TWI645896B - Oil/water separation membrane - Google Patents

Abstract

An oil-water separation membrane for solving the problem that a conventional oil-water separation membrane is susceptible to hydrolysis, comprising: a substrate having a plurality of pores; and a homopolymer layer bonded to at least one surface of the substrate The homopolymer layer is formed by polymerization of a monomer as shown in Formula 1, Formula 2 or Formula 3:

Wherein R ₁ and R ₄ in the formula 3 respectively represent an alkyl group having a carbon number of 1 to 4, and R ₂ , R ₃ and R ₄ in the formula 1 respectively represent an alkyl group having a carbon number of 1 to 4, X. ^- indicates a halogen ion.

Description

Oil-water separation membrane

The present invention relates to an oil-water separation membrane, and more particularly to an oil-water separation membrane having good durability.

The conventional oil-water separation membrane is composed of three monomers including hydroxyethyl acrylate (HEA), methacrylamidopropyl betaine (SPP) and cetyldimethylaminoethyl methacrylate (DMHB). The copolymer layer is polymerized to achieve a good oil-water separation effect. An embodiment similar to the conventional oil-water separation membrane is disclosed in Chinese Patent Publication No. 105413236.

However, it is limited to having an ether group (RO-R') on both hydroxyethyl acrylate and cetyldimethylaminoethyl methacrylate, so that hydrolysis is liable to occur in use, so that Conventional oil-water separation membranes have poor durability and must be frequently replaced, so it is still necessary to provide a durable oil-water separation membrane to solve the above problems.

In order to solve the above problems, an object of the present invention is to provide an oil-water separation membrane which is less prone to hydrolysis.

The oil-water separation membrane of the present invention comprises: a substrate having a plurality of pores; and a homopolymer layer bonded to at least one surface of the substrate, the homopolymer layer being of the formula 2 or one of the monomers shown in Formula 3 is polymerized to form:

Wherein R ₁ and R ₄ in the formula 3 respectively represent an alkyl group having a carbon number of 1 to 4, and R ₂ , R ₃ and R ₄ in the formula 1 respectively represent an alkyl group having a carbon number of 1 to 4, X. ^- indicates a halogen ion.

Accordingly, the oil-water separation membrane of the present invention has a homopolymer layer formed by polymerization of a monomer as shown in Formula 1, Formula 2 or Formula 3, so that the oil-water separation membrane can not only have good oil-water separation efficiency and antibacterial property. Effect ^- and since the monomer which polymerizes to form the homopolymer layer does not have an ether group, the hydrolysis reaction does not occur even after repeated use, so that the oil-water separation membrane has good durability and is effective for the present invention. .

The oil-water separation membrane of the present invention, wherein the homopolymer layer is formed by polymerization of a monomer represented by Formula 1, and R ₁ represents a C 1 alkyl group, R ₂ , R ₃ and R ₄ Respectively denotes an alkyl group having a carbon number of 1, and X ^- represents a monochloride ion; or, the homopolymer layer is formed by polymerization of a monomer as shown in Formula 2, and R ₁ represents an alkylene group having a carbon number of 1 a group, R ₂ and R ₃ each represent an alkyl group having a carbon number of 1, or alternatively, the homopolymer layer is formed by polymerization of a monomer represented by Formula 3, and R ₁ and R ₄ represent a carbon number, respectively. An alkyl group is one alkyl group, and R ₂ and R ₃ each represent an alkyl group having a carbon number of 1. Thus, by the selection of a specific monomer, the effect of improving the durability of the oil-water separation membrane is achieved.

The oil-water separation membrane of the present invention, wherein the oil-water separation membrane is prepared by a method for preparing an oil-water separation membrane, the method for preparing the oil-water separation membrane comprises: mixing a monomer, water, a crosslinking agent and a starter In order to obtain a immersion plating solution, the immersion plating solution comprises 10 to 40% by weight of the monomer, 45 to 85% of water, 1 to 10% of the crosslinking agent, and 0.1 to 5% of the initiator. And immersing the substrate in the immersion plating solution, and then removing the monomer at a temperature of 60 to 90 ° C to polymerize the monomer on the surface of the substrate for 1 to 5 hours to form a surface of the substrate. The homopolymer layer. Thus, the durability of the oil-water separation membrane can be improved by the composition ratio of the monomer, water, the crosslinking agent, the initiator, and the temperature and time at which the monomer undergoes polymerization.

〔this invention〕

1‧‧‧Substrate

11‧‧‧ hole

2‧‧‧Homopolymer layer

Fig. 1 is a side sectional view showing an oil-water separation membrane according to an embodiment of the present invention.

Fig. 2a: Chemical formula (Formula 1) of a monomer used to polymerize the homopolymer layer forming the oil-water separation membrane of the present invention.

Fig. 2b is a chemical structural formula (Formula 2) of a monomer for polymerizing the homopolymer layer forming the oil-water separation membrane of the present invention.

Fig. 2c: Chemical formula (Formula 3) of a monomer for polymerizing the homopolymer layer forming the oil-water separation membrane of the present invention.

Fig. 3a: Chemical formula (Formula 4) of a monomer used to polymerize the homopolymer layer forming the oil-water separation membrane of the present invention.

Fig. 3b: Chemical formula (Formula 5) of a monomer for polymerizing the homopolymer layer forming the oil-water separation membrane of the present invention.

Figure 3c: Chemical formula (Formula 6) of a monomer used to polymerize the homopolymer layer forming the oil-water separation membrane of the present invention.

Figure 4: Hydrolysis rate of the oil-water separation membrane of Group A0 and Group A1.

Figure 5: Oil-water separation efficiency of the oil-water separation membrane of Group A1.

Figure 6: Oil-water separation efficiency of the oil-water separation membrane of Group A1 under different conditions.

The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the appended claims. The oil-water separation membrane of one embodiment of the present invention may comprise a substrate 1 and a homopolymer layer 2 bonded to at least one surface of the substrate 1.

In detail, the substrate 1 has a plurality of holes 11 . For example, the substrate 1 may be various porous substrates such as a stainless steel mesh, a copper mesh, a plastic mesh, a nylon mesh, a sponge, and the like. The pore size is between 4 and 150 μm.

The homopolymer layer 2 can be formed by polymerization of a monomer as shown in the second embodiment, wherein R ₁ and R ₄ in the formula 3 represent an alkyl group having a carbon number of 1 to 4, respectively. R ₂ , R ₃ and R ₄ in the formula 1 each represent a monoalkyl group having a carbon number of 1 to 4, and X ^- represents a halogen ion. For example, R ₄ in R ₁ and Formula 3 may each represent an alkylene group having a carbon number of 1, and R ₂ , R ₃ and R _{4 in} Formula 1 may each represent an alkyl group having a carbon number of 1, and X. ^- may represent a chloride ion, in which case the monomer may be 3-(methacryloylamino)propyltrimethylammonium chloride, as shown in Figure 3a, N-(3-dimethylaminopropyl)methacrylamide (as shown in Figure 3b) or [3-(methacrylamidoamino)propyl] [3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt, as shown in Figure 3c. The homopolymer layer 2 is in a solid state in a dry state, and is swollen to form a colloidal state after soaking in water.

The oil-water separation membrane is prepared by a method for preparing an oil-water separation membrane. For example, the worker may preferentially mix the monomer, water, a crosslinking agent and a starter to obtain a immersion bath containing 10-40% by weight. Body, 45~85% water, 1~10% crosslinker and 0.1~5% initiator. In this embodiment, the monomer may be 3-(methacryloylamino)propyltrimethylammonium chloride, and the crosslinking agent may be N,N'-methylenebisacrylamide ( Methylenebis (acrylamide) or diallyldimethylammonium chloride, the initiator may be ammonium persulfate or potassium persulfate, but the present invention Those with ordinary knowledge in the field can adjust themselves, and there is no restriction here.

Then, the worker can immerse the substrate 1 in the immersion plating solution, attach the immersion plating solution to the surface of the substrate 1 and then take it out, and continue to place the substrate 1 to which the immersion plating solution is attached. In the oven at a temperature of 60 to 90 ° C, the monomer can be subjected to polymerization for 1 to 5 hours, that is, the homopolymer layer 2 (thickness of about 1 to 10 μm) can be formed on the surface of the substrate 1 to obtain The oil-water separation membrane.

Thus, by using the networked homopolymer layer formed by polymerization of the monomer, the oil-water separation membrane has good oil-water separation efficiency even after repeated use, and the tertiary amine group on each monomer or The quaternary amine group (such as the functional group shown in the broken line in Figures 2a to 2c) can further impart a good antibacterial effect to the oil-water separation membrane. Therefore, the worker can arrange the oil-water separation membrane in a pipe member, so that the oily sewage flows vertically or horizontally through the oil-water separation membrane through gravity, that is, the oil-water separation effect can be achieved.

In order to confirm that the oil-water separation membrane of the present invention has good oil-water separation efficiency, antibacterial effect, and good durability, as shown in Table 1, the oil-water separation membrane of the present invention is used (the monomer used is 3-(methacryl oxime). Aminoamino)propyltrimethylammonium chloride, abbreviated as MAPTAC) as Group A1, and oil-water separation formed by a monomer having an ether group ([2-(methacryloyloxy)ethyl]trimethylammonium chloride, abbreviated as MATEAC) As the group A0, the membrane was subjected to the following tests:

The oil-water separation membranes of the A0 and A1 groups were respectively immersed in an aqueous hydrochloric acid solution (0.1 N), and the change of the hydrogen ion concentration in the aqueous hydrochloric acid solution at different times was measured, thereby evaluating the hydrolyzed state of each of the oil-water separation membranes. As a result, as shown in Fig. 4, the oil-water separation membrane of the present invention (Group A1) does not have a hydrolysis reaction, and has good durability.

In this test, an E. coli bacterial solution (concentration of 10 ⁶ CFU/mL) was passed through the oil-water separation membrane of the A0 and A1 groups, and the bacterial liquid was passed through the tray to record the number of colonies on each tray. The antibacterial effect of the oil-water separation membrane of Groups A0 and A1 was converted. As a result, as shown in Table 1, the oil-water separation membrane (Group A1) of the present invention has a preferable antibacterial effect.

In this test, an oil-water mixture (containing 30% by weight of oil) is passed through the oil-water separation membrane of Group A0, Group A1, respectively, and the total amount of oil that has not successfully passed through each group of oil-water separation membranes is measured, thereby The oil-water separation efficiency of each of the oil-water separation membranes was evaluated. As a result, as shown in Table 1, the oil-water separation membrane (Group A1) of the present invention has a preferable oil-water separation efficiency, and please refer to FIG. After 120 uses, it still has good oil-water separation efficiency.

In addition, the oil-water mixture obtained by mixing the oils and fats in different aqueous solutions (containing 30% by weight of oil) was evaluated in different environments, and the oil-water separation efficiency of the oil-water separation membrane (Group A1) of the present invention was observed. The aqueous solution of the oil-water mixture used in the acid environment test is an aqueous solution of hydrochloric acid (1N), and the aqueous solution of the oil-water mixture used in the alkaline environment test is an aqueous solution of sodium hydroxide (1N), which is used in the salt-containing environment test. The oil-water mixture contains an aqueous solution of sodium chloride (7% by weight), which is made in a high temperature environment. The oil-water mixture used comprises an aqueous solution heated to 80 ° C, and the aqueous solution of the oil-water mixture used in the emulsion environment comprises an emulsion (containing 1% by weight of Tween 20). The result is shown in FIG. The oil-water separation membrane of the present invention (Group A1) has good oil-water separation efficiency in various environments.

In summary, the oil-water separation membrane of the present invention has a homopolymer layer formed by polymerization of a monomer as shown in Formula 1, Formula 2 or Formula 3, so that the oil-water separation membrane can not only have good oil-water separation efficiency. And the antibacterial effect, and since the monomer which polymerizes to form the homopolymer layer does not have an ether group, the hydrolysis reaction does not occur even after repeated use, so that the oil-water separation membrane has good durability, which is the present invention. efficacy.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

Claims (5)

An oil-water separation membrane comprising: a substrate having a plurality of pores; and a homopolymer layer bonded to at least one surface of the substrate, the homopolymer layer being of Formula 1, Formula 2 or One of the monomers shown in Formula 3 is polymerized to form: Wherein R ₁ and R ₄ in the formula 3 respectively represent an alkyl group having a carbon number of 1 to 4, and R ₂ , R ₃ and R ₄ in the formula 1 respectively represent an alkyl group having a carbon number of 1 to 4, X. ^- indicates a halogen ion. The oil-water separation membrane according to claim 1, wherein the homopolymer layer is formed by polymerization of a monomer represented by Formula 1, and R ₁ represents an alkyl group having a carbon number of 1, R ₂ , R ₃ and R ₄ each represent an alkyl group having a carbon number of 1, and X ^- represents a monochloro ion. The oil-water separation membrane according to claim 1, wherein the homopolymer layer is formed by polymerization of a monomer represented by Formula 2, and R ₁ represents an alkyl group having a carbon number of 1, R ₂ and R ₃ each represent an alkyl group having 1 carbon number. The oil-water separation membrane according to claim 1, wherein the homopolymer layer is formed by polymerization of a monomer represented by Formula 3, and R ₁ and R ₄ represent a carbon number of 1 The group, R ₂ and R ₃ respectively represent an alkyl group having a carbon number of 1. The oil-water separation membrane according to claim 1, wherein the oil-water separation membrane is prepared by a method for preparing an oil-water separation membrane comprising: mixing a monomer, water, and a a crosslinking agent and an initiator to obtain a immersion plating solution containing 10 to 40% by weight of the monomer, 45 to 85% of water, 1 to 10% of the crosslinking agent, and 0.1 ~ 5% of the initiator; and the substrate is immersed in the immersion bath and then taken out, at a temperature of 60-90 ° C, the monomer is polymerized on the surface of the substrate for 1 to 5 hours, and The homopolymer layer is formed on the surface of the substrate.