CN112030190A - Application of SSBS-g-AA/SBS-g-DMAEMA bipolar membrane in preparation of lactobionic acid through electrooxidation - Google Patents
Application of SSBS-g-AA/SBS-g-DMAEMA bipolar membrane in preparation of lactobionic acid through electrooxidation Download PDFInfo
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- CN112030190A CN112030190A CN202010887331.7A CN202010887331A CN112030190A CN 112030190 A CN112030190 A CN 112030190A CN 202010887331 A CN202010887331 A CN 202010887331A CN 112030190 A CN112030190 A CN 112030190A
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- sbs
- dmaema
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- lactobionic acid
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- 239000012528 membrane Substances 0.000 title claims abstract description 84
- UOQHWNPVNXSDDO-UHFFFAOYSA-N 3-bromoimidazo[1,2-a]pyridine-6-carbonitrile Chemical compound C1=CC(C#N)=CN2C(Br)=CN=C21 UOQHWNPVNXSDDO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229940099563 lactobionic acid Drugs 0.000 title claims abstract description 61
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 27
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 26
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 239000003960 organic solvent Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 22
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 17
- 239000008101 lactose Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 16
- 229910001509 metal bromide Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000004973 liquid crystal related substance Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 238000010345 tape casting Methods 0.000 claims description 7
- 239000007832 Na2SO4 Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 7
- 238000005266 casting Methods 0.000 abstract description 6
- 238000006277 sulfonation reaction Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 150000003254 radicals Chemical class 0.000 abstract description 4
- 210000004379 membrane Anatomy 0.000 abstract 2
- 210000002469 basement membrane Anatomy 0.000 abstract 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 59
- 239000000047 product Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000005341 cation exchange Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- NFTVTXIQFYRSHF-UHFFFAOYSA-N 1-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)C(C)OC(=O)C=C NFTVTXIQFYRSHF-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- -1 Carboxyl Chemical group 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides application of an SSBS-g-AA/SBS-g-DMAEMA bipolar membrane in preparing lactobionic acid through electrooxidation. The invention takes SBS as basement membrane material, which is grafted and polymerized with free radical of acrylic acid after sulfonation, and introduces sulfonic group and carboxyl group as positive membrane (SSBS-g-AA) on the main chain; DMAEMA chain segment is grafted on the SBS main chain to be used as a negative film (SBS-g-DMAEMA); the SBS BPM is prepared by a casting method. The study showed that the current density and electrolysis time had a large influence on the yield and current efficiency of lactobionic acid when the current density was 30mA/cm2The yield of lactobionic acid reached a maximum at an electrolysis time of 180min, with an average yield of 49.03%, at which the current efficiency also reached a higher value. Compared with the traditional chemical synthesis method, the method has the advantages of mild reaction conditions, low cost and capability of avoiding environmental pollution.
Description
Technical Field
The invention relates to application of an SSBS-g-AA/SBS-g-DMAEMA bipolar membrane in preparation of lactobionic acid by electrooxidation.
Background
Bipolar membranes (BPM) are an extremely important branch of the field of membrane science, consisting of having selective permeationThe anion exchange layer and the cation exchange layer are compounded. Under the action of a direct current electric field, acidic and basic groups on the bipolar membrane can catalyze the water in the interface layer to be electrolyzed into H+And OH-. In order to obtain a bipolar membrane with excellent performances such as proper water-splitting capacity, low resistance, high permselectivity, high mechanical strength and the like, the bipolar membrane can be obtained by selecting proper membrane-forming materials and a membrane-casting method. The current tape casting method is often used for preparing bipolar membranes due to the advantages of simple steps, mature technology and the like. For film-forming materials without ion exchange groups, the performance of bipolar membranes is limited by the ratio and ease of introduction of the anionic and cationic active groups. The electrodialysis technology of the bipolar membrane brings new vitality and vitality for solving the technical problems in the fields of environment, chemical industry, biology, ocean chemical industry and the like.
Lactobionic acid is a new type of polyhydroxy organic acid formed by linking a molecule of galactose and a molecule of gluconic acid through an alpha-1, 4-glycosidic linkage. Lactobionic acid has the characteristics of strong oxidation resistance, ageing resistance, acceleration of cell renewal, promotion of skin metabolism and the like, so that the lactobionic acid is widely applied to the fields of cosmetics, medicines, foods and the like. At present, methods for preparing lactobionic acid include biological preparation methods and chemical oxidation methods, but both methods have the defects of high production cost, large environmental pollution and the like. In recent years, a method by organic electrosynthesis using a bipolar membrane has attracted considerable attention. It has been studied to use SBS-g- (AA/StSO)3Preparation of lactobionic acid (Chenwenjian-SBS bipolar membrane) by Na/SBS-g-DMAEMA bipolar membrane electrooxidation and application thereof in organic electrosynthesis [ D ]]Professor academic thesis of university of fujian, 2010), but the yield and current efficiency thereof are to be further improved. At present, the preparation of lactobionic acid by using the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane for electrooxidation is not seen.
Disclosure of Invention
In order to solve the problems, the invention provides the application of the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane in preparing lactobionic acid by electrooxidation.
Further, the current density is 10-40 mA/cm when the lactobionic acid is prepared by electrooxidation2；
And/or the electrolysis time for preparing lactobionic acid by electrooxidation is 100-200 min;
preferably, the first and second electrodes are formed of a metal,
the current density is 30mA/cm when the electrooxidation is used for preparing the lactobionic acid2；
And/or the electrolysis time for preparing lactobionic acid by electrooxidation is 180 min.
Further, when the lactobionic acid is prepared by electro-oxidation, the temperature is 20-40 ℃; and/or the anolyte is a mixed solution of lactose and metal bromide; and/or the catholyte is a sulfate solution;
preferably, the first and second electrodes are formed of a metal,
when the lactobionic acid is prepared by electrooxidation, the temperature is 30 ℃;
and/or the concentration of lactose in the anolyte is 0.1-1 mol/L; the concentration of the metal bromide is 0.1-1 mol/L;
and/or the concentration of a sulfate solution in the catholyte is 0.1-1 mol/L;
more preferably still, the first and second liquid crystal compositions are,
in the anolyte, the concentration of lactose is 0.15 mol/L; the concentration of the metal bromide is 0.3 mol/L;
and/or, in the catholyte, the concentration of the sulfate solution is 0.3 mol/L;
it is further preferred that the first and second liquid crystal compositions,
the metal bromide is KBr or NaBr;
and/or the sulfate solution is Na2SO4Solutions or K2SO4And (3) solution.
Furthermore, the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane consists of an SSBS-g-AA anode membrane and an SBS-g-DMAEMA cathode membrane;
preferably, the preparation method of the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane comprises the following steps: the SBS-g-DMAEMA emulsion and the SSBS-g-AA emulsion are prepared by a tape casting method;
more preferably, the thickness of the anode film is 10 to 100 μm; and/or the thickness of the cathode film is 10-100 μm;
further preferably, the thickness of the anode film is 20-80 μm; and/or the thickness of the cathode film is 20-80 μm;
still further preferably, the thickness of the anodic film is 40 μm; and/or the thickness of the cathode film is 40 μm.
Further, the preparation method of the SBS-g-DMAEMA emulsion comprises the following steps:
dissolving SBS in organic solvent, adding DMAEMA and AIBN, and reacting to obtain the product;
preferably, the first and second electrodes are formed of a metal,
the organic solvent is a mixed solution of toluene and dioxane;
and/or the mass volume ratio of the SBS to the organic solvent is 1g to (8-10) mL;
and/or the mass ratio of SBS to DMAEMA is 1: 0.1-0.7;
and/or the mass of the AIBN is 1.0 percent of the mass of the DMAEMA;
and/or reacting for 1-3 h at 80-100 ℃ under the protection of nitrogen;
more preferably, the volume ratio of toluene to dioxane is 1: 1.
Further, the preparation method of the SSBS-g-AA emulsion comprises the following steps:
(1) dissolving SBS in organic solvent, adding concentrated sulfuric acid to react to obtain sulfonated product SSBS;
(2) dissolving the sulfonated product SSBS in an organic solvent, adding acrylic acid and BPO, and reacting to obtain the sulfonated product;
preferably, the first and second electrodes are formed of a metal,
in the step (1), the organic solvent is cyclohexane;
and/or in the step (1), the mass-volume ratio of the SBS to the organic solvent to the concentrated sulfuric acid is 1g to (5-10) mL to (0.5-1) mL;
and/or in the step (1), the reaction is carried out for 1-2 h at the temperature of 30-35 ℃;
and/or, in the step (2), the organic solvent is a mixed solution of toluene and dioxane;
and/or in the step (2), the mass-volume ratio of the SBS to the organic solvent is 1g to (8-10) mL;
and/or in the step (2), the mass ratio of SBS to acrylic acid is 1: 0.1-0.5;
and/or, in the step (2), the BPO accounts for 1.0 percent of the mass of the acrylic acid;
and/or in the step (2), reacting for 1-3 h at 80-100 ℃ under the protection of nitrogen;
more preferably, the volume ratio of toluene to dioxane is 3: 1.
The invention also provides a method for preparing lactobionic acid by electrooxidation, which uses SSBS-g-AA/SBS-g-DMAEMA bipolar membrane as a diaphragm of a cathode electrode and an anode electrode;
preferably, the first and second electrodes are formed of a metal,
the current density is 10-40 mA/cm when the lactobionic acid is prepared by electrooxidation2；
And/or the electrolysis time for preparing lactobionic acid by electrooxidation is 100-200 min;
and/or when the lactobionic acid is prepared by electro-oxidation, the temperature is 20-40 ℃;
and/or the anolyte is a mixed solution of lactose and metal bromide;
and/or the catholyte is a sulfate solution;
more preferably still, the first and second liquid crystal compositions are,
the current density is 30mA/cm when the electrooxidation is used for preparing the lactobionic acid2；
And/or the electrolysis time for preparing lactobionic acid by electrooxidation is 180 min;
and/or, when the lactobionic acid is prepared by electro-oxidation, the temperature is 30 ℃;
and/or the concentration of lactose in the anolyte is 0.1-1 mol/L; the concentration of the metal bromide is 0.1-1 mol/L;
and/or the concentration of a sulfate solution in the catholyte is 0.1-1 mol/L;
it is further preferred that the first and second liquid crystal compositions,
in the anolyte, the concentration of lactose is 0.15 mol/L; the concentration of the metal bromide is 0.3 mol/L;
and/or, in the catholyte, the concentration of the sulfate solution is 0.3 mol/L;
it is still further preferred that the first and second substrates are,
the metal bromide is KBr or NaBr;
and/or the sulfate solution is Na2SO4Solutions or K2SO4And (3) solution.
Furthermore, the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane consists of an SSBS-g-AA anode membrane and an SBS-g-DMAEMA cathode membrane;
preferably, the preparation method of the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane comprises the following steps: the SBS-g-DMAEMA emulsion and the SSBS-g-AA emulsion are prepared by a tape casting method;
more preferably, the thickness of the anode film is 10 to 100 μm; and/or the thickness of the cathode film is 10-100 μm;
further preferably, the thickness of the anode film is 20-80 μm; and/or the thickness of the cathode film is 20-80 μm;
still further preferably, the thickness of the anodic film is 40 μm; and/or the thickness of the cathode film is 40 μm.
Further, the preparation method of the SBS-g-DMAEMA emulsion comprises the following steps:
dissolving SBS in organic solvent, adding DMAEMA and AIBN, and reacting to obtain the product;
preferably, the first and second electrodes are formed of a metal,
the organic solvent is a mixed solution of toluene and dioxane;
and/or the mass volume ratio of the SBS to the organic solvent is 1g to (8-10) mL;
and/or the mass ratio of SBS to DMAEMA is 1: 0.1-0.7;
and/or the mass of the AIBN is 1.0 percent of the mass of the DMAEMA;
and/or reacting for 1-3 h at 80-100 ℃ under the protection of nitrogen;
more preferably, the volume ratio of toluene to dioxane is 1: 1.
Further, the preparation method of the SSBS-g-AA emulsion comprises the following steps:
(1) dissolving SBS in organic solvent, adding concentrated sulfuric acid to react to obtain sulfonated product SSBS;
(2) dissolving the sulfonated product SSBS in an organic solvent, adding acrylic acid and BPO, and reacting to obtain the sulfonated product;
preferably, the first and second electrodes are formed of a metal,
in the step (1), the organic solvent is cyclohexane;
and/or in the step (1), the mass-volume ratio of the SBS to the organic solvent to the concentrated sulfuric acid is 1g to (5-10) mL to (0.5-1) mL;
and/or in the step (1), the reaction is carried out for 1-2 h at the temperature of 30-35 ℃;
and/or, in the step (2), the organic solvent is a mixed solution of toluene and dioxane;
and/or in the step (2), the mass-volume ratio of the SBS to the organic solvent is 1g to (8-10) mL;
and/or in the step (2), the mass ratio of SBS to acrylic acid is 1: 0.1-0.5;
and/or, in the step (2), the BPO accounts for 1.0 percent of the mass of the acrylic acid;
and/or in the step (2), reacting for 1-3 h at 80-100 ℃ under the protection of nitrogen;
more preferably, the volume ratio of toluene to dioxane is 3: 1.
The invention selects polymer SBS (styrene-butadiene-styrene block copolymer) with reaction functional group as base membrane material, firstly sulfonates it, then introduces carboxyl with controllable content through free radical graft polymerization, prepares SSBS-g-AA, and uses it as cation exchange membrane; SBS and DMAEMA graft polymerization prepare SBS-g-DMAEMA containing tertiary amine group, used as anion exchange membrane, have avoided using carcinogenic substance chloromethyl methyl ether to carry on chloromethylation traditionally; finally, preparing the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane (marked as SBS BPM) by a tape casting method. SBS BPM is used as a diaphragm between a yin chamber and a yang chamber and is applied to electrochemical oxidation for preparing lactobionic acid.
The invention takes SBS as base membrane material, which is grafted and polymerized with Acrylic Acid (AA) free radical after sulfonation, and introduces sulfonic group and carboxyl group as positive membrane (SSBS-g-AA) on the main chain; in SBS main chainThe upper grafted DMAEMA chain segment is used as a negative film (SBS-g-DMAEMA); the SBS BPM is prepared by a casting method. SBS BPM is used as a diaphragm of an electrolytic cell for preparing lactobionic acid by electrooxidation. H generated by water ionization in bipolar membrane interface layer+And OH-Ions can respectively permeate the anode membrane and the cathode membrane to electrolyze with OH generated by the cathode chamber and the anode chamber-And H+The neutralization reaction proceeds to promote the forward progress of the reaction. The study showed that the current density and electrolysis time had a large influence on the yield and current efficiency of lactobionic acid when the current density was 30mA/cm2The electrolysis time is 180 min. The yield of lactobionic acid was maximized at an average yield of 49.03%, where the current efficiency was also over 50%. Compared with the traditional chemical synthesis method, the method has the advantages of mild reaction conditions, low cost and capability of avoiding environmental pollution.
Preparation and application of SBS bipolar membrane in organic electrosynthesis (Chenwenjia, Fuzhou: Master academic thesis of university of Fujian province, 2010.) use SBS-g- (AA/StSO)3The Na)/SBS-g-DMAEMA bipolar membrane electrooxidation is used for preparing the lactobionic acid, but the optimal average yield is only 47.39%, and the current efficiency is only 42.11%, while the average yield of the lactobionic acid can reach 49.03% and the average current effect is higher than 50.42%. Compared with the paper, the invention has the advantages of obviously improved yield and current efficiency.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 shows the contact angles before and after SBS modification: a is the contact angle of SBS before modification; b is the contact angle of the modified SSBS-g-AA; c is the contact angle of the modified SBS-g-DMAEMA.
FIG. 2 is an infrared spectrum of SBS, SSBS-g-AA and SBS-g-DMAEMA.
FIG. 3 is an I-V operating curve of SBS BPM.
FIG. 4 is a scanning electron micrograph of a bipolar membrane of the present invention.
FIG. 5 is a schematic diagram of the preparation of lactobionic acid by electro-oxidation of SBS BPM.
FIG. 6 shows the change in lactobionic acid yield and current efficiency at different current densities.
FIG. 7 shows the variation of lactobionic acid yield and current efficiency at different electrolysis times.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
1. Experimental materials
Styrene-butadiene-styrene block copolymer (SBS): 792, S/B: 30/70, white porous granular structure, product of the chemical general company Yueyang in Hunan. Dioxane: a CP stage; toluene, Acrylic Acid (AA), N-dimethylaminoethyl acrylate (DMAEMA), AR grade; benzoyl Peroxide (BPO), Azobisisobutyronitrile (AIBN) were recrystallized before use. The drugs used in the experiments such as lactose, KBr, phenolphthalein and the like are all commercial analytical pure reagents.
2. Laboratory apparatus
NEXUS670 intelligent fourier infrared spectrometer (nigaforce corporation); model SL200B contact angle measuring instrument (shanghai barron information technology ltd); XL30ESEM/TMP environmental scanning Electron microscope (PHILIPS Corp.); DF1720SB5A type dc regulated power supply (ningbo zhongshi electronics ltd); electrochemical workstation model CHI 660C.
Example 1 preparation of SSBS-g-AA/SBS-g-DMAEMA Bipolar Membrane
1. Synthesis of SBS graft copolymer
(1) Synthesis of SBS-g-DMAEMA copolymer
5g SBS was dissolved in 20mL toluene and 20mL dioxane mixed solution and 3.5g DMAEMA and 1.0% AIBN (by mass of DMAEMA) were added. In N2Reacting at the temperature of 80 ℃ for 3 h. Obtain SBS-g-DMAEMA graft copolymer (SBS-g-DMAEMA emulsion). Will be provided withThe product is poured into methanol to separate out a precipitate, filtered, washed by methanol and finally dried in vacuum at 40 ℃ to constant weight. The graft ratio of DMAEMA was 26.7% as calculated by the formula (1).
Wherein rho is the grafting rate of SBS; w1、W2The mass of SBS before and after grafting, g, respectively.
(2) Synthesis of SSBS-g-AA copolymer
Fully dissolving 5g SBS in 25mL cyclohexane, slowly dripping 2.5mL concentrated sulfuric acid under rapid stirring, reacting for 2h at 35 ℃, pouring the obtained product into water to boil, and removing the residual sulfuric acid to obtain the sulfonated product SSBS.
And measuring the sulfonic acid group content of the SSBS by an acid amount method. A certain amount of SSBS was dissolved in cyclohexane, phenolphthalein was used as an indicator, and the degree of sulfonation DS (mmol/g) was calculated by titration with 0.1mol/L KOH-ethanol standard solution according to the following formula:
in the formula, V is the volume of a KOH-ethanol standard solution, mL; c is the concentration of KOH-ethanol standard solution, mol/L; m is SSBS sample mass, g.
SSBS polymer was synthesized in this experiment, and the sulfonation degree of SSBS was 0.53mmol/g as calculated by the formula (2).
5g of SSBS are dissolved in 40mL of a mixed solution of toluene and dioxane (V/V-3/1), 2.5g of freshly distilled acrylic acid (AA, which is chemically reactive and readily polymerizable in air and therefore used after refining by distillation under reduced pressure before use) and 1.0% of BPO (based on the mass of AA) are added, and the mixture is purified in N2Reacting at medium 80 ℃ for 3h, and cooling to stop the reaction to obtain the microemulsion (SSBS-g-AA copolymer). The product was poured into methanol to precipitate, filtered, rinsed many times, vacuum dried, and the grafting ratio of AA in SSBS-g-AA copolymerization was calculated as 16.0% according to formula (1).
2. Preparation of SBS BPM
Taking 2g of SBS-g-DMAEMA emulsion, casting the emulsion on a clean and smooth glass plate, and air-drying the emulsion at room temperature to form a film, namely a tertiary amine type SBS-g-DMAEMA positive film layer (a colorless film, the thickness of the film is 20-80 mu m); and (3) taking 2g of SSBS-g-AA emulsion, casting the emulsion on the colorless film, and air-drying at room temperature to form a film, thus obtaining the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane (SBS BPM).
The unit for connecting anion and cation exchange groups in the bipolar membrane is respectively shown as the formula (a) and the formula (b), wherein (a) is-COOH and-SO3Attachment of H cation exchange groups; (b) is-CH2N(CH3)2Attachment of anion exchange groups.
Example 2 characterization of SSBS-g-AA/SBS-g-DMAEMA Bipolar Membrane
First, experiment method
1. Determination of ion exchange Capacity and hydrophilicity of Membrane
The water content and ion exchange capacity of SSBS-g-AA and SBS-g-DMAEMA were determined according to the method described in the literature (Xu C X, Chen R Y, Zheng X, et al, preparation of PVA-GA-CS/PVA-Fe-SA bipolar Membrane and its application in electro-generation of 2, 2-dimethyl-3-hydroxypironic acid [ J ]. Journal of Membrane Science,2008,307(2): 218. 224.). The contact angle of the redistilled water on the membrane surface was measured using a contact angle measuring instrument model SL200B to examine the hydrophilicity.
2. Composition and morphology analysis of membranes
And (3) measuring the infrared spectrum of the membrane by using a Fourier infrared spectrometer, and observing the interface morphology of the bipolar membrane by using a scanning electron microscope.
3. I-V working curve of membrane
Test apparatus reference (Lezhonggui et al, research on paired electrosynthesis of succinic acid and p-chlorobenzaldehyde using bipolar membrane technology [ J)]Application of chemical engineering, 2015,44(09):1687-1690.), a bipolar membrane is used as a diaphragm between a cathode chamber and an anode chamber, and 200mL of Na with the concentration of 1mol/L is respectively injected into the two chambers2SO4Solutions ofAs an electrolyte, a graphite electrode (apparent contact area of 2 cm) was inserted2). The DC regulated power supply is used to measure the variation of the cell voltage between cathode and anode with current density. Under the same conditions, cell voltage vs. current density curves were determined without the separator. The difference between the two measured voltages is the actual voltage drop of the membrane.
Second, experimental results
1. Water content and ion exchange capacity
The water contents of the SBS-g-DMAEMA anion exchange membrane and the SSBS-g-AA cation exchange membrane measured by experiments are respectively as follows: 65.8% and 51.2%. Contact angle results show (fig. 1): the SBS before modification has a relatively poor hydrophilicity, so that the contact angle is relatively large (97.50 degrees), and after sulfonation, AA grafting modification is carried out, so that the hydrophilicity of the surface of the SBS is obviously improved, the contact angle is reduced to 61.3 degrees, and the contact angle of the SBS and the DMAEMA graft copolymer is 23.2 degrees.
As the water content of the SSBS-g-AA is close to that of the SBS-g-DMAEMA, and the ion exchange capacity of the SSBS-g-AA and the SBS-g-DMAEMA is equivalent to 1.54mmol/g and 1.42mmol/g respectively, the SBS BPM is prepared by adopting a tape casting method.
2. FT-IR analysis
FIG. 2 shows the IR spectra of SBS, SSBS-g-AA and SBS-g-DMAEMA at 3025 and 3006cm in SBS-1And 1601, 1632cm-1The absorption peak is the C ═ C stretching vibration absorption in the benzene ring and the double bond in the SBS molecular chain. Compared with SBS, SSBS and SSBS-g-AA are at 1600cm-1The infrared absorption peak of C-C is obviously weakened, and 1252 and 1018 cm-added1And the stretching vibration absorption peak of O ═ S ═ O in the sulfonic acid group shows that the SBS molecular chain introduces sulfonic acid group. Furthermore, SSBS-g-AA increased by 3410cm-1Carboxyl middle-OH stretching vibration absorption peak, 1726cm-1And the carbonyl stretching vibration absorption peak indicates that the SSBS successfully introduces the acrylic chain segment. 1710cm is increased in the SBS-g-DMAEMA infrared spectrogram-1Ester group stretching vibration absorption peak, 2760cm-1And a tertiary amine group stretching vibration absorption peak indicates that DMAEMA is grafted on the SBS molecular chain.
3. I-V working curve of SBS BPM
FIG. 3 is an I-V operating curve of SBS BPM, from the figureIt can be seen that: greater than 30mA/cm2The SBS BPM cell voltage rose sharply when the current density increased due to H produced after ionization of water in the middle layer+、OH-The speed of diffusion to the cathode and anode chambers is increased, water outside the membrane cannot be timely supplemented into the middle layer of the bipolar membrane, a depletion layer is generated in the middle layer, and the impedance is increased. When the current density is less than 30mA/cm2The SBS BPM cell voltage is maintained at about 3.5V.
4. Interface morphology of SBS BPM bipolar membrane
The interface morphology of the SBS BPM bipolar membrane measured by a scanning electron microscope is shown in FIG. 4, a clear interface is arranged between a negative membrane and a positive membrane in the bipolar membrane, the average membrane thickness is about 80 μm, the upper layer is an SBS-g-DMAEMA negative membrane with the thickness of about 40 μm, and the lower layer is an SSBS-g-AA positive membrane with the thickness of about 40 μm. The film was dense with no bubble voids found.
EXAMPLE 3 preparation of lactobionic acid by bipolar membrane electrooxidation with SSBS-g-AA/SBS-g-DMAEMA
1. Experimental methods
As shown in figure 5, the anode and the cathode are both graphite, and under the action of the direct current electric field, water in the interface layer in the middle of the bipolar membrane is ionized into H+And OH-Ion, H+Enters the cathode chamber through the SSBS-g-AA anode membrane and is electrolyzed with OH generated by water-Binding to form H2O, and the generated OH-enters the anode chamber through the SBS-g-DMAEMA cathode membrane and is electrically oxidized with lactose to generate H generated in the process of generating lactobionic acid+Binding to form H2O, thereby promoting the reaction to proceed in the forward direction. KBr as a medium for indirect electrocatalytic oxidation, Br-Oxidized to Br at the anode2Followed by oxidation of lactose to lactobionic acid, which is itself reduced to Br-The reaction mechanism is shown below:
anode: 2Br--2e-→Br2
C12H22O11+Br2+H2O→C12H22O12+2H++2Br-
Cathode: 2H2O+2e-→H2+2OH-
2. Results of the experiment
In industrial production, it is always desirable to carry out organic electrosynthesis at higher current densities in order to achieve high space-time yields, but too high a current density often leads to increased side reactions, which lead to a reduction in current efficiency and selectivity. In order to select the proper current density, the SBS BMP prepared in example 1 is used as a diaphragm, the anolyte is a mixed solution of 0.15mol/L lactose and 0.3mol/L KBr, and the catholyte is 0.3mol/L Na at 30 DEG C2SO4Electrolyzing the solution with graphite as cathode and anode for 180 min. Examining the effect of current density on the reaction, it can be seen from FIG. 6 that as the current density increases, the yield of lactobionic acid increases and the current efficiency η decreases, which may be due to the decrease of current efficiency caused by the increase of cell voltage, hydrogen evolution and oxygen evolution due to the too high current density. When the current density reaches 30mA/cm2The yield reached a maximum, and the current efficiency reached 50.87% at this time.
FIG. 7 shows the current density at 30mA/cm2The yield and current efficiency of lactobionic acid was measured as a function of electrolysis time. The results show that the lactobionic acid yield increases and then decreases with increasing electrolysis time, reaches a maximum at a reaction time of 180min, and decreases over a time of 180min, while the current efficiency decreases significantly. This is because the electrolysis time is too long, part of lactobionic acid will continue to oxidize and polymerize into oily high molecular polymer, resulting in a decrease in yield of lactobionic acid and a corresponding rapid decrease in current efficiency.
Under the above suitable conditions (30 ℃, the anolyte is a mixture of 0.15mol/L lactose and 0.3mol/L KBr, and the catholyte is 0.3mol/L Na2SO4Solution at 30mA/cm2Lower electrolysis for 180min), 4 parallel experiments were performed, and the results showed (see table 1): the repeatability is good, the average yield of the lactobionic acid can reach 49.03 percent, and the average current effect is 50.42 percent.
TABLE 1 results of parallel experiments
In conclusion, SBS is used as a base membrane material, and is grafted and polymerized with Acrylic Acid (AA) free radicals after sulfonation, and sulfonic groups and carboxyl groups are introduced to a main chain to serve as a positive membrane (SSBS-g-AA); DMAEMA chain segment is grafted on the SBS main chain to be used as a negative film (SBS-g-DMAEMA); the SBS BPM is prepared by a casting method. SBS BPM is used as a diaphragm of an electrolytic cell for preparing lactobionic acid by electrooxidation. H generated by water ionization in bipolar membrane interface layer+And OH-Ions can respectively permeate the anode membrane and the cathode membrane to electrolyze with OH generated by the cathode chamber and the anode chamber-And H+The neutralization reaction proceeds to promote the forward progress of the reaction. The study showed that the current density and electrolysis time had a large influence on the yield and current efficiency of lactobionic acid when the current density was 30mA/cm2The yield of lactobionic acid reached a maximum at an electrolysis time of 180min, with an average yield of 49.03%, and a current efficiency of 50.42% was achieved. Compared with the traditional chemical synthesis method, the method has the advantages of mild reaction conditions, low cost and capability of avoiding environmental pollution.
Claims (10)
- The application of an SSBS-g-AA/SBS-g-DMAEMA bipolar membrane in preparing lactobionic acid through electrooxidation.
- 2. Use according to claim 1, characterized in that: the current density is 10-40 mA/cm when the lactobionic acid is prepared by electrooxidation2；And/or the electrolysis time for preparing lactobionic acid by electrooxidation is 100-200 min;preferably, the first and second electrodes are formed of a metal,the current density is 30mA/cm when the electrooxidation is used for preparing the lactobionic acid2；And/or the electrolysis time for preparing lactobionic acid by electrooxidation is 180 min.
- 3. Use according to claim 1, characterized in that: when the lactobionic acid is prepared by electrooxidation, the temperature is 20-40 ℃; and/or the anolyte is a mixed solution of lactose and metal bromide; and/or the catholyte is a sulfate solution;preferably, the first and second electrodes are formed of a metal,when the lactobionic acid is prepared by electrooxidation, the temperature is 30 ℃;and/or the concentration of lactose in the anolyte is 0.1-1 mol/L; the concentration of the metal bromide is 0.1-1 mol/L;and/or the concentration of a sulfate solution in the catholyte is 0.1-1 mol/L;more preferably still, the first and second liquid crystal compositions are,in the anolyte, the concentration of lactose is 0.15 mol/L; the concentration of the metal bromide is 0.3 mol/L;and/or, in the catholyte, the concentration of the sulfate solution is 0.3 mol/L;it is further preferred that the first and second liquid crystal compositions,the metal bromide is KBr or NaBr;and/or the sulfate solution is Na2SO4Solutions or K2SO4And (3) solution.
- 4. Use according to claim 1, characterized in that: the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane consists of an SSBS-g-AA anode membrane and an SBS-g-DMAEMA cathode membrane;preferably, the preparation method of the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane comprises the following steps: the SBS-g-DMAEMA emulsion and the SSBS-g-AA emulsion are prepared by a tape casting method;more preferably, the thickness of the anode film is 10 to 100 μm; and/or the thickness of the cathode film is 10-100 μm;further preferably, the thickness of the anode film is 20-80 μm; and/or the thickness of the cathode film is 20-80 μm;still further preferably, the thickness of the anodic film is 40 μm; and/or the thickness of the cathode film is 40 μm.
- 5. Use according to claim 4, characterized in that: the preparation method of the SBS-g-DMAEMA emulsion comprises the following steps:dissolving SBS in organic solvent, adding DMAEMA and AIBN, and reacting to obtain the product;preferably, the first and second electrodes are formed of a metal,the organic solvent is a mixed solution of toluene and dioxane;and/or the mass volume ratio of the SBS to the organic solvent is 1 g: (8-10) mL;and/or the mass ratio of SBS to DMAEMA is 1:0.1 to 0.7;and/or the mass of the AIBN is 1.0 percent of the mass of the DMAEMA;and/or reacting for 1-3 h at 80-100 ℃ under the protection of nitrogen;more preferably, the volume ratio of toluene to dioxane is 1: 1.
- 6. Use according to claim 4, characterized in that: the preparation method of the SSBS-g-AA emulsion comprises the following steps:(1) dissolving SBS in organic solvent, adding concentrated sulfuric acid to react to obtain sulfonated product SSBS;(2) dissolving the sulfonated product SSBS in an organic solvent, adding acrylic acid and BPO, and reacting to obtain the sulfonated product;preferably, the first and second electrodes are formed of a metal,in the step (1), the organic solvent is cyclohexane;and/or in the step (1), the mass-to-volume ratio of SBS, organic solvent and concentrated sulfuric acid is 1 g: (5-10) mL: (0.5-1) mL;and/or in the step (1), the reaction is carried out for 1-2 h at the temperature of 30-35 ℃;and/or, in the step (2), the organic solvent is a mixed solution of toluene and dioxane;and/or, in the step (2), the mass volume ratio of the SBS to the organic solvent is 1 g: (8-10) mL;and/or in the step (2), the mass ratio of SBS to acrylic acid is 1: 0.1-0.5;and/or, in the step (2), the BPO accounts for 1.0 percent of the mass of the acrylic acid;and/or in the step (2), reacting for 1-3 h at 80-100 ℃ under the protection of nitrogen;more preferably, the volume ratio of toluene to dioxane is 3: 1.
- 7. A method for preparing lactobionic acid by electrooxidation, comprising the steps of: the bipolar membrane is characterized in that an SSBS-g-AA/SBS-g-DMAEMA bipolar membrane is used as a diaphragm of a cathode electrode and a diaphragm of an anode electrode;preferably, the first and second electrodes are formed of a metal,the current density is 10-40 mA/cm when the lactobionic acid is prepared by electrooxidation2；And/or the electrolysis time for preparing lactobionic acid by electrooxidation is 100-200 min;and/or when the lactobionic acid is prepared by electro-oxidation, the temperature is 20-40 ℃;and/or the anolyte is a mixed solution of lactose and metal bromide;and/or the catholyte is a sulfate solution;more preferably still, the first and second liquid crystal compositions are,the current density is 30mA/cm when the electrooxidation is used for preparing the lactobionic acid2；And/or the electrolysis time for preparing lactobionic acid by electrooxidation is 180 min;and/or, when the lactobionic acid is prepared by electro-oxidation, the temperature is 30 ℃;and/or the concentration of lactose in the anolyte is 0.1-1 mol/L; the concentration of the metal bromide is 0.1-1 mol/L;and/or the concentration of a sulfate solution in the catholyte is 0.1-1 mol/L;it is further preferred that the first and second liquid crystal compositions,in the anolyte, the concentration of lactose is 0.15 mol/L; the concentration of the metal bromide is 0.3 mol/L;and/or, in the catholyte, the concentration of the sulfate solution is 0.3 mol/L;it is still further preferred that the first and second substrates are,the metal bromide is KBr or NaBr;and/or the sulfate solution is Na2SO4Solutions or K2SO4And (3) solution.
- 8. The method of claim 7, wherein: the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane consists of an SSBS-g-AA anode membrane and an SBS-g-DMAEMA cathode membrane;preferably, the preparation method of the SSBS-g-AA/SBS-g-DMAEMA bipolar membrane comprises the following steps: the SBS-g-DMAEMA emulsion and the SSBS-g-AA emulsion are prepared by a tape casting method;more preferably, the thickness of the anode film is 10 to 100 μm; and/or the thickness of the cathode film is 10-100 μm;further preferably, the thickness of the anode film is 20-80 μm; and/or the thickness of the cathode film is 20-80 μm;still further preferably, the thickness of the anodic film is 40 μm; and/or the thickness of the cathode film is 40 μm.
- 9. Use according to claim 8, characterized in that: the preparation method of the SBS-g-DMAEMA emulsion comprises the following steps:dissolving SBS in organic solvent, adding DMAEMA and AIBN, and reacting to obtain the product;preferably, the first and second electrodes are formed of a metal,the organic solvent is a mixed solution of toluene and dioxane;and/or the mass volume ratio of the SBS to the organic solvent is 1 g: (8-10) mL;and/or the mass ratio of SBS to DMAEMA is 1:0.1 to 0.7;and/or the mass of the AIBN is 1.0 percent of the mass of the DMAEMA;and/or reacting for 1-3 h at 80-100 ℃ under the protection of nitrogen;more preferably, the volume ratio of toluene to dioxane is 1: 1.
- 10. Use according to claim 8, characterized in that: the preparation method of the SSBS-g-AA emulsion comprises the following steps:(1) dissolving SBS in organic solvent, adding concentrated sulfuric acid to react to obtain sulfonated product SSBS;(2) dissolving the sulfonated product SSBS in an organic solvent, adding acrylic acid and BPO, and reacting to obtain the sulfonated product;preferably, the first and second electrodes are formed of a metal,in the step (1), the organic solvent is cyclohexane;and/or in the step (1), the mass-to-volume ratio of SBS, organic solvent and concentrated sulfuric acid is 1 g: (5-10) mL: (0.5-1) mL;and/or in the step (1), the reaction is carried out for 1-2 h at the temperature of 30-35 ℃;and/or, in the step (2), the organic solvent is a mixed solution of toluene and dioxane;and/or, in the step (2), the mass volume ratio of the SBS to the organic solvent is 1 g: (8-10) mL;and/or in the step (2), the mass ratio of SBS to acrylic acid is 1: 0.1-0.5;and/or, in the step (2), the BPO accounts for 1.0 percent of the mass of the acrylic acid;and/or in the step (2), reacting for 1-3 h at 80-100 ℃ under the protection of nitrogen;more preferably, the volume ratio of toluene to dioxane is 3: 1.
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