CROSS-LINKED POROUS MEMBRANE FROM HYDROLYSIS OF ESTER-CONTAINING SIDE CHAIN AND PREPARATION METHOD THEREOF

Abstract

The present invention relates to a cross-linked porous membrane from hydrolysis of ester-containing side chain and a preparation method thereof. Firstly, membrane material is obtained through copolymerization of four monomers including butyl methacrylate, styrene, sodium sulfonated styrene and vinylbenzyl chloride. In membrane formation, a small amount of lithium chloride micromolecule porogen is added and cross-linked by using tetramethyl hexamethylene diamine to prepare a nanoscale dense membrane through hydrolysis under the alkaline condition. Through the characteristic of hydrolysis of a butyl ester side chain in the polymer under the alkaline condition, the space originally occupied by the butyl ester in the hydrolyzed membrane is vacated; and after hydrolysis, with the appearance of carboxylic acid ionic conduction groups, a large quantity of ester bonds is hydrolyzed, so that the patency of ion transfer channels in the membrane is enhanced. Thus, ionic conductivity of the membrane is greatly enhanced. The nanoscale porous membrane prepared by the present invention not only has good selectivity and battery performance, but also reduces the preparation cost of the membrane to a great extent, and is suitable for application in all vanadium flow batteries.

Claims

1. A cross-linked porous membrane from hydrolysis of an ester-containing side chain, characterized in that the cross-linked porous membrane is prepared through hydrolysis of a copolymer of ester-containing side chain in the presence of a micromolecule porogen under the alkaline condition; the copolymer of the ester-containing side chain is prepared by copolymerization of styrene, an ester-containing monomer, a vinylbenzyl chloride (VBC) monomer and an azodiisobutyronitrile initiator; the ester-containing monomer comprises butyl methacrylate, ethyl methacrylate and propyl methacrylate; the micromolecule porogen is lithium chloride; alkalis in the alkaline hydrolysis condition are sodium hydroxide and potassium hydroxide; the chemical structural formula of the cross-linked porous membrane is shown below: ##STR00004##

2. The cross-linked porous membrane from hydrolysis of the ester-containing side chain according to claim 1, wherein the concentrations of the sodium hydroxide and the potassium hydroxide are 3-6 mol/L.

3. A preparation method for the cross-linked porous membrane according to claim 1, comprising the following steps: (1) synthesizing the copolymer dissolving sodium sulfonated styrene (Nass) in solvent A at room temperature; respectively adding styrene (st), the ester-containing monomer, the VBC monomer and the azodiisobutyronitrile initiator (AIBN) under nitrogen protection; precipitating the obtained solution in a mixture of ethanol and water after reaction for 16-24 h at 50-80 C.; and washing the obtained precipitate with a detergent and drying at vacuum to obtain a yellowish granular product which is the copolymer, wherein the ester-containing monomer comprises butyl methacrylate (BMA), methyl methacrylate (MMA) and ethyl methacrylate (HMA); and a molar ratio of the st to the ester-containing monomer to the VBC to the Nass to the AIBN is 0-35:50-85:12.5:2.5:0.1, wherein the concentration of the Nass solvent is 0.125 mmol/ml; (2) cross-linked membrane forming dissolving the polymer prepared in the step (1) in solvent B at room temperature; adding a cross-linking agent and the micromolecule porogen after dissolving; molar weights of the cross-linking agent and the micromolecule porogen being 12.5% and 7.5% of the molar weight of the polymer; generating a cross-linking reaction for 30-60 minutes at room temperature to obtain a mixture; dropwise adding the mixture to a glass plate; and drying to obtain a dense membrane, wherein the mass ratio of the polymer to the solvent is 3%-10%; and the cross-linking agent is tetramethyl hexamethylene diamine, and the micromolecule porogen is lithium chloride; (3) preparing the porous membrane through alkaline thermal hydrolysis stripping the above dense membrane from the surface of the glass plate at room temperature, and placing the dense membrane in deionized water; taking out the dense membrane, placing the dense membrane in aqueous alkali of 4-6M, and hydrolyzing for 7-12 days at 60-90 C.; flushing the above hydrolyzed dense membrane with deionized water and then immersing the hydrolyzed dense membrane in the deionized water for 24-48 h until the surface of the membrane is neutral; immersing the membrane with a neutral surface in sulfuric acid solution of 1M, and placing the membrane into the deionized water after 24 h for standby.

4. The preparation method for the cross-linked porous membrane according to claim 3, wherein in the step (1) of synthesizing the copolymer, the solvent A is N,N-dimethylformamide, and the detergent is the mixture of ethanol and water.

5. The preparation method for the cross-linked porous membrane according to claim 3, wherein in the step (1) of synthesizing the copolymer, vacuum drying temperature is 40-80 C., and time is 24-48 h.

6. The preparation method for the cross-linked porous membrane according to claim 3, wherein in the step (2) of cross-linked membrane forming, the solvent 13 is N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), and the ratio of a solvent polymer is 0.2 ml/mmol.

7. The preparation method for the cross-linked porous membrane according to claim 3, wherein in the step (2) of cross-linked membrane forming, drying temperature is 40-80 C., and drying time is 24-48 h.

Description

DESCRIPTION OF DRAWINGS

[0028] FIG. 1 is an SEM graph of a cross-linked porous membrane.

[0029] FIG. 2 is a pore size distribution diagram of a cross-linked porous membrane BET.

[0030] FIG. 3 is an apparent diagram of a hydrolyzed cross-linked porous membrane.

[0031] FIG. 4 is a battery performance diagram of a cross-linked porous membrane under gradient current density.

DETAILED DESCRIPTION

[0032] The present invention is further described below in combination with specific embodiments.

Embodiment 1

[0033] 0.5725 g of Nass is added to 20 ml of DMF solvent at room temperature and is dissolved. 1.72 ml of st, 11.23 ml of BMA and 1.96 ml of VBC monomer are respectively added in nitrogen atmosphere. After the temperature is increased to 65 C., 0.0167 g of AIBN is added. The reaction is conducted for 20 h at a constant temperature of 65 C. The obtained solution is precipitated in a mixture of ethanol and water, and washed repeatedly for three times (3 h each time) with the mixed solution of ethanol and water. The ratio of the ethanol to the water is 7:1. The obtained solution is subjected to suction filtration with a funnel. Finally, the obtained solution is dried in a vacuum drying oven of 50 C. for 24 h to obtain a yellowish granular polymer.

[0034] 0.195 g of copolymer and 0.015 g of lithium chloride are dissolved in 5 ml of N,N-dimethylacetamide. After complete dissolving, 21 microlitres of tetramethyl hexamethylene diamine are added, and cross-linked for 30 minutes at room temperature. The above casting solution is cast on a glass plate into a membrane. The membrane is dried for 24 h at 50 C. to obtain a cross-linked dense membrane.

[0035] The above obtained membrane is stripped from the surface of the glass plate, and is placed in deionized water for 24 h. Then, the membrane is placed in aqueous alkali of 4.0 M, and hydrolyzed for 7 days at 70 C. The sodium hydroxide solution is changed every two days in order to promote the hydrolysis of ester bond.

[0036] The above hydrolyzed membrane is flushed with flowing deionized water for 5 minutes and then placed in the deionized water for 24-48 h until the surface of the membrane is neutral. The membrane with a neutral surface is immersed in sulfuric acid solution of 1M, and placed into the deionized water after 24 h for standby.

[0037] The obtained membrane has a water absorption rate of 30% and a swelling rate of 11%.

Embodiment 2

[0038] 0.5725 g of Nass is added to 20 ml of DMF solvent at room temperature and is dissolved. 4 ml of st, 8 ml of BMA and 1.96 ml of VBC monomer are respectively added in nitrogen atmosphere. After the temperature is increased to 50 C., 0.0167 g of AIBN is added. The reaction is conducted for 16 h at a constant temperature of 50 C. The obtained solution is precipitated in a mixture of ethanol and water, and washed repeatedly for three times (1 h each time) with ethanol and water. The ratio of the ethanol to the water is 3:5. The obtained solution is subjected to suction filtration with a funnel. Finally, the obtained solution is dried in a vacuum drying oven of 60 C. for 24 h to obtain a yellowish granular polymer.

[0039] 0.195 g of copolymer and 0.015 g of lithium chloride are dissolved in 5 ml of N,N-dimethylacetamide. After complete dissolving, 18 microlitres of tetramethyl hexamethylene diamine are added, and cross-linked for 15 minutes at room temperature. The above reaction solution is cast on a glass plate into a membrane. The membrane is dried for 24 h at 40 C. to obtain a cross-linked dense membrane.

[0040] The above membrane is stripped from the surface of the glass plate, and is placed in deionized water for 24 h. Then, the membrane is placed in aqueous alkali of 6.0 M, and hydrolyzed for 10 days at 70 C. The sodium hydroxide solution is changed every two days in order to promote the hydrolysis of ester bond.

[0041] The above hydrolyzed membrane is flushed with flowing deionized water for 5 minutes and then placed in the deionized water for 24-48 h until the surface of the membrane is neutral. The membrane with a neutral surface is immersed in sulfuric acid solution of 1M, and placed into the deionized water after 24 h for standby.

[0042] The obtained membrane has a water absorption rate of 30% and a swelling rate of 12%.

Embodiment 3

[0043] 0.5725 g of Nass is added to 20 ml of DMF solvent at room temperature and is dissolved. 20 ml of MMA and 3.92 ml of VBC monomer are respectively added in nitrogen atmosphere. After the temperature is increased to 80 C., 0.0167 g of AIBN is added. The reaction is conducted for 20 h at a constant temperature of 80 C. The obtained solution is precipitated in a mixture of ethanol and water, and washed repeatedly for three times (3 h each time) with ethanol and water. The ratio of the ethanol to the water is 9:1. Finally, the obtained solution is dried in a vacuum drying oven of 50 C. for 36 h to obtain a yellowish granular polymer.

[0044] 0.195 g of copolymer and 0.015 g of lithium chloride are dissolved in 5 ml of N,N-dimethylacetamide. After complete dissolving, 17.4 microlitres of tetramethyl hexamethylene diamine are added, and cross-linked for 60 minutes at room temperature. The above reaction solution is cast on a glass plate into a membrane. The membrane is dried for 24 h at 50 C. to obtain a cross-linked dense membrane.

[0045] The above obtained membrane is stripped from the surface of the glass plate, is placed in aqueous alkali of 5.0 M, and hydrolyzed for 10 days at 90 C. The sodium hydroxide solution is changed every two days in order to promote the hydrolysis of ester bond.

[0046] The above hydrolyzed membrane is flushed with flowing deionized water for 5 minutes and then placed in the deionized water for 24-48 h until the surface of the membrane is neutral. The membrane with a neutral surface is immersed in sulfuric acid solution of 1M, and placed into the deionized water after 24 h for standby.

[0047] The obtained membrane has a water absorption rate of 29% and a swelling rate of 13%.