CN103055710A - Hollow fiber membrane for chiral separation and preparation method thereof - Google Patents
Hollow fiber membrane for chiral separation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hollow fiber membrane for chiral separation and a preparation method of the hollow fiber membrane for the chiral separation. The preparation method of the hollow fiber membrane for the chiral separation comprises using L- phenylalanine (L-Phe) as separation agent, synthetizing chiral amino acid monomers through modification, copolymerizing the chiral amino acid monomers with temperature-sensitive monomer N-isopropyl acrylamide (NIPAAm) to synthetize temperature-sensitive chiral copolymer microgel P (NIPAAm-co-AAc-L-PheEt); carrying out graft copolymerization on the NIPAAm monomers and polyvinylidene fluoride (PVDF) by using a free radical polymerization method to synthesize temperature-sensitive membrane building substrate PVDF-g-PNIPAAm; and mixing the temperature-sensitive chiral copolymer microgel and a temperature-sensitive membrane building substrate solution to obtain spinning feed liquid, using a dry-wet spinning technology to prepare the hollow fiber membrane for amino acid chiral separation which has functions of chiral recognition and separation and is capable of achieving L-Phe efficient separation by controlling changes of environment temperature. Selection overload quantity of the hollow fiber membrane for the amino acid chiral separation can reach 15%-25%. Separation coefficient of the hollow fiber membrane for the amino acid chiral separation can reach 1.5-1.8. The hollow fiber membrane of the chiral separation combines chiral temperature-sensitive copolymer and thermosensitivity of the temperature-sensitive membrane building substrate into a whole, strengthens the thermosensitivity, and improves chiral separation efficiency and intelligent regulating effect of temperature to chiral separation. Compared with a flat sheet membrane, the hollow fiber membrane for the chiral separation has the advantages of being good in pressure-resistant performance, free from supporting bodies, arbitrary in size and shape of a membrane component, large in filling intensity in the membrane component, large in membrane area and flux of unit volume and the like.
Description
Technical field
The invention belongs to functional high polymer material field, particularly a kind of chiral separation hollow-fibre membrane and preparation method thereof with Selective Separation chiral molecules.This film can be applicable to phenylalanine chiral separation field.
Background technology
Many chiral materials extensively are present in the medicine, and are closely related with our life.Because different enantiomer molecules has different optical activities in the chiral material, can produce significant difference in pharmacologically active, metabolism and toxic and side effect etc., clinical drug shows as wherein, and a kind of enantiomer molecule has certain drug action, but another kind of enantiomer molecule does not have pharmacological action, even can cause disadvantageous negative effect.Therefore, chiral separation has great importance in the medicine preparation process.
In recent years, membrane separation technique is increasingly burning hot in research and the application in chiral separation field, wherein the chiral resolution film comes the separating chiral material by chiral Recognition point to the selective absorption of different enantiomers, have energy consumption low, be easy to the advantages such as continued operation, be considered to carry out one of very potential method of extensive chiral separation, become the new focus of diffusion barrier research
The chiral resolution film can be divided into chiral resolution liquid film and chiral separation solid film by the form of film.The chiral resolution liquid film has higher selective and economy (the use chiral selector is less), but less stable, its application is limited by very large.Chiral separation solid film can overcome the deficiency of liquid film, thereby extremely this area research person's concern.But the greatest drawback of chiral separation solid film is that split process is unstable state, when the adsorption site caudacoria that reaches capacity no longer has the fractionation ability, need carry out desorb, and desorption process is controlled trouble, causes separative efficiency lower, and is difficult to possess simultaneously high flux and high selectivity.
For the separative efficiency and the applicability that improve chiral separation solid film, the R and D of intelligent chiral separation film receive much attention.Intelligence chiral separation film can produce response to environmental stimulis such as temperature, pH value, ion concentration, electric fields, can come controlled material internal void size by changing external environmental condition, realizes high selectivity, the high flux of film, improves separative efficiency.Because temperature control is relatively easy in the external environmental condition, utilizes temperature sensitive macromolecular material to have the characteristics of lower critical solution temperature (LCST), researches and develops temperature sensitive chiral separation film and then has more realistic meaning.But there is following several large problem that need solve in the temperature sensitive chiral separation film of at present research and development:
(1) preparation method of temperature sensitive chiral separation film modifies the graft modification of basal lamina material, exists the modification preparation process complicated, and stability of material variation, the grafting layer defective such as be easy to come off is difficult to realize suitability for industrialized production after the modification.
(2) Thermo-sensitive of temperature sensitive chiral separation film is obvious not, and temperature remains further to be improved to Intelligentized regulating and controlling effect and the regulation and control stability of chiral Recognition and fractionation.
(3) chiral selectivity of film, separative efficiency, flux etc. are not high, realize comparatively difficulty of stable state separation.
Phenylalanine is a kind of of a-amino acid, is one of essential amino acid, and having bioactive optical isomer is L-Phe (L-Phe).The L-Phe human body can not synthesize, and is widely used in the primary raw material of medicine and Aspartame.Phenylalanine can pass through the method preparation of microbial fermentation, proteolysis and organic synthesis.The yield that synthetic method prepares phenylalanine is low, usually extract from natural products, but chiral separating efficiency is the subject matter that restricts at present L-Phe output.
Summary of the invention
The problems referred to above for temperature sensitive chiral separation film existence, and the difficult problem of separating of the potential application of chiral separation film and phenylalanine chiral molecules, the technical problem that quasi-solution of the present invention is determined is: provide a kind of amino acid chiral that the phenylalanine chiral molecules is had good adsorption and a separation function to separate with hollow-fibre membrane and preparation method thereof.
One aspect of the present invention with L-Phe as splitting object, by modification synthesis of chiral amino acid monomer, and then with temperature sensitive monomer NIPA (NIPAAm) copolymerization, synthetic temperature sensitive Chiral Copolymer microgel P (NIPAAm-co-AAc-L-PheEt).On the other hand, adopt free radical copolymerization method with NIPAAm monomer and Kynoar (PVDF) graft copolymerization, synthetic temperature sensitive film becomes membrane matrix PVDF-g-PNIPAAm.At last, temperature sensitive Chiral Copolymer microgel and the blend of PVDF-g-PNIPAAm copolymer solution are made into spinning liquid, adopt the preparation of dry-wet spinning technique to have chiral Recognition and fractionation function, and can separate by the efficient amino acid chiral that separates of variations in temperature realization L-Phe that controls environment and use hollow-fibre membrane.
A kind of amino acid chiral separation of the present invention comprises the steps: with hollow-fibre membrane and preparation method thereof
(1) the temperature sensitive copolymer microgel of chirality is synthetic: the L-Phe esterification is generated L-Phe carbethoxy hydrochloride (L-PheEt), and then with acryloyl chloride acylation reaction synthesis of chiral monomer N-(L-1-ethoxycarbonyl-2-phenyl) acrylamide (AAc-L-PheEt).Take the there-necked flask device, add 50ml through oxolane (THF) condensing reflux except water treatment, add the NIPAAm monomer in there-necked flask, control NIPAAm concentration is 0.1～0.18mol/L.R is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, and behind 0.05～0.20g crosslinking agent MBAA, logical nitrogen gas stirrings are 30～60 minutes under 20～30 ℃, slowly be warming up to 50～70 ℃, stablized 20～40 minutes, add 0.04～0.08g initator azodiisobutyronitrile (AIBN), isothermal reaction 6～10 hours.After reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration obtains the temperature sensitive copolymer microgel of chirality P (NIPAAm-co-AAc-L-PheEt), and drying is placed on sombre place and preserves.
Described mass ratio r=AAc-L-PheEt/ (AAc-L-PheEt+NIPAAm), the i.e. ratio of the quality of AAc-L-PheEt and AAc-L-PheEt and NIPAAm quality sum.
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, logical nitrogen, the solvent N that adds 6～12 times of PVDF quality, dinethylformamide (DMF), stirring and dissolving under heating condition under 50～80 ℃ of water-baths, in the situation of logical nitrogen, add NIPAAm, the mass ratio of control PVDF powder and NIPAAm is 1: (0.5～1.25), the initiator A IBN that adds PVDF quality 1%～2.5%, after the dissolving, logical nitrogen is 10～20 minutes again, continues stirring reaction 8～12 hours fully, after reaction finishes, to add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drain to get temperature sensitive film forming matter PVDF-g-PNIPAAm, putting into 60 ℃ in baking oven, to be dried to constant weight stand-by.
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF, mass percent concentration is controlled at 15%～20%, add microgel P (NIPAAm-co-AAc-L-PheEt), the mass ratio of control microgel and PVDF-g-PNIPAAm is 1: 3～10, add at last pore-foaming agent polyethylene glycol (PEG), the mass percent concentration that makes PEG account for mixed liquor is 5%～10%.Heating under 30～60 ℃ of conditions, stirring are until then fully dissolving pours spinning liquid in the spinning-drawing machine material still, and spinning-drawing machine material still is heated in sealing, and making the spinning liquid temperature is 25～50 ℃, vacuum defoamation 20～60 minutes.
After the spinning liquid deaeration is disposed; open material still gate out switch; in still, pass into the nitrogen pressurization; open the measuring pump switch; adjust 8～20 rev/mins of rotating speeds; the beginning spinning; the doughnut that to extrude from spinneret is wound up on the take up roll after by 20～30 ℃ coagulating bath; 10～25 rev/mins of control take up roll rotating speeds, coiler device is shut down, and takes off fiber; spun hollow-fibre membrane is soaked a week in distilled water; change water every day 2 times, then be dipped in the glycerine water solution 1～2 day, clean to dry with distilled water and namely get amino acid chiral and separate and use hollow-fibre membrane.
In the described step (1), described L-PheEt building-up process is as follows: build experimental provision, comprise spherical condensation tube, 100ml there-necked flask, water bath with thermostatic control, thermometer.In there-necked flask, add the 55ml absolute ethyl alcohol, put into ice bath constant temperature at 0 ℃, slowly splash into the 5ml thionyl chloride with dropper, remain temperature under 5 ℃, stirred 1 hour, add 10g L-Phe powder, remove ice bath, naturally be warming up to room temperature, then progressively be warming up to 65 ℃, constant temperature stirred 3 hours, stopped to stir.Reaction under 85 ℃ of bath temperatures, distills out partial solvent after finishing, crystallisation by cooling, and suction filtration, with a small amount of ethanol washing, oven dry obtains the L-PheEt solid.
In the described step (1), described AAc-L-PheEt building-up process is as follows: the THF of the rear 30ml that will anhydrate first joins in the 100ml there-necked flask, takes by weighing 6g L-PheEt and adds in the flask.Prefabricated cryosel piece is smashed to pieces, made the cryosel bath and be placed on around the there-necked flask, reach liquid level and get final product, be cooled to 0 ℃.Keep system temperature slowly to drip the 7.5ml triethylamine at 0 ℃, slowly drip the 4ml acryloyl chloride, after dropwising, constant temperature progressively is warming up to room temperature after a period of time in cryosel is bathed, and stirs 1 hour, is warming up to 60 ℃ of reactions 3 hours again.After reaction finishes, add 30mL distilled water to reactant liquor, dissolve unreacted hydrochloride and acryloyl chloride, dilute solution is used 30mL chloroform extraction three times simultaneously, adds anhydrous sodium sulfate drying, boil off solvent, obtain dark yellow oily thing AAc-L-PheEt, place sombre place stand-by.
In the described step (2), the PVDF powder preparation process of described alkali treatment is as follows: add the PVDF powder of 150g in the 1LNaOH solution, add subsequently the absolute ethyl alcohol of 30ml and stir, so that PVDF fully disperses in solution.The mixed solution reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 10 minutes.The suction filtration products therefrom constantly washs with distilled water, to remove fluoride and the ethanol in the product.Gained alkali treatment PVDF powdered product is put into 60 ℃ in baking oven and is dried to constant weight after the washing.
Beneficial effect
The present invention is in the hollow-fibre membrane preparation process, adopt and use water as the coagulating bath forming film with phase transformation method, hydrophily makes P (NIPAAm-co-AAc-L-Phe) high polymer chiral separation group to film and fenestra surface enrichment in the film forming procedure, is conducive to the sorption and desorption to chirality D-Phe.Therefore, the blend hollow fiber membrane of the present invention preparation can realize sorption and desorption to D-Phe by the height of control parting liquid temperature, and can realize the variation of membrane pore size by the height of control parting liquid temperature.(T＞LCST), the chirality adsorptivity of membrane material is adsorbed D-Phe in a large number, and L-Phe is then separated by fenestra smoothly under the high temperature, because this moment, fenestra diminished, membrane flux reduces, so be conducive to the absorption to the D-Phe enantiomer, has improved the separative efficiency of L-Phe.(T＜LCST), film reduces the adsorption capacity of D-Phe, thereby discharges the D-Phe of absorption, and this moment, fenestra increased, and membrane flux raises, and is conducive to improve the D-Phe desorption efficiency, and two kinds of enantiomers separately the most at last to reduce the parting liquid temperature.This separation process can be regulated and control by the stimulation of ambient temperature, adsorbance is large, but efficient selective sorption and desorption, and can alternately repeat to carry out continuously, solved the defective of traditional absorption selection type chiral resolution film, amino acid chiral of the present invention separates selects overload quantity (e.e%) can reach 15%-25% with hollow-fibre membrane, and separation (α) can reach 1.5-1.8.
The present invention combines with absorption selection type chiral separation solid film by the environment-responsive with intellectual material, utilizes the chiral Recognition characteristic realization of chirality high polymer to selective efficient adsorption and the desorb of chiral molecules, thereby realizes chiral resolution.The present invention integrates the temperature sensitive copolymer of chirality and the temperature sensitive Thermo-sensitive that becomes membrane matrix, has strengthened the Thermo-sensitive of film, has improved chiral separating efficiency and temperature to the Intelligentized regulating and controlling effect of chiral separation.In addition, the chiral separation film of the present invention's preparation utilizes into membrane matrix and the structural general character of chiral polymer, has solved the problem such as two-phase dispersion and compatibility in the blend chiral separation film preparation process.
The prepared chiral separation hollow-fibre membrane of the present invention adopts ripe in the market PVDF to make raw material, and function monomer be the temperature sensitive raw material monomer NIPAAm of routine, membrane preparation method simply, do not need special installation, production cost low, be suitable for industrial applications.The advantages such as in addition, the prepared chiral separation hollow-fibre membrane of the present invention has good pressure-resistant performance, need not supporter than Flat Membrane, and membrane module can be made arbitrary size and shape, and the loading density in membrane module is large, and the membrane area of unit volume is large, flux is large.
Select the mensuration of overload quantity and separation
By selecting overload quantity (e.e.%) and separation (α) to characterize chiral Recognition and the fractionation ability of blend film, its computing formula is as follows:
In the formula: e.e.%-selects overload quantity, %;
A
DThe peak area value of-D-phenylalanine component in chromatogram;
A
LThe peak area value of-L-Phe component in chromatogram;
In the formula: α-separation;
A
DThe peak area value of-D-phenylalanine component in chromatogram;
A
LThe peak area value of-L-Phe component in chromatogram;
The specific embodiment
The following examples can make the present invention of those skilled in the art comprehend, but do not limit the present invention in any way.
Embodiment 1:
(1) the temperature sensitive copolymer microgel of chirality is synthetic: take the there-necked flask device, add 50ml through the THF condensing reflux except water treatment, add the NIPAAm monomer in there-necked flask, control NIPAAm concentration is 0.1mol/L.R is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, and behind the 0.10g crosslinking agent MBAA, logical nitrogen gas stirrings are 30 minutes under 30 ℃, slowly be warming up to 50 ℃, stablized 20 minutes, and added 0.04g initator azodiisobutyronitrile (AIBN), isothermal reaction 6 hours.After reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration gets microgel, and drying is placed on sombre place and preserves.
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, and logical nitrogen adds the solvent DMF (DMF) of 6 times of PVDF quality, stirring and dissolving under heating condition under 50 ℃ of water-baths.Add NIPAAm in the situation of logical nitrogen, the mass ratio of control PVDF and NIPAAm is 1: 0.5, adds the initiator A IBN of PVDF quality 1%, and after the dissolving, logical nitrogen is 10 minutes again, continues stirring reaction 8 hours fully.After reaction finishes, will add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drains to get temperature sensitive film forming matter PVDF-g-PNIPAAm, and putting into 60 ℃ in baking oven, to be dried to constant weight stand-by.
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF, mass percent concentration is controlled at 15%, add microgel, the mass ratio of control microgel and PVDF-PNIPAAm is 1: 3, add at last pore-foaming agent polyethylene glycol (PEG), the mass percent concentration that makes PEG account for mixed liquor is 5%.Heating under 30 ℃ of conditions, stirring are until then fully dissolving pours spinning liquid in the spinning-drawing machine material still, and spinning-drawing machine material still is heated in sealing, and making the spinning liquid temperature is 25 ℃, vacuum defoamation 60 minutes.
After the spinning liquid deaeration is disposed; open material still gate out switch; in still, pass into the nitrogen pressurization; open the measuring pump switch; adjust 8 rev/mins of rotating speeds; the beginning spinning; the doughnut that to extrude from spinneret is wound up on the take up roll after by 20 ℃ coagulating bath, 10 rev/mins of control take up roll rotating speeds, and coiler device is shut down; take off fiber; spun hollow-fibre membrane is soaked a week in distilled water, change water every day 2 times, then be dipped in the glycerine water solution 2 days; dry with distilled water is clean, namely get amino acid chiral separation hollow-fibre membrane.
It is 25% that the amino acid chiral separation that makes is selected overload quantity (e.e%) with hollow-fibre membrane, and separation (α) is 1.8.
Embodiment 2:
(1) the temperature sensitive copolymer microgel of chirality is synthetic: take the there-necked flask device, add 50ml through the THF condensing reflux except water treatment, add the NIPAAm monomer in there-necked flask, control NIPAAm concentration is 0.13mol/L.R is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, and behind the 0.20g crosslinking agent MBAA, logical nitrogen gas stirrings are 60 minutes under 30 ℃, slowly be warming up to 70 ℃, stablized 40 minutes, and added 0.08g initator azodiisobutyronitrile (AIBN), isothermal reaction 10 hours.After reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration gets microgel, and drying is placed on sombre place and preserves.
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, and logical nitrogen adds the solvent DMF (DMF) of 12 times of PVDF quality, stirring and dissolving under 50 ℃ of condition of water bath heating.Add NIPAAm in the situation of logical nitrogen, the mass ratio of control PVDF and NIPAAm is 1: 0.5, adds the initiator A IBN of PVDF quality 2.5%, and after the dissolving, logical nitrogen is 20 minutes again, continues stirring reaction 12 hours fully.After reaction finishes, will add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drains to get temperature sensitive film forming matter PVDF-g-PNIPAAm, and putting into 60 ℃ in baking oven, to be dried to constant weight stand-by.
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF, mass percent concentration is controlled at 16%, add microgel, the mass ratio of control microgel and PVDF-PNIPAAm is 1: 10, add at last pore-foaming agent polyethylene glycol (PEG), the mass percent concentration that makes PEG account for mixed liquor is 6%.Heating under 40 ℃ of conditions, stirring are until then fully dissolving pours spinning liquid in the spinning-drawing machine material still, and spinning-drawing machine material still is heated in sealing, and making the spinning liquid temperature is 30 ℃, vacuum defoamation 40 minutes.
After the spinning liquid deaeration is disposed, open material still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 20 rev/mins of rotating speeds, the beginning spinning, the doughnut that will extrude from spinneret is wound up on the take up roll after by 30 ℃ coagulating bath, 10 rev/mins of control take up roll rotating speeds.Coiler device is shut down, and takes off fiber, and spun hollow-fibre membrane is soaked a week in distilled water, changes water every day 2 times, then is dipped in the glycerine water solution 2 days, cleans with distilled water and dries, and namely gets amino acid chiral separation hollow-fibre membrane.
It is 23% that the amino acid chiral separation that makes is selected overload quantity (e.e.%) with hollow-fibre membrane, and separation (α) is 1.7.
Embodiment 3:
(1) the temperature sensitive copolymer microgel of chirality is synthetic: take the there-necked flask device, add 50ml through the THF condensing reflux except water treatment, add the NIPAAm monomer in there-necked flask, control NIPAAm concentration is 0.15mol/L.R is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, and behind the 0.1g crosslinking agent MBAA, logical nitrogen gas stirrings are 60 minutes under 30 ℃, slowly be warming up to 50 ℃, stablized 30 minutes, and added 0.05g initator azodiisobutyronitrile (AIBN), isothermal reaction 10 hours.After reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration gets microgel, and drying is placed on sombre place and preserves.
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, and logical nitrogen adds the solvent DMF (DMF) of 12 times of PVDF quality, stirring and dissolving under heating condition under 60 ℃ of water-baths.Add NIPAAm in logical nitrogen situation, the mass ratio of control PVDF and NIPAAm is 1: 1.25, adds the initiator A IBN of PVDF quality 1.5%, and after the dissolving, logical nitrogen is 20 minutes again, continues stirring reaction 12 hours fully.After reaction finishes, will add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drains to get temperature sensitive film forming matter PVDF-g-PNIPAAm, and putting into 60 ℃ in baking oven, to be dried to constant weight stand-by.
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF, mass percent concentration is controlled at 18%, add microgel, the mass ratio of control microgel and PVDF-PNIPAAm is 1: 5, add at last pore-foaming agent polyethylene glycol (PEG), the mass percent concentration that makes PEG account for mixed liquor is 10%.Heating under 40 ℃ of conditions, stirring are until then fully dissolving pours spinning liquid in the spinning-drawing machine material still, and spinning-drawing machine material still is heated in sealing, and making the spinning liquid temperature is 50 ℃, vacuum defoamation 20 minutes.
After the spinning liquid deaeration is disposed, open material still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 10 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 30 ℃ coagulating bath, 25 rev/mins of control take up roll rotating speeds.Coiler device is shut down, and takes off fiber, and spun hollow-fibre membrane is soaked a week in distilled water, changes water every day 2 times, then is dipped in the glycerine water solution 1 day, cleans with distilled water and dries, and namely gets amino acid chiral separation hollow-fibre membrane.
It is 22% that the amino acid chiral separation that makes is selected overload quantity (e.e.%) with hollow-fibre membrane, and separation (α) is 1.6.
Embodiment 4:
(1) the temperature sensitive copolymer microgel of chirality is synthetic: take the there-necked flask device, add 50ml through the THF condensing reflux except water treatment, add the NIPAAm monomer in there-necked flask, control NIPAAm concentration is 0.18mol/L.R is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, and behind the 0.20g crosslinking agent MBAA, logical nitrogen gas stirrings are 60 minutes under 30 ℃, slowly be warming up to 50 ℃, stablized 30 minutes, and added 0.06g initator azodiisobutyronitrile (AIBN), isothermal reaction 8 hours.After reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration obtains microgel, and drying is placed on sombre place and preserves.
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, and logical nitrogen adds the solvent DMF (DMF) of 12 times of PVDF quality, stirring and dissolving under heating condition under 60 ℃ of water-baths.Add NIPAAm in the situation of logical nitrogen, the mass ratio of control PVDF and NIPAAm is 1: 1, adds the initiator A IBN of PVDF quality 1.5%, and after the dissolving, logical nitrogen is 20 minutes again, continues stirring reaction 12 hours fully.After reaction finishes, will add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drains to get temperature sensitive film forming matter PVDF-g-PNIPAAm, and putting into 60 ℃ in baking oven, to be dried to constant weight stand-by.
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF, mass percent concentration is controlled at 20%, add microgel, the mass ratio of control microgel and PVDF-PNIPAAm is 1: 5, add at last pore-foaming agent polyethylene glycol (PEG), the mass percent concentration that makes PEG account for mixed liquor is 10%.Heating under 40 ℃ of conditions, stirring are until then fully dissolving pours spinning liquid in the spinning-drawing machine material still, and spinning-drawing machine material still is heated in sealing, and making the spinning liquid temperature is 30 ℃, vacuum defoamation 30 minutes.
After the spinning liquid deaeration is disposed, open material still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 15 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 25 ℃ coagulating bath, 20 rev/mins of control take up roll rotating speeds.Coiler device is shut down, and takes off fiber, and spun hollow-fibre membrane is soaked a week in distilled water, changes water every day 2 times, then is dipped in the glycerine water solution 2 days, cleans with distilled water and dries, and namely gets amino acid chiral separation hollow-fibre membrane.
It is 20% that the amino acid chiral separation that makes is selected overload quantity (e.e%) with hollow-fibre membrane, and separation (α) is 1.6.
Embodiment 5:
(1) the temperature sensitive copolymer microgel of chirality is synthetic: take the there-necked flask device, add 50ml through the THF condensing reflux except water treatment, add the NIPAAm monomer in there-necked flask, control NIPAAm concentration is 0.125mol/L.R is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, and behind the 0.10g crosslinking agent MBAA, logical nitrogen gas stirrings are 45 minutes under 25 ℃, slowly be warming up to 60 ℃, stablized 30 minutes, and added 0.05g initator azodiisobutyronitrile (AIBN), isothermal reaction 8 hours.After reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration obtains microgel, and drying is placed on sombre place and preserves.
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, and logical nitrogen adds the solvent DMF (DMF) of 10 times of PVDF quality, stirring and dissolving under heating condition under 60 ℃ of water-baths.Add NIPAAm in the situation of logical nitrogen, the mass ratio of control PVDF and NIPAAm is 1: 0.8, adds the initiator A IBN of PVDF quality 2.2%, and after the dissolving, logical nitrogen is 15 minutes again, continues stirring reaction 12 hours fully.After reaction finishes, will add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drains to get temperature sensitive film forming matter PVDF-g-PNIPAAm, and putting into 60 ℃ in baking oven, to be dried to constant weight stand-by.
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF, mass percent concentration is controlled at 16%, add microgel, the mass ratio of control microgel and PVDF-PNIPAAm is 1: 5, add at last pore-foaming agent polyethylene glycol (PEG), the mass percent concentration that makes PEG account for mixed liquor is 10%.Heating under 40 ℃ of conditions, stirring are until then fully dissolving pours spinning liquid in the spinning-drawing machine material still, and spinning-drawing machine material still is heated in sealing, and making the spinning liquid temperature is 30 ℃, vacuum defoamation 50 minutes.
After the spinning liquid deaeration is disposed, open material still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 10 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 30 ℃ coagulating bath, 22 rev/mins of control take up roll rotating speeds.Coiler device is shut down, and takes off fiber, and spun hollow-fibre membrane is soaked a week in distilled water, changes water every day 2 times, then is dipped in the glycerine water solution 1.5 days, cleans with distilled water and dries, and namely gets amino acid chiral separation hollow-fibre membrane.
It is 18% that the amino acid chiral separation that makes is selected overload quantity (e.e%) with hollow-fibre membrane, and separation (α) is 1.5.
Embodiment 6:
(1) the temperature sensitive copolymer microgel of chirality is synthetic: take the there-necked flask device, add 50ml through the THF condensing reflux except water treatment, add the NIPAAm monomer in there-necked flask, control NIPAAm concentration is 0.16mol/L.R is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, and behind the 0.18g crosslinking agent MBAA, logical nitrogen gas stirrings are 50 minutes under 30 ℃, slowly be warming up to 55 ℃, stablized 40 minutes, and added 0.07g initator azodiisobutyronitrile (AIBN), isothermal reaction 10 hours.After reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration obtains microgel, and drying is placed on sombre place and preserves.
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, and logical nitrogen adds the solvent DMF (DMF) of 12 times of PVDF quality, stirring and dissolving under heating condition under 70 ℃ of water-baths.Add NIPAAm in the situation of logical nitrogen, the mass ratio of control PVDF and NIPAAm is 1: 1.25, adds the initiator A IBN of PVDF quality 2.5%, and after the dissolving, logical nitrogen is 20 minutes again, continues stirring reaction 12 hours fully.After reaction finishes, will add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drains to get temperature sensitive film forming matter PVDF-g-PNIPAAm, and putting into 60 ℃ in baking oven, to be dried to constant weight stand-by.
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF, mass percent concentration is controlled at 18%, add microgel, the mass ratio of control microgel and PVDF-PNIPAAm is 1: 5, add at last pore-foaming agent polyethylene glycol (PEG), the mass percent concentration that makes PEG account for mixed liquor is 10%.Heating under 40 ℃ of conditions, stirring are until then fully dissolving pours spinning liquid in the spinning-drawing machine material still, and spinning-drawing machine material still is heated in sealing, and making the spinning liquid temperature is 30 ℃, vacuum defoamation 60 minutes.
After the spinning liquid deaeration is disposed, open material still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 12 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 28 ℃ coagulating bath, 18 rev/mins of control take up roll rotating speeds.Coiler device is shut down, and takes off fiber, and spun hollow-fibre membrane is soaked a week in distilled water, changes water every day 2 times, then is dipped in the glycerine water solution 2 days, cleans with distilled water and dries, and namely gets amino acid chiral separation hollow-fibre membrane.
It is 15% that the amino acid chiral separation that makes is selected overload quantity (e.e%) with hollow-fibre membrane, and separation (α) is 1.5.
Claims (10)
1. an amino acid chiral separates the preparation method who uses hollow-fibre membrane, comprises the steps:
(1) the temperature sensitive copolymer microgel of chirality is synthetic: the L-Phe esterification is generated L-Phe carbethoxy hydrochloride (L-PheEt), and then with acryloyl chloride acylation reaction synthesis of chiral monomer N-(L-1-ethoxycarbonyl-2-phenyl) acrylamide (AAc-L-PheEt): take the there-necked flask device, add 50ml through oxolane (THF) condensing reflux except water treatment, in there-necked flask, add the NIPAAm monomer, r is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, then after adding crosslinking agent MBAA, logical nitrogen gas stirrings are 30～60 minutes under 20～30 ℃, slowly be warming up to 50～70 ℃, stablized 20～40 minutes, add initator azodiisobutyronitrile (AIBN), isothermal reaction 6～10 hours, after reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration obtains the temperature sensitive copolymer microgel of chirality P (NIPAAm-co-AAc-L-PheEt), and drying is placed on sombre place and preserves;
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, logical nitrogen, the solvent N that adds 6～12 times of PVDF quality, dinethylformamide (DMF), stirring and dissolving under heating condition under 50～80 ℃ of water-baths, in the situation of logical nitrogen, add NIPAAm and initiator A IBN, after the dissolving, logical nitrogen is 10～20 minutes again, continues stirring reaction 8～12 hours fully, after reaction finishes, to add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drain to get temperature sensitive film forming matter PVDF-g-PNIPAAm, putting into 60 ℃ in baking oven, to be dried to constant weight stand-by;
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF; add microgel P (NIPAAm-co-AAc-L-PheEt); add at last pore-foaming agent polyethylene glycol (PEG); under 30～60 ℃ of conditions, heat; stir until fully dissolving; then spinning liquid is poured in the spinning-drawing machine material still; sealing; heating spinning-drawing machine material still; making the spinning liquid temperature is 25～50 ℃; vacuum defoamation 20～60 minutes; after the spinning liquid deaeration is disposed; open material still gate out switch; in still, pass into the nitrogen pressurization; open the measuring pump switch; adjust 8～20 rev/mins of rotating speeds; the beginning spinning; the doughnut that to extrude from spinneret is wound up on the take up roll after by 20～30 ℃ coagulating bath; 10～25 rev/mins of control take up roll rotating speeds; coiler device is shut down; take off fiber, spun hollow-fibre membrane is soaked a week in distilled water, change water every day 2 times; then be dipped in the glycerine water solution 1～2 day, clean to dry with distilled water and namely get amino acid chiral and separate and use hollow-fibre membrane.
2. a kind of amino acid chiral separates the preparation method who uses hollow-fibre membrane according to claim 1, it is characterized in that: add the NIPAAm monomer in the described step (1), control NIPAAm concentration is 0.1～0.18mol/L.
3. a kind of amino acid chiral separates the preparation method who uses hollow-fibre membrane according to claim 1, it is characterized in that: the addition of crosslinking agent MBAA is 0.05～0.20g in the described step (1).
4. a kind of amino acid chiral separates the preparation method who uses hollow-fibre membrane according to claim 1, it is characterized in that: the addition of initator azodiisobutyronitrile (AIBN) is 0.04～0.08g in the described step (1).
5. a kind of amino acid chiral separates the preparation method who uses hollow-fibre membrane according to claim 1, it is characterized in that: the mass ratio of PVDF powder and NIPAAm is 1 in the described step (2): (0.5～1.25).
6. a kind of amino acid chiral separates the preparation method who uses hollow-fibre membrane according to claim 1, it is characterized in that: the addition of initiator A IBN is 1%～2.5% of PVDF quality in the described step (2).
7. a kind of amino acid chiral separates the preparation method who uses hollow-fibre membrane according to claim 1, it is characterized in that: in the described step (3) film forming matter PVDF-g-PNIPAAm adding is filled in the container of DMF, mass percent concentration is controlled at 15%～20%.
8. a kind of amino acid chiral separates the preparation method who uses hollow-fibre membrane according to claim 1, it is characterized in that: the mass ratio of microgel and film forming matter PVDF-g-PNIPAAm is 1: 3～10 in the described step (3).
9. a kind of amino acid chiral separates the preparation method who uses hollow-fibre membrane according to claim 1, it is characterized in that: add pore-foaming agent polyethylene glycol (PEG) in the described step (3), the mass percent concentration that makes PEG account for mixed liquor is 5%～10%.
10. a kind of amino acid chiral of any one separates amino acid chiral that the preparation method with hollow-fibre membrane makes and separates and use hollow-fibre membrane according to claim 1-9, and it is characterized in that: described amino acid chiral separation comprises the steps: with the preparation method of hollow-fibre membrane
(1) the temperature sensitive copolymer microgel of chirality is synthetic: the L-Phe esterification is generated L-Phe carbethoxy hydrochloride (L-PheEt), and then with acryloyl chloride acylation reaction synthesis of chiral monomer N-(L-1-ethoxycarbonyl-2-phenyl) acrylamide (AAc-L-PheEt): take the there-necked flask device, add 50ml through oxolane (THF) condensing reflux except water treatment, in there-necked flask, add the NIPAAm monomer, r is 0.2 adding chiral monomer AAc-L-PheEt in mass ratio, then after adding crosslinking agent MBAA, logical nitrogen gas stirrings are 30～60 minutes under 20～30 ℃, slowly be warming up to 50～70 ℃, stablized 20～40 minutes, add initator azodiisobutyronitrile (AIBN), isothermal reaction 6～10 hours, after reaction finishes, add petroleum ether precipitation to reactant liquor, suction filtration obtains the temperature sensitive copolymer microgel of chirality P (NIPAAm-co-AAc-L-PheEt), and drying is placed on sombre place and preserves;
(2) temperature sensitive film forming matter is synthetic: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, logical nitrogen, the solvent N that adds 6～12 times of PVDF quality, dinethylformamide (DMF), stirring and dissolving under heating condition under 50～80 ℃ of water-baths, in the situation of logical nitrogen, add NIPAAm and initiator A IBN, after the dissolving, logical nitrogen is 10～20 minutes again, continues stirring reaction 8～12 hours fully, after reaction finishes, to add methanol extraction after the reactant liquor cooling, suction filtration washes repeatedly with distilled water, then drain to get temperature sensitive film forming matter PVDF-g-PNIPAAm, putting into 60 ℃ in baking oven, to be dried to constant weight stand-by;
(3) chiral separation is with the preparation of hollow-fibre membrane: film forming matter PVDF-g-PNIPAAm is added fill in the container of DMF; add microgel P (NIPAAm-co-AAc-L-PheEt); add at last pore-foaming agent polyethylene glycol (PEG); under 30～60 ℃ of conditions, heat; stir until fully dissolving; then spinning liquid is poured in the spinning-drawing machine material still; sealing; heating spinning-drawing machine material still; making the spinning liquid temperature is 25～50 ℃; vacuum defoamation 20～60 minutes; after the spinning liquid deaeration is disposed; open material still gate out switch; in still, pass into the nitrogen pressurization; open the measuring pump switch; adjust 8～20 rev/mins of rotating speeds; the beginning spinning; the doughnut that to extrude from spinneret is wound up on the take up roll after by 20～30 ℃ coagulating bath; 10～25 rev/mins of control take up roll rotating speeds; coiler device is shut down; take off fiber, spun hollow-fibre membrane is soaked a week in distilled water, change water every day 2 times; then be dipped in the glycerine water solution 1～2 day, clean to dry with distilled water and namely get amino acid chiral and separate and use hollow-fibre membrane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880689A (en) * | 2014-03-05 | 2014-06-25 | 上海师范大学 | Method for separating amino acid enantiomer based on polydopamine nano-channel |
| CN109385685A (en) * | 2018-11-09 | 2019-02-26 | 东华大学 | A kind of preparation method for the thermal response nano fibrous membrane that phase transition temperature is controllable |
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| CN101711951A (en) * | 2009-11-23 | 2010-05-26 | 天津工业大学 | Method for preparing fiber separation film |
| CN101985086A (en) * | 2009-11-23 | 2011-03-16 | 天津工业大学 | Temperature response hollow fiber separation membrane |
| CN102432746A (en) * | 2011-09-26 | 2012-05-02 | 天津工业大学 | Temperature-responsive L-amino-acid-modified chiral high-molecular hydrogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711951A (en) * | 2009-11-23 | 2010-05-26 | 天津工业大学 | Method for preparing fiber separation film |
| CN101985086A (en) * | 2009-11-23 | 2011-03-16 | 天津工业大学 | Temperature response hollow fiber separation membrane |
| CN102432746A (en) * | 2011-09-26 | 2012-05-02 | 天津工业大学 | Temperature-responsive L-amino-acid-modified chiral high-molecular hydrogel |
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| CN103880689A (en) * | 2014-03-05 | 2014-06-25 | 上海师范大学 | Method for separating amino acid enantiomer based on polydopamine nano-channel |
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| CN109385685A (en) * | 2018-11-09 | 2019-02-26 | 东华大学 | A kind of preparation method for the thermal response nano fibrous membrane that phase transition temperature is controllable |
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