CN107266693B - A kind of preparation method of separating medium - Google Patents
A kind of preparation method of separating medium Download PDFInfo
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- CN107266693B CN107266693B CN201710503815.5A CN201710503815A CN107266693B CN 107266693 B CN107266693 B CN 107266693B CN 201710503815 A CN201710503815 A CN 201710503815A CN 107266693 B CN107266693 B CN 107266693B
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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Abstract
The present invention relates to a kind of preparation methods of novel separating medium, a certain amount of inorganic salts and multiple crosslinking agent beta-diimine Zn complex and 1 are added into high molecular weight protein solution first, 2,7,8- diepoxyoctane, the pH for adjusting solution is 2-5.5, and heating water bath can be prepared by saliferous hydrogel after mixing evenly.Saliferous hydrogel obtained is removed into wherein inorganic salts and monomer crosslinked dose of residual through 110-121 DEG C of high-temperature process and distilled water immersion washing, obtains a kind of high intensity, porous hydrogel after drying.The hydrogel elastic is good, and resistance to compression is strong, and respectively up to 70% and 5-6MPa, porosity 75-90% is controllable, has good selectivity separating capacity for maximum compression strain and compression stress, is expected to as a kind of novel separating medium for isolating and purifying field.
Description
Technical field
The present invention relates to a kind of preparation methods of separating medium, and in particular to a kind of preparation side of gel-type separating medium
Method.
Background technique
Hydrogel is a kind of high molecular polymer with tridimensional network rich in moisture, is generally used for a group weaver
The fields such as journey and medicament slow release.Although hydrogel is often hoped the separation for substance often with there is the porous characteristic of controllability.So
And since the low mechanical strength of conventional hydrogel greatly limits their applications in substance separation, how to prepare and provides
The separating medium for having the porous aquagel of good mechanical properties is always a meaningful challenge problem.
The present invention is directed to prepare a kind of Superporous hydrogels.The hydrogel can overcome the defect of Conventional porous hydrogel,
Cellular structure is stablized, and swelling rate is high, and has good mechanical performance, can be used as and isolates and purifies media applications in point of substance
From with purification aspect.
Summary of the invention
The purpose of the present invention is to provide a kind of preparations of Superporous hydrogels separating medium with good separation function
Method, this method prepare simple to operation, ensure that hydrogel has cellular structure stable, good porosity and good machine
Tool performance not only can use the realization of its pore size and be separated by filtration, also has the function of Selective Separation (such as Dye Adsorption and oil
Water separation).
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of preparation method of separating medium: high molecular weight protein is dissolved in ultrapure water, multiple crosslinking agent is added thereto
And inorganic salt solution, and adjusting solution ph is 2-5.5, mixed liquor, which is then placed in progress cross-linking reaction in water-bath, to obtain
Saliferous hydrogel, then after high steam processs and ultrapure water embathe and remove salinity and crosslinkers monomers residual, be dried i.e.
Obtain a kind of porous gel separating medium；
The multiple crosslinking agent be beta-diimine Zn complex and 1,2,7,8- diepoxyoctanes, mass ratio 3:1-1:
3。
The high molecular weight protein is selected from human-like collagen (LHC), human serum albumins (HSA), bovine serum albumin(BSA)
(BSA), one of lactalbumin (WP) water soluble protein or a variety of, ultimate density is after high molecular weight protein is dissolved in ultrapure water
50-400 mg/mL。
The inorganic salts are selected from sodium chloride, sodium phosphate, dibastic sodium phosphate, ammonium sulfate, ammonium nitrate, potassium nitrate, potassium sulfate, chlorination
Potassium, the concentration of inorganic salt solution are 10-350 mg/mL, and it is 1:2-1 that volume and high molecular weight protein liquor capacity ratio, which is added:
20。
The mass percent of the crosslinking agent beta-diimine Zn complex solution and 1,2,7,8- diepoxyoctane solution is dense
Degree is 0.1-5.0%, preferably 0.5-2.0%, and volume is the 1-20% of protein solution volume, preferably 5-10%.
It is 2-5.5 that above-mentioned reaction solution pH value hydrochloric acid and sodium hydroxide solution, which regulate and control its pH value,；The temperature of cross-linking reaction
It can be 40-80 DEG C, retention time 0.5-5h, preferably 1-3 h.
Above-mentioned high steam processs temperature is 110-121 DEG C, handles time 5-30min, preferred process time 10-20min.
Above-mentioned sample washing uses ultrapure water washing by soaking method, washs 2-5 days to remove salinity and have neither part nor lot in cross-linking reaction
Crosslinking agent.
Above-mentioned drying mode chooses vacuum freeze-drying method or supercritical carbon dioxide seasoning.
Above-mentioned crosslinking agent beta-diimine Zn complex is according to document (Catalytic Reactions Involving C1
Feedstocks: New High-Activity Zn(II)-Based Catalysts for the Alternating
Copolymerization of Carbon Dioxide and Epoxides, J. Am. Chem. Soc. 1998, 120,
11018-11019.) method synthesize and obtain, molecular formula is as shown in Figure 1.
The reaction solution pH value of above-mentioned cross-linking reaction in a water bath can be regulated and controled with hydrochloric acid and sodium hydroxide solution, and pH value is
2-5.5。
Preferred 40-80 DEG C of reaction temperature in above-mentioned reaction, retention time preferred 1-3 h.
Above-mentioned high steam processs temperature is 110-121 DEG C, and retention time 5-30min preferably remains time 10-20min.
The washing of above-mentioned sample uses ultrapure water washing by soaking method, and it is primary that every 6h changes water, washs 2-5 days to remove salinity and not
Participate in the crosslinking agent of cross-linking reaction.
Above-mentioned drying mode chooses vacuum freeze-drying method or supercritical carbon dioxide seasoning.
The formation mechenism of Superporous hydrogels of the present invention: protein molecule carboxyl rich in and amino are intermolecular
Crosslinking provides two kinds of good functional groups.The unoccupied orbital of beta-diimine Zn complex intramolecular chelated zinc can in protein molecular
Amino formed coordinate bond, realize the intermolecular cross-linking of protein molecule.Beta-diimine Zn complex has not epoxy alkyl
Symmetrical open loop catalysis, can accelerate the molecule both ends epoxy alkyl open loop of 1,2,7,8- diepoxyoctanes and in protein molecular
Carboxyl formed covalent bond, realize the intermolecular cross-linking of protein molecule.Therefore by beta-diimine Zn complex to 1,2,7,8-
The open loop of diepoxyoctane is catalyzed and two kinds of crosslinking agents are to double crosslinked actions between the intermolecular different groups of protein, effectively
Realize and enhance the intermolecular crosslinking of water-solubility protein.The addition of inorganic salts effectively destroys point of water soluble protein
The outer hydration shell of son, promotes the cross-linking reaction between crosslinking agent and protein molecule, furthermore appropriate inorganic salts are also simultaneous plays into
Hole agent effect, has advanced optimized the pore-forming effect of hydrogel.
The invention has the following advantages that compared to conventional hydrogels, the raw materials used macromolecular of porous aquagel in the present invention
Globulin has good biocompatibility, has been used widely in biomedicine field；The multiple crosslinking agent of use
Cross-linking effect is good, and residual is easily removed；Hydrogel in the present invention coagulates after high-temperature heating treatment (such as 110-121 DEG C)
Glue can will not completely fall off, and high-temperature process can also further be conducive to going for unreacted crosslinking agent with container adhesion from wall
Remove and enhance the mechanical strength of gel；The porous aquagel excellent in mechanical performance, more general hydrogel is partially hard, but anti-compression elasticity
Fabulous, maximum compression strain and compression stress are respectively up to 70% and 5-6 MPa；Gel porosity height (being typically in the range of 75-90%),
Gel duct stable structure, stable in physicochemical property is good, not only has the function of serving as filter membrane, also has water-oil separating and dyestuff
Selective absorption function.
Detailed description of the invention
The molecular structure of Fig. 1 beta-diimine Zn complex；
Fig. 2 is the SEM figure of porous aquagel separating medium prepared by embodiment 1；
Fig. 3 is that oil is schemed with the SEM of filter medium prepared by the present invention and its separated to 0.22 μm of filter media of commercialization
The effect contrast figure of water-in-oil emulsion (oleic acid or edible oil), crystal violet, dimethyl diaminophenazine chloride and bromine water；
Fig. 4 is adsorption capacity and desorption characteristic test figure of the medium samples prepared by the present invention to crystal violet.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified；Material used, reagent
Deng being commercially available unless otherwise specified.
The preparation of 1 porous aquagel separating medium of embodiment
Step 1: BSA is dissolved in 10 mL ultrapure waters, obtains the BSA solution that concentration is 100 mg/mL, concentration is added
It is 1% crosslinking agent beta-diimine Zn complex and 1, each 1 mL of 2,7,8- diepoxyoctanes adds the NaCl of 20mg/mL
2mL is uniformly mixed, and adjusting pH value of solution with dilute hydrochloric acid is 2.6；
Step 2: the mixed solution in step 1 is sub-packed in mold, keeps 3h that brackish water is made under 40 DEG C of environment
Gel；
Step 3: the hydrogel in step 2 is transferred in high-pressure steam sterilizing pan after 121 DEG C of holding 20min, with steaming
Distilled water washing by soaking 5 days, every 6h changed once washing water, removed salinity and residual cross-linker；
Step 4: the gel after the washing in step 3 is subjected to vacuum freeze drying after -80 DEG C of 3 h of pre-freeze
The porous aquagel separating medium of acquisition.
Fig. 2 is the SEM figure of hydrogel separating medium prepared by embodiment 1, it is seen that its microscopic appearance is porous structure, hole
Wall is that spheric granules stick to each other forms, and aperture is generally differed at tens nanometers to several microns, and pore structure more uniformly and causes
Close perforation, being detected the hydrogel porosity is about 85%.The strain of its maximum compression is corresponding up to 73% known to mechanics properties testing
Compression stress is about 5.2 MPa, and sample elastic is good, can be restored to the original state after being compressed.
The preparation of 2 porous aquagel separating medium of embodiment
Step 1: HSA is dissolved in 10 mL ultrapure waters, obtains the HSA solution that concentration is 150 mg/mL, concentration is added
It is 1% crosslinking agent beta-diimine Zn complex and 1, each 1 mL of 2,7,8- diepoxyoctanes adds the KCl of 50mg/mL
2mL is uniformly mixed, and adjusting pH value of solution with dilute hydrochloric acid is 3.5；
Step 2: the mixed solution in step 1 is sub-packed in mold, keeps 2h that brackish water is made under 50 DEG C of environment
Gel；
Step 3: the hydrogel in step 2 is transferred in high-pressure steam sterilizing pan after 115 DEG C of holding 30min, with steaming
Distilled water washing by soaking 5 days, every 6h changed once washing water, removed salinity and residual cross-linker；
Step 4: the gel after the washing in step 3 is subjected to vacuum freeze drying after -80 DEG C of 3 h of pre-freeze
The porous aquagel separating medium of acquisition.
The porous hydrosol obtained in the embodiment is similar to the porous hydrosol physicochemical property of gained in embodiment 1.
The preparation of 3 porous aquagel separating medium of embodiment
Step 1: LHC is dissolved in 10 mL ultrapure waters, obtains the LHC solution that concentration is 100 mg/mL, concentration is added
It is 2% crosslinking agent beta-diimine Zn complex and 1, each 1 mL of 2,7,8- diepoxyoctanes adds 100mg/mL's
NaNO3Solution 2mL is uniformly mixed, and adjusting pH value of solution with dilute hydrochloric acid is 5；
Step 2: the mixed solution in step 1 is sub-packed in mold, keeps 2h that brackish water is made under 60 DEG C of environment
Gel；
Step 3: the first product gel in step 2 is transferred in high-pressure steam sterilizing pan after 121 DEG C of holding 15min, is used
Distilled water immersion washs 5 days, and every 6h changes once washing water, removes salinity and residual cross-linker；
Step 4: the gel after the washing in step 3 is dry through supercritical carbon dioxide process, it can be obtained porous water
Gel separation media.
The porous hydrosol obtained in the embodiment is similar to the porous hydrosol physicochemical property of gained in embodiment 1.
The separating experiment of 4 porous aquagel separating medium of embodiment
Step 1: the porous aquagel separating medium film for preparing suitable size forms small-sized separate with disposable syringe
Device, respectively carry out oil-water emulsion (oleic acid or edible oil), crystal violet, dimethyl diaminophenazine chloride and bromine water separation test, and with it is commercially available
0.22 μm of filter separating effect is compared.
Step 2: being that be immersed in concentration be 1% to the gel sample prepared in embodiment 1 that 10mm thickness is about 3mm by diameter
It in crystal violet solution after about 48 h, then is soaked in ethanol solution, it is real to impregnate desorption using the absorption of crystal violet and ethyl alcohol
It tests, verifies the adsorbing separation and desorption performance of the porous aquagel separating medium of preparation.
Fig. 3 is the scanning electricity of 0.22 μm of filter filler being commercialized and the separating medium prepared in the embodiment of the present invention 1
Mirror figure.Wherein, a is 0.22 μm of filter internal morphology SEM figure, and b~e is respectively 0.22 μm of filter filtering oil-water emulsion (oleic acid
Or edible oil), operation and the filtered solution figure of crystal violet, dimethyl diaminophenazine chloride and bromine water；F is the internal structure SEM that embodiment 1 prepares sample
Figure, g~j are respectively operation and the filtered solution of sample filtering oil-water emulsion prepared by the present invention, crystal violet, dimethyl diaminophenazine chloride and bromine water
Figure.Know from Fig. 3, porous aquagel separating medium prepared by the present invention and the 0.22 μm of filter internal structure bought in the market are extremely
It is similar, it is also roughly the same from size interception capacity, but the two has great difference in terms of Selective Separation.From dyestuff mistake
Filter and oil hydrosol separating experiment it is found that 0.22 μm of filter regardless of to oil hydrosol, or to crystal violet, dimethyl diaminophenazine chloride and bromine water etc.
All without separating capacity, and water-oil separating not only may be implemented in porous gel prepared by the present invention, also to crystal violet, dimethyl diaminophenazine chloride and
The coloured substance such as bromine water has good separating effect, this illustrates that hydrogel prepared by the present invention is no longer limited to simply
Filter membrane function is also used as specific isolation medium.
Adsorption capacity of the hydrogel that Fig. 4 is shown to crystal violet.It can be seen from the figure that the crystal violet in solution can be inhaled
It is attached on gel sample.The sample for adsorbing crystal violet is immersed in dehydrated alcohol to the dyestuff that can wash off its absorption.This table
Bright hydrogel prepared by the present invention not only has dye separation ability, and can also can quilt by renaturation after ethyl alcohol impregnates
Recycling.
Embodiment experiment shows that there is prepared porous aquagel separating medium excellent adsorption separation performance to conciliate
Characterization of adsorption is a kind of separating medium with very big application potential.
The different crosslinking method comparative experimentss of 5 porous aquagel of embodiment
Step 1: repeating 1 experimentation of embodiment, and it is sub- that two kinds of crosslinking agents in reaction are only changed to a kind of crosslinking agent β-two
Amine Zn complex obtains porous aquagel.The hydrogel is soft, is detected by mechanical property and finds its compression stress about
520KPa no longer has good water absorption and swelling and recoverability energy that hydrogel in embodiment 1 has；
Step 2: repeating 1 experimentation of embodiment, and two kinds of crosslinking agents in reaction are only changed to a kind of crosslinking agent 1, and 2,7,
8- diepoxyoctane obtains porous aquagel.Equally, the hydrogel compression strength is smaller, and compression stress is about 680KPa,
Water absorption and swelling performance and recoverability can weaken significantly.
Above-mentioned experiment show only change multiple crosslinking agent be it is therein any one, obtained hydrogel no longer has
Excellent mechanical mechanical characteristic originally illustrates the novelty that the crosslinking agent collaboration crosslinking experiments scheme in embodiment 1 has had.
Claims (8)
1. a kind of preparation method of separating medium, it is characterised in that: high molecular weight protein is dissolved in ultrapure water, is added thereto multiple
Cross-linking agent aqueous solution and inorganic salt solution are closed, and adjusting solution ph is 2-5.5, and then mixed liquor is placed in water-bath and is carried out
Cross-linking reaction can obtain saliferous hydrogel, then embathe through high steam processs and ultrapure water and remove salinity and crosslinkers monomers residual
Afterwards, it is dried up to a kind of porous gel separating medium；
The multiple crosslinking agent is beta-diimine Zn complex and 1,2,7,8- diepoxyoctanes, mass ratio 3:1-1:3.
2. the preparation method of separating medium according to claim 1, it is characterised in that: high molecular weight protein is selected from class people's collagen egg
One of white, human serum albumins, bovine serum albumin(BSA), lactalbumin water soluble protein are a variety of, and high molecular weight protein is molten
Ultimate density is 50-400 mg/mL after ultrapure water.
3. the preparation method of separating medium according to claim 1, it is characterised in that: the inorganic salts are selected from sodium chloride, phosphorus
Sour sodium, dibastic sodium phosphate, ammonium sulfate, ammonium nitrate, potassium nitrate, potassium sulfate, potassium chloride, the concentration of inorganic salt solution are 10-350
Mg/mL, is added volume and high molecular weight protein liquor capacity ratio is 1:2-1:20.
4. the preparation method of separating medium according to claim 1, it is characterised in that: crosslinking agent beta-diimine Zn complex is molten
Liquid and 1, the mass percent concentration of 2,7,8- diepoxyoctane solution are 0.1-5.0%, and volume is protein solution volume
1-20%.
5. the preparation method of separating medium according to claim 1, it is characterised in that: reaction solution pH value hydrochloric acid and hydrogen-oxygen
Changing sodium solution to regulate and control its pH value is 2-5.5；The temperature of cross-linking reaction is 40-80 DEG C, retention time 0.5-5h.
6. the preparation method of separating medium according to claim 1, it is characterised in that: high steam processs temperature is 110-
121 DEG C, handle time 5-30min.
7. the preparation method of separating medium according to claim 1, it is characterised in that: above-mentioned sample washing uses ultrapure water logging
Washing method is steeped, the 2-5 days crosslinking agents to remove salinity He have neither part nor lot in cross-linking reaction are washed.
8. the preparation method of separating medium according to claim 1, it is characterised in that: drying mode chooses vacuum freeze drying
Method or supercritical carbon dioxide seasoning.
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| CN103992499A (en) * | 2014-04-21 | 2014-08-20 | 陕西巨子生物技术有限公司 | 3D (three-dimensional) uniform porous scaffold material and preparing method thereof |
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| CN103992499A (en) * | 2014-04-21 | 2014-08-20 | 陕西巨子生物技术有限公司 | 3D (three-dimensional) uniform porous scaffold material and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Catalytic Activity of a Series of Zn(II) Phenoxides for the Copolymerization of Epoxides and Carbon Dioxide";Donald J.Darensbourg et al.;《J.Am.Chem.Soc.》;19981219;第121卷;第107-116页 * |
| "羧基交联剂的研究和应用现状";林毅伟等;《广州化工》;20140731;第42卷(第14期);第30-32页 * |
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