CN101301593A - Preparation of thermosensitive paper-based membrane - Google Patents
Preparation of thermosensitive paper-based membrane Download PDFInfo
- Publication number
- CN101301593A CN101301593A CNA2008101146715A CN200810114671A CN101301593A CN 101301593 A CN101301593 A CN 101301593A CN A2008101146715 A CNA2008101146715 A CN A2008101146715A CN 200810114671 A CN200810114671 A CN 200810114671A CN 101301593 A CN101301593 A CN 101301593A
- Authority
- CN
- China
- Prior art keywords
- filter paper
- deionized water
- solution
- membrane
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a method for preparing a temperature sensing paper-based membrane, which belongs to the filed of the separation membrane. The method comprises the steps of: dipping a filter paper basement membrane in the deionized water, washing and drying, putting in a reactor full of nitrogen after cutting out; adding 0.5%-3% solute of the photosencitizer as the N-Isopropyl acrylamide or copolymer of N-Isopropyl acrylamide and acrylic ester employed as solute, and the mixed solution of the deionized water and the ketone displaced by nigrogen employed as solvent; adding the monomer solution on the filter paper, wetting the filter paper thoroughly, irradiating 10-15 minutes by ultraviolet light to initiate grafted hydrophilic polymers; drying the filter paper of grafted polymer after eliminating the polymeric monomer and the residual photosencitizer. The separation membrane realizes the absorption, leaching and desorption of albumen only by changing the temperature to separate and purify. The membrane prepared by the present invention has merits of small operation voltage drop, good biocompatibility (pollution proof), facile material, low cost, circumstance friendly and simple operation.
Description
Technical field
The present invention relates to a kind of is the preparation method that basement membrane prepares temperature sensitive property diffusion barrier with paper.
Background technology
As a kind of separation, purification technique of novelty, the column chromatography that membrane chromatography is more traditional has a large amount of advantages, and is fast as low pressure drop, big adsorbance, mass transfer, be easy to amplify etc.The operation principle of membrane chromatography is to adopt the film with certain pore size as medium, connects aglucon, utilizes the interaction between the target molecules such as film aglucon and protein to carry out separation and purification.Therefore membrane material is the key factor of decision membrane chromatography separating effect.
Chromatographic membrane material commonly used have modified cellulose, shitosan with and natural based high molecular material and artificial synthesized polymer material such as polysulfones, polyamide such as modifier.Because artificial synthesized polymer material mostly is single homopolymers, and most polymer film is hydrophobicity, easily causes the biofouling to produce (film pollution).
Cellulose family is resourceful natural polymer, and hydrophily and good biocompatibility, is that film base material is expected to reduce the film pollution with it.Filter paper utilizes fiber to make, and has the porous morphosis, is widely used as filter medium, and has certain mechanical strength, can be used as film medium.People (Wei Guo such as Eli Ruckenstein, Eli Ruckenstein.Separation and purification of horseradishperoxidase by membrane affinity chromatography.Journal of Membrane Science211 (2003) 101～111) once was that base material makes affinity film chromatography, was used for the separation and purification of large biological molecules such as horseradish peroxidase with filter paper.In addition, people (Deqiang Yu such as Deqiang Yu, Xiaonong Chen, Robert Pelton, Raja Ghos.Paper-PEG-Based Membranes forHydrophobicInteraction Chromatography:Purification of Monoclonal Antibody.Biotechnology and Bioengineering, 2008,99 (6): 1434～1442) PEG is grafted on the filter paper, made the HC film, utilization has realized absorption and drip washing separation and purification to hIgG1-CD4 in salting-out effect.These studies show that filter paper can be used as the base material of diffusion barrier.
Summary of the invention
The present invention is intended to prepare a kind of novel paper substrate diffusion barrier, and this diffusion barrier is only realized the absorption and the drip washing desorption of albumen by the change of temperature, thereby reaches the separation and purification purpose.The operation principle of this film be under relative higher temperature from aqueous medium adhesion protein, and drip washing at a lower temperature makes the albumen desorption.Therefore, the grafting temperature sensing polymer is the key that obtains this film on the filter paper basement membrane.Graft polymers of the present invention is poly-N-isopropyl acrylamide and copolymer thereof, and the temperature sensitive transition temperature of these polymer is between 5-32 ℃.Owing to kept the loose structure of filter paper after the grafting, therefore this film has the little advantage of operation pressure drop, and good biocompatibility (antipollution), material are easy to get, cost is low, free from environmental pollution, equipment is simple to operate.
The preparation method of above-mentioned paper substrate albumen chromatographic isolation film comprises following processing step:
1, the processing of matrix membrane
With the filter paper basement membrane with deionized water soak, to clean the back dry, is cut into the reactor of putting into nitrogen atmosphere behind the suitable size.
2, the preparation of monomer solution
The preparation of monomer solution: monomer solution is a solvent with the ketone crossed through nitrogen replacement and the mixture of deionized water, both mass ratioes are 0.5～2: 1, the copolymer of N-N-isopropylacrylamide or N-N-isopropylacrylamide and acrylate is a solute, total monomer mass concentration is 3%～30%, the sensitising agent (for example benzophenone, but be not limited to benzophenone) that in this solution, adds monomer mass 0.5-3%.
3, glycerol polymerization
The monomer solution for preparing is added on the filter paper, makes the filter paper complete wetting.With UV-irradiation with the initiation grafting polymerization.
4, the post processing of diffusion barrier
Reaction finishes mixed solution immersion, the washing resulting polymers grafting filter paper film of back with acetone and distilled water, to remove unconverted monomer, remaining sensitising agent.At last, with the filter paper drying of graft polymers.
Paper substrate chromatographic isolation film provided by the invention is to the separation process of protein: when temperature is higher than the lower critical solution temperature (LCST) of poly-N-isopropyl acrylamide (PNIPAM) or its copolymer, grafted chain is in hydrophobic state, with the hydrophobic grouping generation hydrophobic interaction of protein, adsorbed proteins; And when temperature was lower than the LCST of grafted chain, it is hydrophilic that grafted chain becomes, with the hydrophobic interaction disappearance of protein, protein generation desorption.Utilize the hydrophobic difference of different proteins, promptly the difference of grafted chain hydrophobic interaction power realizes Separation of Proteins.
The present invention has following effect:
1, the filter paper that adopted of the paper substrate chromatographic isolation film that makes of the present invention is the hydrophilic natural material, has good biocompatibility, reduces the sex change risk and the film pollution risk of protein.
2, the polymerization of ultraviolet light initiation grafting can be controlled percent grafting, has kept the loose structure of film, thereby makes film have low operation pressure drop and high flux.
3, the paper substrate diffusion barrier that makes of the present invention is formed and temperature sensitive transition temperature by the control grafted chain, can realize protein adsorption at a lower temperature, thus energy efficient, and reduce the albumen risk of distortion.
4, need not the haline water medium during protein adsorption, separation process is environmental protection more.
5, the filter paper base material is easy to get, cost is low.
Description of drawings
Fig. 1 is example 1 electromicroscopic photograph;
Fig. 2 is example 2 electromicroscopic photographs;
Fig. 3 is example 6 electromicroscopic photographs.
The specific embodiment
Embodiment 1:
Adopting analytical paper (the qualitative analysis filter paper of Hangzhou Special Paper Industry Co., Ltd.) in this example is matrix membrane, by the polymerization of ultraviolet light initiation grafting, at matrix membrane surface grafting poly-N-isopropyl acrylamide chain.
Concrete steps are as follows:
1. 10 * 10 centimetres of filter paper of cutting place printing opacity and have filled the reactor of nitrogen;
2. preparation monomer solution, monomer solution is a solvent with the acetone crossed through nitrogen replacement and the mixture (acetone 1.6g, deionized water 1.3g) of deionized water, is solute with N-N-isopropylacrylamide (0.25g), monomer concentration is 7.9%, and sensitising agent is benzophenone (0.005g).
With syringe with the injection of solution for preparing to filter paper, make the filter paper complete wetting, carry out polymerisation.Irradiation time is 10 minutes.
4. reaction finishes mixed solution immersion, the washing filter paper of back with acetone and deionized water, soaks repeatedly with deionized water, to remove unconverted monomer, remaining sensitising agent again.
5. last, filter paper is dried the back naturally in 60 ℃ of drying boxes, dry, weigh after being placed to room temperature again, calculating percent grafting is 4.2% (wt).The temperature sensitive transition temperature (LCST) of graft polymers is 32 ℃.
The separation membrane surface loose structure that this example makes is shown in Fig. 1 electromicroscopic photograph:
Embodiment 2:
Adopt filter paper identical in this example, by the polymerization of ultraviolet light initiation grafting, at matrix membrane surface grafting poly-N-isopropyl acrylamide chain with example 1.Concrete steps are as follows:
1. 10 * 10 centimetres of filter paper of cutting place printing opacity and have filled the reactor of nitrogen;
2. preparation monomer solution, monomer solution is a solvent with the acetone crossed through nitrogen replacement and the mixture (acetone 1.2g, deionized water 1.0g) of deionized water, is solute with N-N-isopropylacrylamide (0.5g), monomer concentration is 18.5%, and sensitising agent is benzophenone (0.01g).
With syringe with the injection of solution for preparing to filter paper, make the filter paper complete wetting, carry out polymerisation.Irradiation time is 15 minutes.
4. reaction finishes mixed solution immersion, the washing filter paper of back with acetone and deionized water, soaks repeatedly with deionized water, to remove unconverted monomer, remaining sensitising agent again.
5. last, filter paper is dried the back naturally in 60 ℃ of drying boxes, dry, to weigh after being placed to room temperature again, percent grafting is 38% (wt).Our transition temperature (LCST) of graft polymers is 32 ℃.
The separation membrane surface loose structure that this example makes is shown in Fig. 2 electromicroscopic photograph:
Embodiment 3:
Adopt filter paper identical in this example, by the polymerization of ultraviolet light initiation grafting, at matrix membrane surface grafting poly-N-isopropyl acrylamide chain with example 1.Concrete steps are as follows:
1. 10 * 10 centimetres of filter paper of cutting place printing opacity and have filled the reactor of nitrogen;
2. preparation monomer solution, monomer solution is a solvent with the acetone crossed through nitrogen replacement and the mixture (acetone 3g, deionized water 1.5g) of deionized water, is solute with N-N-isopropylacrylamide (0.5g), monomer concentration is 10%, and sensitising agent is benzophenone (0.01g).
With syringe with the injection of solution for preparing to filter paper, make the filter paper complete wetting, carry out polymerisation.Irradiation time is 15 minutes.
4. reaction finishes mixed solution immersion, the washing filter paper of back with acetone and deionized water, soaks repeatedly with deionized water, to remove unconverted monomer, remaining sensitising agent again.
5. last, filter paper is dried the back naturally in 60 ℃ of drying boxes, dry, to weigh after being placed to room temperature again, percent grafting is 12.2% (wt).Our transition temperature (LCST) of graft polymers is 32 ℃.
Embodiment 4:
Adopt filter paper identical in this example, by the polymerization of ultraviolet light initiation grafting, at matrix membrane surface grafting poly-N-isopropyl acrylamide chain with example 1.Concrete steps are as follows:
1. 10 * 10 centimetres of filter paper of cutting place printing opacity and have filled the reactor of nitrogen;
2. preparation monomer solution, monomer solution is a solvent with the acetone crossed through nitrogen replacement and the mixture (acetone 2.2g, deionized water 4.4g) of deionized water, is solute with N-N-isopropylacrylamide (1.8g), monomer concentration is 21.4%, and sensitising agent is xanthone (0.009g).
With syringe with the injection of solution for preparing to filter paper, make the filter paper complete wetting, carry out polymerisation.Irradiation time is 15 minutes.
4. reaction finishes mixed solution immersion, the washing filter paper of back with acetone and deionized water, soaks repeatedly with deionized water, to remove unconverted monomer, remaining sensitising agent again.
5. last, filter paper is dried the back naturally in 60 ℃ of drying boxes, dry, to weigh after being placed to room temperature again, percent grafting is 41.0% (wt).Our transition temperature (LCST) of graft polymers is 32 ℃.
Embodiment 5:
Adopt filter paper identical in this example, by the polymerization of ultraviolet light initiation grafting, at matrix membrane surface grafting poly-N-isopropyl acrylamide chain with example 1.Concrete steps are as follows:
1. 10 * 10 centimetres of filter paper of cutting place printing opacity and have filled the reactor of nitrogen;
2. preparation monomer solution, monomer solution is a solvent with the butanone crossed through nitrogen replacement and the mixture (butanone 2.2g, deionized water 1.8g) of deionized water, is solute with N-N-isopropylacrylamide (0.17g), monomer concentration is 4.0%, and sensitising agent is benzophenone (0.0051g).
With syringe with the injection of solution for preparing to filter paper, make the filter paper complete wetting, carry out polymerisation.Irradiation time is 15 minutes.
4. reaction finishes mixed solution immersion, the washing filter paper of back with butanone and deionized water, soaks repeatedly with deionized water, to remove unconverted monomer, remaining sensitising agent again.
5. last, filter paper is dried the back naturally in 60 ℃ of drying boxes, dry, to weigh after being placed to room temperature again, percent grafting is 3.0% (wt).Our transition temperature (LCST) of graft polymers is 32 ℃.
Embodiment 6:
Adopt filter paper identical in this example, by the polymerization of ultraviolet light initiation grafting, at matrix membrane surface grafting poly-N-isopropyl acrylamide chain with example 1.Concrete steps are as follows:
1. 10 * 10 centimetres of filter paper of cutting place printing opacity and have filled the reactor of nitrogen;
2. preparation monomer solution, monomer solution is with the acetone crossed through nitrogen replacement and mixture (the acetone 2.6g of deionized water, deionized water 2.1g) is solvent, with N-N-isopropylacrylamide (0.6g) and ethyl acrylate (0.11g) is solute, monomer concentration is 11.3%, and sensitising agent is benzophenone (0.012g).
With syringe with the injection of solution for preparing to filter paper, make the filter paper complete wetting, carry out polymerisation.Irradiation time is 15 minutes.
4. reaction finishes mixed solution immersion, the washing filter paper of back with acetone and deionized water, soaks repeatedly with deionized water, to remove unconverted monomer, remaining sensitising agent again.
5. last, filter paper is dried the back naturally in 60 ℃ of drying boxes, dry, to weigh after being placed to room temperature again, percent grafting is 25% (wt).The temperature sensitive transition temperature of graft polymers is 20 ℃ for (LCST).
The separation membrane surface loose structure that this example makes is shown in Fig. 3 electromicroscopic photograph:
Adopting embodiment 3 percent graftings is that 12.2% diffusion barrier carries out the absorption of proteins experiment.Testing used protein is bovine serum albumin(BSA) (BSA).Come the variation of profiling protein matter concentration with the variation of ultraviolet specrophotometer mensuration protein solution light transmittance.Detailed process comprises:
1, compound concentration is the BSA aqueous solution (pH=6.0) of 500 μ g/ml.
2, absorption: film is cut into 3cm * 3cm size, puts into the bottle that volume is 50ml, add protein solution 20ml (film immerses in the solution fully), put into constant temperature oscillator after the sealing, absorption is 2 hours under 37 ℃ of conditions.
3, pass through the urporotein solution of ultraviolet specrophotometer determination step 1, the light transmittance of the protein solution after step 2 absorption, calculate corresponding protein concentration, and then calculate adsorbance.
Measurement result: the BSA solution light transmittance without absorption is 26.1% (BSA concentration is 500 μ g/ml), and the light transmittance of BSA solution is 44.2% after filter membrane absorption, and corresponding proteins concentration is 225 μ g/ml.According to the cumulative volume (20ml) of protein solution and the area (18cm of paper substrate diffusion barrier in BSA concentration drop-out value (275 μ g/ml), the adsorption experiment
2) to calculate this diffusion barrier be 611.1 μ g/cm to the adsorption capacity of BSA
2).
Claims (1)
1. the preparation method of a thermosensitive paper-based membrane is characterized in that, may further comprise the steps:
(1), the processing of matrix membrane
The filter paper basement membrane is soaked, cleans the back drying with deionized water, put into the reactor of nitrogen atmosphere after the cutting;
(2), the preparation of monomer solution
The preparation of monomer solution: with the ketone crossed through nitrogen replacement and the mixed solution of deionized water is solvent, the mass ratio of ketone and deionized water is 0.5～2: 1, the copolymer of N-N-isopropylacrylamide or N-N-isopropylacrylamide and acrylate is a solute, total monomer mass concentration is 3%～30%, adds the sensitising agent of solute quality 0.5%-3% in this solution;
(3), glycerol polymerization
The above-mentioned monomer solution for preparing is added on the filter paper, makes the filter paper complete wetting, with UV-irradiation 10-15 minute with the initiation grafting polymerization;
(4), the post processing of diffusion barrier
Reaction finishes the back and soaks, washs resulting polymers grafting filter paper film with above-mentioned ketone and deionized water mixed solution, to remove unconverted monomer, remaining sensitising agent; At last, with the filter paper drying of graft polymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101146715A CN101301593A (en) | 2008-06-06 | 2008-06-06 | Preparation of thermosensitive paper-based membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101146715A CN101301593A (en) | 2008-06-06 | 2008-06-06 | Preparation of thermosensitive paper-based membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101301593A true CN101301593A (en) | 2008-11-12 |
Family
ID=40111796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101146715A Pending CN101301593A (en) | 2008-06-06 | 2008-06-06 | Preparation of thermosensitive paper-based membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101301593A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565489B (en) * | 2009-06-02 | 2011-05-11 | 中山大学 | Preparation method of polystyrene with thermo-sensitive surface |
| CN105111486A (en) * | 2015-09-15 | 2015-12-02 | 廖张洁 | Intelligent material |
| CN107261868A (en) * | 2017-06-28 | 2017-10-20 | 安庆师范大学 | A kind of temperature sensitive type amphipathic nature polyalcohol is modified paper substrate filter membrane and preparation method thereof |
| CN114225725A (en) * | 2022-01-04 | 2022-03-25 | 天津工业大学 | Thermo-sensitive ultrafiltration composite membrane and preparation method thereof |
-
2008
- 2008-06-06 CN CNA2008101146715A patent/CN101301593A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565489B (en) * | 2009-06-02 | 2011-05-11 | 中山大学 | Preparation method of polystyrene with thermo-sensitive surface |
| CN105111486A (en) * | 2015-09-15 | 2015-12-02 | 廖张洁 | Intelligent material |
| CN107261868A (en) * | 2017-06-28 | 2017-10-20 | 安庆师范大学 | A kind of temperature sensitive type amphipathic nature polyalcohol is modified paper substrate filter membrane and preparation method thereof |
| CN107261868B (en) * | 2017-06-28 | 2020-12-22 | 安庆师范大学 | Temperature-sensitive amphiphilic polymer modified paper-based filter membrane and preparation method thereof |
| CN114225725A (en) * | 2022-01-04 | 2022-03-25 | 天津工业大学 | Thermo-sensitive ultrafiltration composite membrane and preparation method thereof |
| CN114225725B (en) * | 2022-01-04 | 2023-07-28 | 天津工业大学 | Thermosensitive ultrafiltration composite membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5209849A (en) | Hydrophilic microporous polyolefin membrane | |
| Takegami et al. | Pervaporation of ethanol/water mixtures using novel hydrophobic membranes containing polydimethylsiloxane | |
| Fadeev et al. | Fouling of poly [-1-(trimethylsilyl)-1-propyne] membranes in pervaporative recovery of butanol from aqueous solutions and ABE fermentation broth | |
| JP2011510280A5 (en) | ||
| Cristallini et al. | Acrylonitrile‐Acrylic Acid copolymer membrane imprinted with uric acid for clinical uses | |
| JP5254903B2 (en) | Western blot membrane with hydrophilic, high protein binding and low fluorescence | |
| WO2002087734A1 (en) | Novel coated membranes and other articles | |
| JP6896642B2 (en) | How to remove water from asymmetric composite membranes and feed streams | |
| Shantora et al. | Separation of liquid mixtures by using polymer membranes. III. Grafted poly (vinyl alcohol) membranes in vacuum permeation and dialysis | |
| JP2005533146A (en) | Molecularly imprinted polymer material | |
| KR20080010402A (en) | Highly porous polymeric materials comprising biologically active molecules via covalent grafting | |
| CN101301593A (en) | Preparation of thermosensitive paper-based membrane | |
| Hoshi et al. | Separation of aqueous phenol through polyurethane membranes by pervaporation | |
| Sun et al. | Preparation of supermacroporous cryogels with improved mechanical strength for efficient purification of lysozyme from chicken egg white | |
| US4595707A (en) | Membranes comprising microporous structure | |
| JP2021522992A (en) | Hybrid polymer membrane | |
| Kurkuri et al. | Pervaporation separation of water and dioxane mixtures with sodium alginate‐g‐polyacrylamide copolymeric membranes | |
| CN1175922C (en) | Preparing process and application of composite biolipid/cellulose acetate membrane | |
| CN109265722B (en) | Ethylene-vinyl alcohol copolymer intelligent film with Janus structure, and preparation method and application thereof | |
| Wang et al. | Poly (vinylidene fluoride) membranes fabricated by vapor‐induced phase separation (VIPS) for the adsorption removal of VB12 from aqueous solution | |
| Garipcan et al. | Synthesis of Poly [(hydroxyethyl methacrylate)‐co‐(methacrylamidoalanine)] Membranes and Their Utilization as an Affinity Sorbent for Lysozyme Adsorption | |
| JP2007313391A (en) | Trapping material, its manufacturing method and cartridge for solid phase extraction | |
| Wei et al. | Hemocompatibility and ultrafiltration performance of PAN membranes surface‐modified by hyperbranched polyesters | |
| Junfu et al. | PVDF hollow fiber membrane with high flux and high rejection ratio prepared by irradiation induced grafting of PAA | |
| CN108956917B (en) | Method for detecting concentration of organic pollutants in water body by using polymer adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20081112 |