weight or more, the water permeability is particularly improved, and when it is 40% by weight or less, a uniform film forming solution is easily obtained.
- the solution adjustment step includes a step of mixing the components of the film-forming stock solution listed in the column (1) above.
- this process can comprise a plurality of steps.
- the solution adjustment step may include stirring the solution containing each component while heating.
- the mixing ratio and addition order of the substances (A) to (D) are not particularly limited.
- the amount of each substance added to the volume of the film forming solution is preferably set so as to ensure the uniformity of the film forming solution.
- it may be removed by a separation method such as filtration, and the filtrate may be used as a membrane-forming solution.
- a pressure filter can be used according to the high viscosity of the solution.
- the filtration diameter is 3 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.4 ⁇ m or less, and further preferably 0.2 ⁇ m or less.
- the manufacturing method may include a step of forming a liquid film with a film forming solution (liquid film formation step).
- Various methods such as dip coating, spin coating, and application using an applicator can be used to form the liquid film.
- application by spin coating is particularly preferable.
- the formation of the liquid film can be realized by applying a film forming solution to the substrate.
- the production method of the present invention includes carrying out solvent removal and, if necessary, crosslinking after the liquid film forming step.
- solvent removal step as a method for removing the solvent, a method by heating and drying, and immersion in a liquid that is compatible with the substance (B) as a solvent and is a poor solvent for the substance (A) as a polymer. There are two methods:
- the material (B) is evaporated by heat drying to promote polymer aggregation and form a film.
- the crosslinking may proceed simultaneously by heating, and the crosslinking ⁇ may be formed.
- the cross-linking ⁇ may be formed by various methods such as heat treatment, electron beam irradiation, ultraviolet irradiation, and plasma treatment. These steps may be performed before or after the solvent removal, and can be appropriately incorporated as necessary.
- the substance (C) is used while the strong intermolecular interaction of the substance (A) is relaxed to form pores that serve as water flow paths, and good water permeability is exhibited. Sufficient mechanical strength can be maintained. Furthermore, as described above, the water permeability can be further improved by the substance (D).
- the liquid film is made of water, a monohydric or higher alcohol, a mixture of water and a monohydric or higher alcohol, or a mixture of the substance (B) and at least one of water or a monohydric or higher alcohol.
- Solvent removal may be performed by contacting any of them.
- the substance (A) is a water-insoluble polymer and a salt is used for the substance (C) for the purpose of swelling the polymer, water that can solubilize this is used for the dipping liquid.
- the immersion liquid may be dissolved in advance with additives such as salts, alcohols, and good solvents for the polymer, if necessary.
- the solvent (D) may be evaporated at the same time by heat drying, and therefore, solvent removal by liquid immersion is preferable.
- the boiling point of the substance (B) is lower than the boiling point of the substance (D)
- the substance (D) does not evaporate by heat drying and remains in the film.
- the method of solvent removal may be performed by either the liquid immersion method or the liquid immersion method, and which method is selected may be appropriately selected according to the type of the substance to be used. Liquid immersion may be performed later, or heat drying may be performed after liquid immersion.
- the production method may further include other steps.
- the semipermeable membrane formed in the solvent removal process is washed with hot water.
- Such hot water washing treatment improves the mobility of the polymer and promotes the reorganization of the polymer phase. As a result, a denser film can be obtained. Since this step can improve the desalting property of the semipermeable membrane, it may be carried out as necessary.
- the hot water cleaning treatment refers to immersing the semipermeable membrane in hot water at a predetermined temperature for a predetermined time. Specifically, it may be immersed in hot water at 90 ° C. for 5 minutes.
- the substance (D) in the semipermeable membrane of the present invention exists in the membrane even after the hot water cleaning treatment.
- the substance (D) finally present in the film can be confirmed from the presence of a peak derived from the substance (D) by analyzing the film by a technique such as FT-IR, solid state NMR, DSC or the like. Furthermore, it is possible to quantify from the peak intensity.
- Tables 1 to 7 summarize the film production conditions, the membrane structure parameters, and the performance values obtained from the water permeation experiments.
- Table 8 shows the chemical structure of the substance (A).
- the mixing ratios of the substances (A) to (D) are (A) vs. (B) vs. (C) vs. (D1) vs. all experiment numbers in Table 1 unless otherwise specified in the remarks column of Table 1.
- (D2) 15: 60: 10: 10: 5 (weight ratio).
- D1 and D2 both correspond to the substance (D).
- Substances A-6 to A-10 do not correspond to the definition of the substance (A) described above, but are represented as the substance (A) for convenience.
- the pure water permeability coefficient A (m 3 / m 2 / day / MPa) and the salt (solute) permeability coefficient B (m / day) are expressed by the following transport equation (1 ) And (2).
- Jv A ( ⁇ P ⁇ ⁇ ⁇ ) (1)
- Js B (Cm ⁇ Cp) + (1 ⁇ ) C ⁇ Flux (2)
- Cm Cp + (salt concentration of feed solution ⁇ Cp) ⁇ exp (Jv / Js) (3)
- Jv is the water membrane permeation flux (mol / m 2 / s)
- ⁇ P the pressure difference (MPa) on both sides of the membrane
- ⁇ is the solute reflection coefficient
- ⁇ is the osmotic pressure difference (MPa) on both sides of the membrane
- Js is Membrane flux of solute (mol / m 2 / s)
- Cm is the concentration of solute on the membrane surface (mol / m 3 )
- Cp is the concentration of solute
- this value is referred to as an A / B value.
- the performance as a semipermeable membrane is superior or inferior in comparison between a plurality of membrane samples by evaluating the A / B value. The higher the A / B value, the better the semipermeable membrane.
- EG ethylene glycol
- Gly glycerin MA: maleic anhydride
- PVA polyvinyl alcohol
- NMP N-methyl-2-pyrrolidone
- DMF N, N-dimethylformamide
- LiCl lithium chloride
- MgCl 2 magnesium chloride
- ZnCl 2 zinc chloride
- a / B represents the ratio of pure water permeability coefficient / salt permeability coefficient. From Table 1, in No. 1, water permeability was not obtained. On the other hand, water permeability was observed in Nos. 2 to 4 in which an inorganic salt was added to the film forming solution. In particular, in the case of No. 3 to which magnesium chloride was added, the highest A / B value among the experimental results of Nos. 2 to 4 was obtained.
- numbers 5 to 7 are the results when various aqueous solutions or water were further added. Addition of water or an aqueous solution further improved the water permeability as compared with Nos. 2-4. Among them, the case of No. 5 to which only water was added had the highest A / B value.
- the metal cation derived from the inorganic salt interacts with the anionic portion of the polymer chain, and furthermore, water or ethylene glycol can be solubilized in the solution only through this metal cation.
- the space between the chains is considered to be swollen with water or ethylene glycol.
- the materials of Nos. 28 to 33 are all amide groups, imide groups, sulfonyl groups, complex groups, because it is difficult to produce a uniform film-forming solution itself or there is a problem with the mechanical strength of the thin film. It was judged to be inferior to a polymer having a repeating unit structure containing a ring.
- Nos. 34 and 35 made a water-permeable film, and confirmed the effect of the present invention.
- a membrane (No. 2) whose main component is a polymer having a repeating unit structure including one or more kinds of structural sites selected from the group consisting of an amide group, an imide group, a sulfonyl group, and a heterocyclic ring.
- -14, 18-27, and 34-37 did not cause any defects even after the above-mentioned pressurized water permeability test, and could realize strength as a film.
- good water permeability was obtained in Experiment Nos. 2-14, 18-27, and 34-37 due to the effect of salt during film formation.
- the silicon wafer coated with the polymer solution was heated and dried to remove the solvent and form the cross-linking ⁇ . After removing the solvent, the membrane was peeled off in pure water at room temperature and then used for a water permeability test.
- This shift indicates that the bonding force between the carbon and oxygen atoms of the carbonyl group is enhanced by the presence of the substance (C), that is, the intermolecular hydrogen bond of the carbonyl group is weakened. From this, it was found that the intermolecular hydrogen bond formed by the carbonyl group was cleaved at a certain rate, and that the magnesium ion derived from the substance (C) was ion-bonded, that is, a bridge ⁇ was newly formed. .
- the fabricated films were thermally decomposed with sulfuric acid and nitric acid, dissolved by warming with dilute nitric acid to obtain a constant volume, and then subjected to ICP emission spectroscopic analysis. Analysis was performed to determine the abundance of magnesium as the substance (C). The results are shown in Table 11. In Experiment Nos. 38 and 47 where the substance (C) was not added, magnesium was not detected. On the other hand, in the experiment numbers 42, 44, 53, and 55, unlike the experiment numbers 38 and 47, magnesium was detected, and it was found that magnesium was present inside the film.
- DSC device DSC Q100 manufactured by TA Instruments Data processing: Toray Research Center analysis program "TRC-THADAP-DSC” Measurement temperature range: about -55 to 5 ° C Temperature increase rate: 0.3 ° C / min Sample amount: about 5mg Sample container: Aluminum sealed sample container Temperature / calorie calibration: Pure water (melting point 0.0 ° C, heat of fusion 79.7 cal / g)
- the experiment numbers 38 and 47 are the results for the substance (A) alone. Although the presence of water was confirmed, the endotherm was as small as about 1 (mcal / sec) and the melting point was 0 ° C. This result was that water slightly remaining on the membrane surface was detected, and the presence of water inside the membrane could not be confirmed.
- the substance (C) was added to form the crosslinked ⁇ , and water was further added as the substance (D). In these cases, the endothermic amount increased significantly to about 10 times the experiment numbers 38 and 47, and at the same time, the melting point of water decreased to below freezing point. From this, it was found that in Experiment Nos.
- the film of Experiment No. 51 was heated with hot water at 90 ° C. for 5 minutes, then vacuum-dried, and subjected to FT-IR measurement and solid-state NMR measurement. In FT-IR measurement, the film was derived from ethylene glycol. Aliphatic hydrocarbon groups and alcohol peaks were observed.
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Abstract
Description
次に、(2)については、膜を正浸透膜として使用する際、支持層に塩分が滞留することで濃度分極が発生し、それによって浸透圧が低下する。その結果、透水量が著しく減少するという問題が起きる(非特許文献1)。正浸透膜の開発においては、特にこのような塩分滞留を軽減ないし克服することが強く求められている。
を備える方法によって、上記課題を解決できることを見いだした。
物質(A):アミド基、イミド基、スルホニル基および複素環からなる群より選択される1種類以上の構造部位を含む繰り返し単位構造を備えるポリマー
物質(B):物質(A)の良溶媒
物質(C):塩
物質(D):ヒドロキシル基およびその塩、アミノ基およびその塩、カルボキシル基、その塩およびその無水物、スルホ基、その塩およびその無水物、並びに、リン酸基、その塩およびその無水物からなる群より選択される親水性基を少なくとも1種類以上含む低分子化合物および水からなる群より選択される1種類以上の低分子化合物
架橋α:物質(A)を構成する窒素原子を介した共有結合
架橋β:物質(A)を構成する酸素原子もしくは窒素原子または親水性基と、上記物質(C)由来のカチオンとのイオン結合
本発明の半透膜(以下、単に「膜」と称することがある)は、アミド基、イミド基、スルホニル基、複素環からなる群より選択される1種類以上の構造部位を含む繰り返し単位構造を備えるポリマーを膜の主成分として使用する。これらは、その繰り返し単位構造中に水素結合性部位を有しているので、膜中で強力な分子間水素結合を形成する。その結果、高い機械的強度を有する膜が得られる。
架橋αは、物質(A)の主鎖骨格中の窒素原子を介した共有結合性の架橋である。架橋αは、熱処理、電子線照射、紫外線照射、プラズマ処理など、種々の方法により形成させることができ、物質(A)と、種々の架橋剤との化学反応を利用して形成されてもよい。架橋剤としては、物質(A)中の窒素原子と化学反応により共有結合の形成が可能な種々の化合物を使用することができ、種類は特に限定されない。一例として、多官能ハロゲン化物や、メラミン系化合物が挙げられる。架橋剤は、製膜溶液中に予め混合しておくとよい。架橋αの形成により、半透性の向上、機械的強度の向上といった効果が得られる。架橋αの形成は、FT-IR(フーリエ変換型赤外分光法)やNMR(核磁気共鳴)、X線分析といった測定により検出できるが、より簡単には、得られた半透膜を物質(A)の良溶媒中に浸漬させ、適宜加熱するなどして膜が溶解するかどうかで確認することができる。共有結合性の架橋αが存在する場合、膜は不溶化するので、可溶/不溶により架橋αの有無を確認することができる。
架橋βは、物質(A)の主鎖骨格中の水素結合性原子団中の酸素原子もしくは窒素原子または親水性基と、物質(C)由来のカチオンとの間で形成される。架橋βは、塩を物質(A)を含む溶液中に溶解することで形成される。水素結合性原子団とは、例えば、ポリアミドの場合、主鎖のアミド結合を指し、ポリベンズイミダゾールの場合、イミダゾール環構造を指す。架橋βは、アニオン性原子と、塩由来のカチオンとの間の静電的な相互作用により形成される。架橋βにより、半透性の向上、機械強度の向上といった効果が得られる。架橋βの形成は、FT-IRやNMR、X線分析といった測定や、半透膜の構成成分の元素分析により検出できる。元素分析は、ICP発光分光分析法、ESCA,EPMA,SIMSなど、種々の方法を選択でき、これにより半透膜中の物質(C)由来のカチオンを定量できる。例えば、膜を硫酸や硝酸、あるいはそれらの混合溶液などで加熱分解し、その後溶液化し、ICP発光分光分析を行うことで、膜中に含有される物質(C)の量を明らかにすることができる。さらに、FT-IR分析によっても確認が可能である。架橋βが形成されている場合、物質(A)中のアニオン性原子のピークがシフトするので、このことにより判断できる。本発明において、物質(C)由来のカチオンは、膜の重量に対し、質量%で0.1%以上含有されることが好ましく、1%以上含有されるとより好ましい。
上記膜の製造方法として、後述の物質(A)~(C)を含む製膜溶液により液膜を形成する工程と、その液膜から溶媒を除去する脱溶媒工程と、を備える製造方法が挙げられる。以下では、より具体的な製造方法について説明する。
本実施形態の膜の製造方法は、下記物質(A)~(C)を含む製膜溶液を準備することを備える。
(1)製膜溶液
<物質(A)>
半透膜の強度を確保する観点から、発明者らは、製膜に用いる溶液(以下、「製膜溶液」と称する。)は高粘性であることが好ましいと考える。したがって、製膜溶液のポリマー濃度および製膜溶液に含まれるポリマーの分子量は、物質(B)への溶解性を損なわず、かつ濾過の容易さを確保できる範囲で、高いことが好ましい。
なお、上記原子団を有するポリマーとは、上記原子団のうち1種のみを含んでいても良いし、複数の上記原子団を備えてもよい。
なお、これら分極性原子団を含有することは、物質(A)の必須の要件ではない。
例えば、製膜溶液は、ポリアミドおよびポリベンズイミダゾールから選ばれ、かつ繰り返し単位構造中に親水性基を含む1種類以上のポリマーを含有してもよい。また、製膜溶液は、メタ置換芳香族ポリアミドがエーテル結合および親水性基を含む繰り返し単位を備えるメタ置換型芳香族ポリアミドを含有してもよい。
物質(B)は物質(A)の良溶媒である。物質(B)としては、種々の汎用有機溶媒が主に用いられる。溶液準備工程では、物質(B)として、単一の溶媒のみを使用してもよいし、2種類以上から成る混合溶媒を使用してもよい。物質(B)は、物質(A)の溶解性を損なわない範囲で選択可能である。
物質(C)は塩である。物質(C)により、得られる膜の透水性が向上するという効果が得られる。
膜の透水性が向上する理由について、発明者らは以下のように考えている。一般的には、製膜溶液を加熱乾燥することによって膜を形成すると、ポリマー鎖間での相互作用が非常に強く働くので、水の流路である孔が形成されにくく、膜の透水性が低くなる。これに対して、物質(C)は、物質(A)と相互作用することで、物質(A)同士の分子間相互作用を弱めることができる。こうして分子間相互作用が弱められた状態で製膜が行われることで、細孔がより多く形成される。
製膜溶液は、物質(D)をさらに含んでもよい。物質(D)は、下記物質(a)および(b)からなる群より選択される少なくとも1種類の化合物である。
(a)ヒドロキシル基およびその塩;アミノ基およびその塩;カルボキシル基、その塩およびその無水物;スルホ基、その塩およびその無水物;並びに、リン酸基、その塩およびその無水物からなる群より選択される少なくとも1種類の親水性基を有する化合物
(b)水
物質(D)は、低分子化合物であってもよい。また、低分子化合物である物質(D)は、1~3個の親水性基、その塩またはその無水物を有してもよい。ここで、「低分子化合物」とは、繰り返し構造を持たない化合物を意味し、特に分子量100未満の化合物を指す。
溶液準備工程として、以下、製膜原液を調製する工程(溶液調整工程)について説明する。具体的には、溶液調整工程は、上記(1)欄に挙げた製膜原液の成分を混合するステップを備える。均一透明な製膜溶液を調製するために、この工程は複数のステップを備えることができる。例えば、溶液調整工程は、各成分を含む溶液を加熱しながら撹拌することを含んでもよい。物質(A)~(D)の混合比および添加順序も特に限定されない。さらに、必要に応じ、架橋剤を混合してもよい。
製造方法は、製膜溶液により液膜を形成する工程(液膜形成工程)を備えてもよい。
液膜の形成には、ディップコート、スピンコート、アプリケーターを用いた塗布など、種々の方法を使用することができる。膜厚を数μm以下としたい場合、特に、スピンコートによる塗布が好ましい。液膜の形成は、具体的には、基板に対する製膜溶液の塗布によって実現可能である。
本発明の製造方法は、液膜形成工程の後に脱溶媒、必要に応じ架橋を行うことを含む。
本脱溶媒工程において、脱溶媒する方法としては、加熱乾燥による方法と、溶媒である物質(B)と相溶性を有しかつポリマーである物質(A)の貧溶媒であるような液体に浸漬する方法、の2通りが挙げられる。
製造方法は、さらに他の工程を含んでいてもよい。他の工程としては、例えば、脱溶媒工程で形成された半透膜を熱水で洗浄することが挙げられる。このような熱水洗浄処理により、ポリマーの運動性が向上し、ポリマー相の再編成が促進されるので、結果としてより緻密な膜とすることができる。本工程により、半透膜の脱塩性を向上させることができるので、必要に応じ実施するとよい。
なお、熱水洗浄処理とは、半透膜を所定の温度の熱水に、所定の時間浸漬させることを指す。具体的には、90℃の熱水中に5分間浸漬すればよい。さらに、本発明の半透膜における物質(D)は、熱水洗浄処理の後も膜内部に存在する。最終的に膜内部に存在する物質(D)は、FT-IR,固体NMR、DSCなどの手法により膜を分析し、物質(D)に由来するピークの存在から確認できる。さらに、ピーク強度から定量することも可能である。
表1~表7に製膜条件と膜構造パラメータ、透水実験により得られた性能値を整理した。表8に物質(A)の化学構造を整理した。物質(A)~(D)の混合率は、表1備考欄にて特に断りのない限り、表1における全ての実験番号において、(A)対(B)対(C)対(D1)対(D2)=15対60対10対10対5(重量比)に統一した。なお、D1およびD2は、いずれも物質(D)に該当する。
なお、物質A-6~A-10は、上述の物質(A)の定義に当てはまらないものであるが、便宜上、物質(A)として表記している。
ガラス容器に物質(A)を所定の量とり、物質(B)を加え、70℃で攪拌して透明均一な溶液を調製した後、物質(C)、(D2)を所定の量加え、さらに同温度で攪拌を行い透明均一な溶液とし、同温度での攪拌を継続したまま、最後に物質(D1)を徐々に添加し、溶解させ、透明均一な製膜溶液を得た。これを孔径0.2μmのPVDF(ポリフッ化ビニリデン)製メンブレンフィルターを用いて濾過した後、真空脱泡し、さらに24時間静置した後、製膜に用いた。
製膜はポリマー溶液のコーティング法により行った。シリコンウェハ上にポリマー溶液をスピンコートを用いて塗布し、膜厚が1μm程度になるように塗布量、回転速度、時間を適宜調節した。
その後、ポリマー溶液を塗布したシリコンウェハを加熱乾燥または水溶液に浸漬させることで脱溶媒を行った。脱溶媒後、常温の純水中で膜を剥離させた後、透水テストに用いた。熱水洗浄処理をした場合は、表1~表7の備考欄にて、特に断っている。
透水テスト前に、膜サンプルは全てイソプロピルアルコール水溶液に一定時間浸漬処理した。透水テストは、圧力:1MPa, 供給液の塩化ナトリウム濃度:500 ppm, 温度:25℃, pH:6.5で行った。全ての実験において、膜面積、測定時間を全て統一して実施した。
Jv=A(ΔP-σ・Δπ) ・・・式(1)
Js=B(Cm-Cp)+(1-σ)C× Flux ・・・式(2)
Cm=Cp+(供給液の塩濃度-Cp)× exp(Jv/Js) ・・・式(3)
ここで、Jvは水の膜透過流束(mol/m2/s)、ΔPは膜両側の圧力差(MPa)、σは溶質反射係数、Δπは膜両側の浸透圧差(MPa)、Jsは溶質の膜透過流束(mol/m2/s)、Cmは膜面における溶質の濃度(mol/m3)、Cpは透過液における溶質濃度(mol/m3)、Cは膜両側の濃度(mol/m3)である。
R=σ(1-F)/(1-aF) ・・・式(4)
なお、Fは式(5)で示される。また、Rは真の阻止率であって、式(6)で表される。
F=exp {-(1-σ) Jv/p} ・・・式(5)
R=1-Cp/Cm ・・・式(6)
ここで、Δpを種々変化させることにより式(1)からAを算出した。また、Jvを種々変化させてRを測定し、Rと1/Jvをプロットしたものに対して式(2)および(4)をカーブフィッティングすることにより、B(塩透過係数)とσ(溶質反射係数)とを同時に求めた。
EG:エチレングリコール
Gly:グリセリン
MA:無水マレイン酸
PVA:ポリビニルアルコール
NMP:N-メチル-2ーピロリドン
DMF:N,N-ジメチルホルムアミド
LiCl:塩化リチウム
MgCl2:塩化マグネシウム
ZnCl2:塩化亜鉛
以下の表1~表7および表9において、A/Bは、純水透過係数/塩透過係数の比率を示す。
表1より、番号1では透水性は得られなかった。これに対し、製膜溶液に無機塩を添加した番号2~4では透水性が見られた。中でも塩化マグネシウムを添加した番号3の場合、番号2~4の実験結果のうち、最も高いA/B値が得られた。
3.膜形成条件と透水性能
製膜条件と膜構造パラメータ、透水実験により得られた性能値を表9に整理した。物質(A)~(D)の混合率は、全て、(A)対(B)対(C)対(D1)対(D2)=15対60対10対10対5(重量比)に統一した。なお、D1およびD2は、いずれも物質(D)に該当する。なお、表9の番号38~55において、物質(B)は全てNMPであり、番号40~46および49~55において、物質(C)は全て塩化マグネシウムである。番号38、39、47および48では、物質(C)は添加しなかった。
ガラス容器に物質(A)を所定の量とり、物質(B)(全て、NMP)を加え、70℃で攪拌して透明均一な溶液を調製した後、物質(C)(全て、塩化マグネシウム)、(D2)を所定の量加え、さらに同温度で攪拌を行い透明均一な溶液とし、同温度での攪拌を継続したまま、最後に物質(D1)を徐々に添加し、溶解させ、続いて架橋剤であるサイメル303を所定量添加し、攪拌後、透明均一な製膜溶液を得た。これを孔径0.2μmのPVDF製メンブレンフィルターを用いて濾過した後、真空脱泡し、さらに24時間静置した後、製膜に用いた。
製膜はポリマー溶液のコーティング法により行った。シリコンウェハ上にポリマー溶液をスピンコートを用いて塗布し、膜厚が1μm程度になるように塗布量、回転速度、時間を適宜調節した。
その後、ポリマー溶液を塗布したシリコンウェハを加熱乾燥させることで脱溶媒と架橋αの形成を行った。脱溶媒後、常温の純水中で膜を剥離させた後、透水テストに用いた。
表9を参照すると、実験番号38、47にあるように、物質(A)単独ではほとんど半透性を示さなかった。一方、実験番号39,48では、架橋αの効果により、半透性の向上が見られ、その向上効果は、概ね0.1~0.15程度であった。実験番号40,49では、架橋αおよび架橋βの効果により、実験番号38、47に比べ、半透性の向上が確認され、向上効果は概ね0.35~0.4程度であった。実験番号41、42、43、および、50、51、52では、架橋α、架橋βに加え、各種の物質(D)を添加したところ、A/Bの劇的な向上を確認した。一方、実験番号44、53では、架橋βのみの効果を検証したところ、物質がA-1である場合は、架橋αおよび架橋βの効果がある実験番号40のA/Bの値に比べて架橋βの効果のみの実験番号44のA/Bの値は低い。しかし、物質がA-13である場合、架橋βの効果のみの実験番号53のA/Bの値は架橋αおよび架橋βの効果がある実験番号49のA/Bの値に比べて高くなっている。さらに、実験番号45、46および、54、55では、架橋βと各種物質(D)の添加効果を検証したところ、A/Bの向上が0.1~0.5程度であった。以上より、架橋α、架橋βの効果はそれぞれ単体でも、これら二者を組合わせても限定的であったが、架橋α、架橋β、物質(D)の三者を組合わせることで、非常に高い半透性向上効果を得た。
<架橋αの確認>
実験番号38~55の膜サンプル各5gを、NMP100mL中に浸漬し、70℃に加熱しながら12時間放置したところ、架橋αありの全てのサンプルで、膜がNMPに溶解しなかった。溶解しなかったサンプルを取り出し、200℃で加熱乾燥することで付着したNMPを蒸発させた後、再度重量を測定したところ、全てのサンプルで重量は不変であった。架橋αなしのサンプルは、全てNMPに溶解し、均一溶液となった。以上より、架橋剤を添加して作製し、表9で架橋αありと表示されているサンプルは、全て架橋αが進行していることを確認した。
FT-IR測定を用いて、物質(A)のアミド結合中のカルボニル基の伸縮振動ピークを追跡した。結果を表10に示す。実験番号38、47では、物質(C)を添加しなかったので、架橋βは形成されておらず、アミド結合間で分子間水素結合が形成されている。一方、実験番号44、42、53、55では、物質(C)を添加したが、これにより物質(A)のアミド結合中のカルボニル基の伸縮振動ピークが、約15程度シフトした。このシフトは、物質(C)の存在によりカルボニル基の炭素―酸素原子間の結合力が増強したことを示しており、つまりは、カルボニル基の分子間水素結合が弱まったことを示している。このことより、該カルボニル基が形成していた分子間水素結合がある程度の割合で切断され、物質(C)由来のマグネシウムイオンとイオン結合、つまりは、架橋βを新たに形成したことがわかった。さらに、実験番号38,47、42,44,53,55について、作製後の膜を硫酸および硝酸で加熱分解し、希硝酸で加温溶解して定容とした後、ICP発光分光分析による元素分析を行い、物質(C)であるマグネシウムの存在量を求めた。結果を表11に示す。物質(C)を添加しなかった実験番号38,47では、マグネシウムは検出されなかった。一方、実験番号42,44,53,55では、実験番号38,47と異なり、マグネシウムが検出され、膜内部にマグネシウムが存在していることが分かった。
膜中の物質(D)の所在を追跡した。結果を表12に示す。分析方法は、示差走査熱量測定法(DSC 法:Differential Scanning Calorimetry)である。ナノサイズの細孔やクラスターに閉じ込められた氷の融点は、通常のバルク氷(融点:0℃)に比べて低下する。この現象を利用して、DSC 曲線の融点の分布からクラスターおよび細孔半径分布、融解熱量から水分量を算出できる。具体的には、水に浸漬された試料をDSC測定直前に取り出し、過剰な表面付着水(バルク水)を除去してから密閉型試料容器に封入した。
DSC装置: TA Instruments 社製 DSC Q100
データ処理: 東レリサーチセンター製解析プログラム ”TRC-THADAP-DSC”
測定温度範囲: 約-55~5℃
昇温速度 :0.3℃/min
試料量 : 約5mg
試料容器: アルミニウム製密閉型試料容器
温度・熱量校正: 純水(融点0.0℃、融解熱量79.7cal/g)
さらに、実験番号51の膜を、90℃の熱水で5分間加熱した後、真空乾燥し、FT-IR測定および固体NMR測定を行ったところ、FT-IR測定では、エチレングリコールに由来する、脂肪族炭化水素基とアルコールのピークが観察された。固体DD/MAS NMR測定でも同様に、15~20ppm、および、55~60ppmにエチレングリコール由来のピークを観測し、膜内部のエチレングリコールの存在を確認した。ピーク強度を元にした換算から、膜内部に存在するエチレングリコールは、全炭素中で7%であった。
Claims (30)
- 下記物質(A)~(C)を含有する製膜溶液により液膜を形成する工程と、
前記液膜から溶媒を除去する脱溶媒工程と、
を備える半透膜の製造方法。
物質(A):アミド基、イミド基、スルホニル基および複素環からなる群より選択される1種類以上の構造部位を含む繰り返し単位構造を備えるポリマー
物質(B):物質(A)の良溶媒
物質(C):塩 - 前記製膜溶液は、下記物質(D)をさらに含有する
請求項1に記載の半透膜の製造方法。
物質(D):ヒドロキシル基およびその塩、アミノ基およびその塩、カルボキシル基、その塩およびその無水物、スルホ基、その塩およびその無水物、並びに、リン酸基、その塩およびその無水物からなる群より選択される親水性基を少なくとも1種類以上含む低分子化合物および水からなる群より選択される1種類以上の低分子化合物 - 前記脱溶媒工程は、前記液膜を、
(1)水、
(2)1価以上のアルコール
(3)水と1価以上のアルコールとの混合物、または
(4)物質(B)と水もしくは1価以上のアルコールの少なくとも一方との混合物のいずれかに接触させることを含む、
請求項1または2に記載の半透膜の製造方法。 - 前記脱溶媒工程は、液膜から物質(B)を乾燥させることを含む、
請求項1または2に記載の半透膜の製造方法。 - 形成された前記半透膜を熱水で洗浄する工程をさらに備える
請求項1~4のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液は、前記物質(A)として、ポリアミド、ポリベンズイミダゾール、ポリアミドイミド、ポリイミド、ポリスルホン、およびポリエーテルスルホンからなる群より選択される少なくとも1種類以上のポリマーを少なくとも含有する、
請求項1~5のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液は、前記物質(A)として親水性基およびハロゲン原子の少なくとも一方を有するポリマーを少なくとも含有する、
請求項1~6のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液は、前記物質(A)として、芳香族ポリアミドを少なくとも含有する、
請求項1~7のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液は、前記物質(A)として、メタ置換型芳香族ポリアミドを少なくとも含有する、
請求項1~8のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液は、前記物質(C)として、1種類以上の1価または2価の無機塩を少なくとも含有する、
請求項1~9のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液における前記物質(C)の含有率が、0.1重量%以上20%重量以下である、
請求項1~10のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液における前記物質(D)の含有率が、0.001重量%以上40重量%以下である、
請求項1~11のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液が、前記物質(D)として、水、ジオール、トリオールおよびジカルボン酸無水物から選択される少なくとも1種の物質を含有する、
請求項1~12のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液が、前記物質(D)として、親水性基またはその塩またはその無水物を有する繰り返し単位を備えるポリマーを少なくとも含む、
請求項1~13のいずれかに記載の半透膜の製造方法。 - 前記製膜溶液が、前記物質(D)として、数平均重合度が500以下であるポリマーを少なくとも含む、
請求項1~14のいずれかに記載の半透膜の製造方法。 - 下記物質(A)~(D)を含有する製膜溶液により液膜を形成した後、溶媒を除去することによって得られる膜を架橋してなる半透膜であって、該架橋が、下記2通りの架橋αおよびβを含むことを特徴とする、半透膜。
物質(A):アミド基、イミド基、スルホニル基および複素環からなる群より選択される1種類以上の構造部位を含む繰り返し単位構造を備えるポリマー
物質(B):物質(A)の良溶媒
物質(C):塩
物質(D):ヒドロキシル基およびその塩、アミノ基およびその塩、カルボキシル基、その塩およびその無水物、スルホ基、その塩およびその無水物、並びに、リン酸基、その塩およびその無水物からなる群より選択される親水性基を少なくとも1種類以上含む低分子化合物および水からなる群より選択される1種類以上の低分子化合物
架橋α:物質(A)を構成する窒素原子を介した共有結合
架橋β:物質(A)を構成する酸素原子もしくは窒素原子または親水性基と、上記物質(C)由来のカチオンとのイオン結合 - 物質(A)が、アミド基、イミド基、および複素環からなる群より選択される1種類以上の構造部位を含む繰り返し単位構造を備えるポリマーであることを特徴とする、請求項16に記載の半透膜。
- 物質(A)が、ポリアミドまたはポリベンズイミダゾールであることを特徴とする、請求項16に記載の半透膜。
- 物質(A)が、ポリアミドであることを特徴とする、請求項16に記載の半透膜。
- 物質(A)が、メタ置換型ポリアミドであることを特徴とする、請求項16に記載の半透膜。
- 物質(A)が、直鎖状のメタ置換型ポリアミドであることを特徴とする、請求項16に記載の半透膜。
- 物質(A)が、ヒドロキシ基、カルボン酸基、スルホン酸基、リン酸基、または、それらの塩から選ばれる親水性基を含むことを特徴とする、請求項16~21のいずれかに記載の半透膜。
- 架橋αが、多官能メラミン系化合物、または、ジビニルスルホンを架橋剤として使用し、形成されることを特徴とする、請求項16~22のいずれかに記載の半透膜。
- 架橋βに使用される物質(C)が、金属塩であることを特徴とする、請求項16~23のいずれかに記載の半透膜。
- 架橋βに使用される物質(C)が、2価以上の金属塩であることを特徴とする、請求項16~24のいずれかに記載の半透膜。
- 物質(D)が、水またはアルコールであることを特徴とする、請求項16~25のいずれかに記載の半透膜。
- 物質(D)が、水またはジオールまたはトリオールであることを特徴とする、請求項16~26のいずれかに記載の半透膜。
- 90℃の熱水で5分間洗浄後も、膜内部に物質(D)が存在することを特徴とする、請求項16~27のいずれかに記載の半透膜。
- 物質(D)としてエチレングリコールを含むことを特徴とする、請求項16~28のいずれかに記載の半透膜。
- 物質(A)~(D)を含有する製膜溶液により液膜を形成する工程と、
前記液膜から溶媒を除去する脱溶媒工程と、
架橋を形成する工程と、
を備える、請求項16~29のいずれかに記載の半透膜の製造方法。
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JPH0263535A (ja) * | 1988-08-30 | 1990-03-02 | Toyobo Co Ltd | 製膜用キャスティングドープ液 |
JPH02126925A (ja) * | 1988-07-28 | 1990-05-15 | Mitsubishi Kasei Corp | 複合分離膜 |
JP2000017002A (ja) | 1998-04-30 | 2000-01-18 | Sumitomo Rubber Ind Ltd | ゴム製品の製造方法およびそれに用いる感熱凝固性ラテックス |
JP2004034031A (ja) * | 2003-09-16 | 2004-02-05 | Toyobo Co Ltd | 中空糸型分離膜 |
JP2004105804A (ja) * | 2002-09-13 | 2004-04-08 | Fuji Photo Film Co Ltd | ポリスルホン微孔性膜及びその製法 |
JP2008114181A (ja) * | 2006-11-07 | 2008-05-22 | Mitsubishi Rayon Co Ltd | 中空状多孔質膜用支持体、中空状多孔質膜およびそれらの製造方法 |
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JP2011255312A (ja) | 2010-06-09 | 2011-12-22 | Fujifilm Corp | 順浸透装置および順浸透法 |
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JP2505631B2 (ja) * | 1990-08-09 | 1996-06-12 | 東レ株式会社 | 複合半透膜およびその製造方法および高純度水の製造方法 |
WO2012137635A1 (ja) * | 2011-04-01 | 2012-10-11 | 東レ株式会社 | 複合半透膜、複合半透膜エレメントおよび複合半透膜の製造方法 |
CN103170250A (zh) * | 2013-04-02 | 2013-06-26 | 天津工业大学 | 一种水过滤用杂化水凝胶平板膜及其制备方法 |
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2014
- 2014-06-11 EP EP14871040.3A patent/EP3085435A4/en not_active Withdrawn
- 2014-06-11 US US15/104,867 patent/US20160317973A1/en not_active Abandoned
- 2014-06-11 WO PCT/JP2014/065456 patent/WO2015093080A1/ja active Application Filing
- 2014-06-11 CN CN201480068326.6A patent/CN105828922B/zh active Active
- 2014-06-11 KR KR1020167017676A patent/KR102193369B1/ko active IP Right Grant
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CN106582307A (zh) * | 2017-02-17 | 2017-04-26 | 中国科学院大连化学物理研究所 | 一种共混膜的制备方法及共混膜的应用 |
Also Published As
Publication number | Publication date |
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KR102193369B1 (ko) | 2020-12-22 |
KR20160098295A (ko) | 2016-08-18 |
EP3085435A4 (en) | 2017-10-11 |
CN105828922A (zh) | 2016-08-03 |
US20160317973A1 (en) | 2016-11-03 |
EP3085435A1 (en) | 2016-10-26 |
CN105828922B (zh) | 2019-06-21 |
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