CN103755967B - A kind of Thermo-sensitive chiral separation additive and Thermo-sensitive polysulfones chiral separation film - Google Patents
A kind of Thermo-sensitive chiral separation additive and Thermo-sensitive polysulfones chiral separation film Download PDFInfo
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Abstract
The Thermo-sensitive polysulfones chiral separation film that the present invention is specifically related to a kind of Thermo-sensitive chiral separation additive and is prepared by this Thermo-sensitive chiral separation additive.This Thermo-sensitive chiral separation additive can effectively be dispersed in the mixing solutions of organic solvent and water.When in the mixing solutions that finished product polysulfone membrane is immersed in organic solvent and water, polysulfones material is in microswelling state, the hydrophobic segment of Thermo-sensitive chiral separation additive is just as " anchor ", and slowly attachment pierces in these spaces, and hydrophilic segment then or is effectively dispersed in water.By adsorbed have the polysulfone membrane of Thermo-sensitive chiral separation additive to be soaked in pure water again time, the hydrophobic segment of Thermo-sensitive chiral separation additive has firmly been fixed on the surface of polysulfone membrane.The present invention just can realize the functional modification of polysulfone membrane by means of only soaking, make it possess Thermo-sensitive chiral separation function; Easy to operate, with low cost.
Description
Technical field
The invention belongs to functional polymer technical field, be specifically related to a kind of Thermo-sensitive chiral separation additive, and the Thermo-sensitive polysulfones chiral separation film prepared by this Thermo-sensitive chiral separation additive.
Background technology
Chemical composition is identical, but its space structure is different, thus constitutes two kinds of structure formations mutually in mirror, is called enantiomorph or optical isomer.Although 2 kinds of enantiomorph structural similitudies, its absorption in vivo, transhipment, there is great difference in metabolism, so need in actual production to obtain enantiomorph pure as far as possible.The method obtaining single enantiomer has several as follows: as obtained from occurring in nature is natural, be that substrate synthesizes, but their kinds are few with natural chiral compound, and restriction is large.Can be obtained by biosynthesizing in addition, but high cost.Racemate resolution then occupies namely important position in industrial application.It is reported, the non-natural chiral drug of nearly more than 65% is obtained by the fractionation of racemic modification or intermediate product at present.Wherein membrane sepn is low, simple to operate because of its energy consumption, can the advantage of operate continuously, is considered to one of latest model, the most promising and challenging method.
Polysulfones is slightly amber armorphous transparent or semitransparent polymkeric substance, excellent in mechanical performance, and rigidity is large, wear-resisting, high strength, thermostability is high, hydrolysis, good stability of the dimension, molding shrinkage is little, nontoxic, radiation hardness, resistance to combustion, has the property put out, chemical stability is good, except concentrated nitric acid, the vitriol oil, halohydrocarbon, and the general acid of ability, alkali, salt, at ketone, swelling in ester.The porous-film prepared based on polysulfones has the superiority the same with polysulfones substrate, and it is all widely used in electric, food and daily necessities, automobile, aviation, the department such as medical treatment and general industry.
Cyclodextrin, have the annular oligose of special structure as one, chiral enantiomorph has recognition performance.Can be used for selective separation mixture of enantiomers.Its outside is hydrophilic surface, inner then be a hydrophobic cavity with certain size, so according to cavity size, hydrophobic forces, hydrogen bond and Van der Waals force etc., cyclodextrin can combine with guest molecule and form mixture.Therefore, cyclodextrin is that one is applicable to for modified membrane very much, makes it the natural molecule possessing chiral recognition function.Meanwhile, it all has Selective recognition effect to multiple amino acids.Refer to document: Anal.Chem.(1992) 64; 1405-1412.
Chiral polymer membrane separation technique is studied in recent years widely.It is normally made up of chiral polymer or surface non-selective porous support membrane with proficiency Sexual behavior mode thin layer.The feature of this polymer film is high specific surface area, low substance transportation resistance, good physical strength and chiral recognition.Its utilizes the object being reached resolution by splitting the difference of the distribution behavior of material in chiral recognition functional polymer film and velocity of diffusion.The topmost mechanism of powder film is torn open for chirality and mainly contains 2 kinds: (1) molecular imprinting splits, in film, namely introduce template enantiomorph molecule, when racemic modification filters, only have template molecule can mistake then cannot be through through, other molecules.Although this mode separating effect is excellent, selectivity is very low, can only be separated specific racemic modification.(2) chiral recognition site splits, and namely introduces the unit with chiral separation function on film surface and fenestra inside, as beta-cyclodextrin, and bovine serum albumin etc.These recognition units selectively can adsorb or complexing a certain class enantiomorph, thus reach the object of chiral separation.This kind of method for splitting universality is higher.Thermo-sensitive chiral separation film then as a kind of mould material of forward position more, by scientific research personnel's growing interest.This kind of mould material possesses a temperature response value, below this value, chiral separation film possesses chiral recognition function, single enantiomer can be adsorbed, more than this temperature, chiral separation film will weaken greatly for the adsorptive power of single enantiomer, and the enantiomorph adsorbed can come off from film surface, makes film be returned to virgin state.This is conducive to repetition and the operate continuously of film.
If in conjunction with polysulfones physical and chemical performance advantage, advantage in the enantiomorph identification of cyclodextrin, by function using polysulfones as film base material, cyclodextrin is as chiral separation site, introduce temperature sensing polymer wherein again, then can prepare the Thermo-sensitive chiral separation film of physical and chemical performance excellence.
Prepare Thermo-sensitive chiral separation film, then need to carry out modification to film, the method for modification has a lot.Such as blended, compound, chemical modification, initiation grafting, light radiation grafting, low-temperature plasma grafting, enzyme initiation grafting.Patent CN1880880C reports and utilizes plasma treatment organic or inorganic material surface, then the cyclodextrin monomer of graft polymerization N-isopropylacrylamide (NIPAAm) and modified.This method simple and effective, but need to use plasma irradiating source, and factory and the laboratory with this equipment are less, and running cost is higher, and large-scale promotion need to promote.Patent CN103007774A and comparatively similar a kind of microgel and the blended method of polyvinylidene difluoride (PVDF) grafts of utilizing that report of CN103055710A two sections of patents prepare Thermo-sensitive chiral separation film, but this kind of film can only be accomplished to split the identification of specific enantiomeric, the component of blend film is too much simultaneously, very easily produce and be separated, affect homogeneity and the stability of film.
The problem preparing the solution of Thermo-sensitive chiral separation film needs at present mainly contains: (1) running cost is low as far as possible, and process is as far as possible simple and easy; (2) avoid polycomponent blended, affect the homogeneity of film internal structure; (3) select the chiral recognition site that enantioselectivity universality is higher as far as possible.
For these three problems, a kind of polymeric additive with chiral recognition unit of diblock of design and synthesis of the present invention, due to the hydrophobe speciality of diblock, it can be introduced in polysulfone membrane substrate surface by infusion method.Form the polysulfone membrane that surface has chiral separation function.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of Thermo-sensitive chiral separation additive.
Another object of the present invention is to the preparation method that above-mentioned Thermo-sensitive chiral separation additive is provided.
Another object of the present invention is that the shortcoming overcoming prior art is with not enough, and provide a kind of Thermo-sensitive polysulfones chiral separation film, this Thermo-sensitive polysulfones chiral separation film is prepared by above-mentioned Thermo-sensitive chiral separation additive.
Object of the present invention is achieved through the following technical solutions:
A kind of Thermo-sensitive chiral separation additive, has following general formula:
A-b-P（NIPAAm-co-CD）
Wherein NIPAAm is N-isopropylacrylamide, and CD is beta-cyclodextrin, and A is hydrophobic segment; B represents block; P(NIPAAm-co-CD) be hydrophilic segment;
The polymkeric substance forming described hydrophobic segment is the one in following polymkeric substance:
The positive butyl ester of alkynyl end polyacrylic acid (PBA-C ≡ CH),
The positive butyl ester of alkynyl end polymethyl (PMBA-C ≡ CH),
Alkynyl end polymethyl acrylate (PMA-C ≡ CH),
Alkynyl end polymethylmethacrylate (PMMA-C ≡ CH),
Alkynyl end saturated alkyl chain ((CH
2)
n-C ≡ CH), wherein n=8 ~ 16;
The polymkeric substance forming described hydrophilic segment is random copolymers (the P(NIPAAm-co-CD)-N of nitrine cardinal extremity NIPA and mono-vinyl cyclodextrin
3);
The preparation method of above-mentioned Thermo-sensitive chiral separation additive, comprises the steps:
(1) synthesis of hydrophobic segment polymkeric substance;
(2) synthesis of hydrophilic segment polymkeric substance;
(3) the click chemistry grafting of hydrophobe segmented polymer: the hydrophilic segment polymkeric substance described in step (2) getting 100 molar part, the hydrophobic segment polymkeric substance described in step (1) of 100 molar part, adds the CuSO of 1 molar part
4, the sodium ascorbate of 1 molar part, the dimethyl formamide of 500 molar part carries out click chemistry, and synthesis obtains Thermo-sensitive chiral separation additive.Reaction conditions reference literature TernaryGraftCopolymersandTheirUseinNanocapsulePreparatio n.Macromolecules, Macromolecules(2013) 46; 2646 ~ 2657;
Hydrophobic segment polymkeric substance described in step (1) is the one in following polymkeric substance:
The positive butyl ester of alkynyl end polyacrylic acid (PBA-C ≡ CH),
The positive butyl ester of alkynyl end polymethyl (PMBA-C ≡ CH),
Alkynyl end polymethyl acrylate (PMA-C ≡ CH),
Alkynyl end polymethylmethacrylate (PMMA-C ≡ CH),
Alkynyl end saturated alkyl chain (CH
2)
n-C ≡ CH, wherein n=8 ~ 16;
Hydrophilic segment polymkeric substance described in step (2) is random copolymers (the P(NIPAAm-co-CD)-N of nitrine cardinal extremity NIPA and mono-vinyl cyclodextrin
3);
The synthetic method of described PBA-C ≡ CH comprises following steps: the PMDETA (PMDETA) getting the bromo acid propynyl ester initiator of 3 ~ 10 molar part, the n-butyl acrylate (BA) of 300 ~ 1000 molar part, the toluene of 300 ~ 1000 molar part, the CuBr of 3 ~ 10 molar part and 3 ~ 10 molar part, 90 DEG C are carried out atom transfer radical polymerization (ATRP) reaction under nitrogen protection, obtain the PBA-C ≡ CH that the polymerization degree (DP) is 33 ~ 100;
The synthetic method of described PMBA-C ≡ CH comprises following steps: the PMDETA (PMDETA) getting the bromo acid propynyl ester initiator of 3 ~ 10 molar part, the n-BMA (MBA) of 300 ~ 1000 molar part, the toluene of 300 ~ 1000 molar part, the CuBr of 3 ~ 10 molar part and 3 ~ 10 molar part, 90 DEG C are carried out atom transfer radical polymerization (ATRP) reaction under nitrogen protection, obtain the PMBA-C ≡ CH that the polymerization degree (DP) is 33 ~ 100;
The synthetic method of described PMA-C ≡ CH comprises following steps: the PMDETA (PMDETA) getting the bromo acid propynyl ester initiator of 3 ~ 10 molar part, the methyl acrylate (MA) of 300 ~ 1000 molar part, the phenyl ether of 300 ~ 1000 molar part, the CuBr of 3 ~ 10 molar part and 3 ~ 10 molar part, 90 DEG C are carried out atom transfer radical polymerization (ATRP) reaction under nitrogen protection, obtain the PMA-C ≡ CH that the polymerization degree (DP) is 33 ~ 100;
The synthetic method of described PMMA-C ≡ CH comprises following steps: the PMDETA (PMDETA) getting the bromo acid propynyl ester initiator of 3 ~ 10 molar part, the methyl methacrylate (MMA) of 300 ~ 1000 molar part, the phenyl ether of 300 ~ 1000 molar part, the CuBr of 3 ~ 10 molar part and 3 ~ 10 molar part, 90 DEG C are carried out atom transfer radical polymerization (ATRP) reaction under nitrogen protection, obtain the PMMA-C ≡ CH that the polymerization degree (DP) is 33 ~ 100;
Described (CH
2)
nthe synthetic method of-C ≡ CH comprises following steps: the alkyl acid ((CH getting 50 ~ 100 molar part
2)
n-COOH), the propiolic alcohol of 80 ~ 120 molar part, be dissolved in the dioxane of 500 ~ 800 molar part, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride of 80 ~ 120 molar part, the Dimethylamino pyridine of 1 ~ 3 molar part, stirred at ambient temperature 24 hours, by revolving steaming, dichloromethane extraction, obtains (CH
2)
n-C ≡ CH; Wherein n=8 ~ 16;
Described hydrophilic segment polymkeric substance (P(NIPAAm-co-CD)-N
3) synthetic method comprise following steps: the bromo acid nitrine ethyl ester getting 3 ~ 10 molar part, the NIPAAm of 300 ~ 500 molar part, the mono-vinyl cyclodextrin monomer of 150 ~ 250 molar part, the Virahol of 500 ~ 1000 molar part, the water of 500 ~ 1000 molar part, the CuCl of 3 ~ 10 molar part and three (2-methylaminoethyl) amine (Me of 3 ~ 10 molar part
6tREN), 25 DEG C are carried out atom transfer radical polymerization (ATRP) reaction under nitrogen protection, and obtaining the polymerization degree (DP) is the P(NIPAAm-co-CD of 38 ~ 92)-N3;
The synthesized reference document of bromo acid propynyl ester: TernaryGraftCopolymersandTheirUseinNanocapsulePreparatio n.Macromolecules(2013) 46; 2646 ~ 2657;
The synthesized reference document of bromo acid nitrine ethyl ester: SynthesisofamphiphilicandthermoresponsiveABCmiktoarmstar terpolymerviaacombinationofconsecutiveclickreactionsanda tomtransferradicalpolymerizationJournalofPolymerScience: PartA:PolymerChemistry (2009) 47; 4001 – 4013;
The synthesized reference document of mono-vinyl cyclodextrin: containing synthesis and the self-assembly of the temperature sensitive polymer of cyclodextrin, SCI (2010) 31; 167 ~ 171;
A preparation method for Thermo-sensitive polysulfones chiral separation film, comprises following steps:
(1) the Thermo-sensitive chiral separation additive of 1 ~ 10 mass parts is dissolved in the solvent orange 2 A of 1000 mass parts;
(2) add the water of 500 ~ 4000 mass parts in the solution obtained in step (1) with the speed of 5 ~ 10mL/min, and constantly stir the reaction heat discharged wherein;
(3) finished product polysulfone membrane is soaked into the solution in step (2), keeps soaking solution temperature to be 5 ~ 30 DEG C, soak 1 ~ 4 day;
(4) taken out by the film soaked, put into water and continue immersion 4 days, taking-up nitrogen dries up afterwards;
Solvent orange 2 A described in step (1) is the one in dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF);
Finished product polysulfone membrane described in step (3) can be the polysulfone membrane product can bought on the market arbitrarily.
Inventive principle:
A kind of Thermo-sensitive chiral separation additive (synthetic route is shown in Fig. 1) of diblock of design and synthesis of the present invention, a segment of this additive is hydrophobic, another segment is hydrophilic.Therefore can effectively be dispersed in the mixing solutions of organic solvent and water.When in the mixing solutions that finished product polysulfone membrane is immersed in organic solvent and water, polysulfones material is in microswelling state, between polysulfones molecular chain attachment and tangling slightly be eased, produce certain space.Now the hydrophobic segment of Thermo-sensitive chiral separation additive is just as " anchor ", and slowly attachment pierces in these spaces, and hydrophilic segment then or is effectively dispersed in water.Afterwards by adsorbed have the polysulfone membrane of Thermo-sensitive chiral separation additive to be soaked in pure water again time, polysulfones molecular chain closely tangles again, space disappears, and sound construction locks, and the hydrophobic segment of Thermo-sensitive chiral separation additive has firmly been fixed on the surface of polysulfone membrane.The Method And Principle of this immersion modification as shown in Figure 3.
The present invention has following advantage and effect relative to prior art:
(1) by means of only soaking the functional modification that just can realize polysulfone membrane, it is made to possess Thermo-sensitive chiral separation function; It is extremely convenient, with low cost to operate;
(2) Thermo-sensitive chiral separation additive is only fixed in the surface of polysulfone membrane material, does not affect the performance of polysulfone membrane material.
Accompanying drawing explanation
The synthetic route of Fig. 1 Thermo-sensitive chiral separation additive.
Fig. 2 is the HNMR figure of the Thermo-sensitive chiral separation additive that embodiment 2 prepares.
Fig. 3 utilizes Thermo-sensitive chiral separation additive to prepare the principle of Thermo-sensitive polysulfones chiral separation film.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The raw material used in embodiment is as follows:
Wherein, the synthesized reference document of bromo acid propynyl ester: TernaryGraftCopolymersandTheirUseinNanocapsulePreparatio n.Macromolecules(2013) 46; 2646 ~ 2657;
The synthesized reference document of bromo acid nitrine ethyl ester: SynthesisofamphiphilicandthermoresponsiveABCmiktoarmstar terpolymerviaacombinationofconsecutiveclickreactionsanda tomtransferradicalpolymerizationJournalofPolymerScience: PartA:PolymerChemistry (2009) 47; 4001 – 4013;
The synthesized reference document of mono-vinyl cyclodextrin: containing synthesis and the self-assembly of the temperature sensitive polymer of cyclodextrin, SCI (2010) 31; 167 ~ 171;
Embodiment 1
A preparation method for Thermo-sensitive chiral separation additive, comprises the steps (number mentioned below is molfraction):
(1) synthesis of hydrophilic segment polymkeric substance: get 3 parts of bromo acid nitrine ethyl esters, 300 parts of NIPAAm, 150 parts of mono-vinyl cyclodextrin monomers, 500 parts of Virahols, 500 parts of water, 3 parts of CuCl and 3 part of three (2-methylaminoethyl) amine (Me
6tREN), 25 DEG C are carried out ATRP reaction under nitrogen protection, and obtaining the polymerization degree (DP) is the P(NIPAAm-co-CD of 75)-N
3;
(2) synthesis of hydrophobic segment polymkeric substance: get 3 parts of bromo acid propynyl ester initiators, 300 parts of BA, 300 parts of toluene, 3 parts of CuBr and 3 part PMDETA, 90 DEG C are carried out ATRP reaction under nitrogen protection, obtain the PBA-C ≡ CH that the polymerization degree (DP) is 50;
(3) the click chemistry grafting of hydrophobe segmented polymer: get hydrophilic side chain 100 parts, hydrophobic side chain 100 parts, adds 1 part of CuSO
4, 1 part of sodium ascorbate, 500 parts of dimethyl formamides carry out click chemistry, and synthesis obtains PBA-b-P(NIPAAm-co-CD) Thermo-sensitive chiral separation additive.
Embodiment 2
A preparation method for Thermo-sensitive chiral separation additive, comprises the steps (number mentioned below is molfraction):
(1) synthesis of hydrophilic segment polymkeric substance: get 3 parts of bromo acid nitrine ethyl esters, 400 parts of NIPAAm, 150 parts of mono-vinyl cyclodextrin monomers, 600 parts of Virahols, 600 parts of water, 3 parts of CuCl and 3 part Me
6tREN, 25 DEG C are carried out ATRP reaction under nitrogen protection, and obtaining the polymerization degree (DP) is the P(NIPAAm-co-CD of 92)-N
3;
(2) synthesis of hydrophobic water segmented polymer: get 10 parts of bromo acid propynyl ester initiators, 1000 parts of MMA(methyl methacrylates), 1000 parts of phenyl ether, 10 parts of CuBr and 10 part PMDETA, 90 DEG C are carried out ATRP reaction under nitrogen protection, obtain the PMMA-C ≡ CH that the polymerization degree (DP) is 100;
(3) the click chemistry grafting of hydrophobe segmented polymer: get hydrophilic side chain 100 parts, hydrophobic side chain 100 parts, adds 1 part of CuSO
4, 1 part of sodium ascorbate, 500 parts of dimethyl formamides carry out click chemistry, and synthesis obtains PMMA-b-P(NIPAAm-co-CD) Thermo-sensitive chiral separation additive, wherein, Fig. 2 is the HNMR figure of this Thermo-sensitive chiral separation additive.
Embodiment 3
A preparation method for Thermo-sensitive chiral separation additive, comprises the steps (number mentioned below is molfraction):
(1) synthesis of hydrophilic segment polymkeric substance: get 6 parts of bromo acid nitrine ethyl esters, 400 parts of NIPAAm, 200 parts of mono-vinyl cyclodextrin monomers, 800 parts of Virahols, 800 parts of water, 6 parts of CuCl and 6 part Me
6tREN, 25 DEG C are carried out ATRP reaction under nitrogen protection, and obtaining the polymerization degree (DP) is the P(NIPAAm-co-CD of 50)-N
3;
(2) synthesis of hydrophobic water segmented polymer: get 50 parts of (CH
2)
8-COOH, 80 parts of propiolic alcohols, be dissolved in 500 parts of dioxane, adds 80 parts of 1-ethyls-(3-dimethylaminopropyl) carbodiimide hydrochloride, 1 part of Dimethylamino pyridine, stirred at ambient temperature 24 hours, by revolving steaming, dichloromethane extraction, obtains solid (CH
2)
8-C ≡ CH;
(3) the click chemistry grafting of hydrophobe segmented polymer: get hydrophilic side chain 100 parts, hydrophobic side chain 100 parts, adds 1 part of CuSO4,1 part of sodium ascorbate, and 500 parts of dimethyl formamides carry out click chemistry, and synthesis obtains (CH
2)
8-b-P(NIPAAm-co-CD) Thermo-sensitive chiral separation additive.
Embodiment 4
A preparation method for Thermo-sensitive chiral separation additive, comprises the steps (number mentioned below is molfraction):
(1) synthesis of hydrophilic segment polymkeric substance: get 10 parts of bromo acid nitrine ethyl esters, 500 parts of NIPAAm, 250 parts of mono-vinyl cyclodextrin monomers, 1000 parts of Virahols, 1000 parts of water, 10 parts of CuCl and 10 part Me
6tREN, 25oC carries out ATRP reaction under nitrogen protection, and obtaining the polymerization degree (DP) is the P(NIPAAm-co-CD of 38)-N
3;
(2) synthesis of hydrophobic water segmented polymer: get 100 parts of (CH
2)
16-COOH, 120 parts of propiolic alcohols, be dissolved in 800 parts of dioxane, adds 120 parts of 1-ethyls-(3-dimethylaminopropyl) carbodiimide hydrochloride, 3 parts of Dimethylamino pyridines, stirred at ambient temperature 24 hours, by revolving steaming, dichloromethane extraction, obtains solid (CH
2)
16-C ≡ CH;
(3) the click chemistry grafting of hydrophobe segmented polymer: get hydrophilic side chain 100 parts, hydrophobic side chain 100 parts, adds 1 part of CuSO
4, 1 part of sodium ascorbate, 500 parts of dimethyl formamides carry out click chemistry, and synthesis obtains (CH
2)
16-b-P(NIPAAm-co-CD) Thermo-sensitive chiral separation additive.
Embodiment 5
A preparation method for Thermo-sensitive polysulfones chiral separation film, comprises following steps (number mentioned below is mass fraction):
(1) the Thermo-sensitive chiral separation additive 1 part of embodiment 1 prepared is dissolved in 1000 parts of DMAc;
(2) in above-mentioned solution, add 500 parts of water with the speed of 5mL/min, and constantly stir the reaction heat discharged wherein;
(3) finished product polysulfone membrane is soaked into this solution, keeps soaking solution temperature to be 5 DEG C, soak 1 day;
(4) taken out by the film soaked, put into water and continue immersion 4 days, taking-up nitrogen dries up afterwards, obtains Thermo-sensitive polysulfones chiral separation film.
Embodiment 6
A preparation method for Thermo-sensitive polysulfones chiral separation film, comprises following steps (number mentioned below is mass fraction):
(1) the Thermo-sensitive chiral separation additive 5 parts of embodiments 3 prepared is dissolved in 1000 parts of DMF;
(2) in above-mentioned solution, add 2500 parts of water with the speed of 8mL/min, and constantly stir the reaction heat discharged wherein;
(3) finished product polysulfone membrane is soaked into this solution, keeps soaking solution temperature to be 20 DEG C, soak 3 days;
(4) taken out by the film soaked, put into water and continue immersion 4 days, taking-up nitrogen dries up afterwards, obtains Thermo-sensitive polysulfones chiral separation film.
Embodiment 7
A preparation method for Thermo-sensitive polysulfones chiral separation film, comprises following steps (number mentioned below is mass fraction):
(1) the Thermo-sensitive chiral separation additive 10 parts of embodiments 4 prepared is dissolved in 1000 parts of NMP;
(2) in above-mentioned solution, add 4000 parts of water with the speed of 10mL/min, and constantly stir the reaction heat discharged wherein;
(3) finished product polysulfone membrane is soaked into this solution, keeps soaking solution temperature to be 30 DEG C, soak 4 days;
(4) taken out by the film soaked, put into water and continue immersion 4 days, taking-up nitrogen dries up afterwards, Thermo-sensitive polysulfones chiral separation film.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a Thermo-sensitive chiral separation additive, is characterized in that having following general formula:
A-b-P（NIPAAm-co-CD）
Wherein NIPAAm is N-isopropylacrylamide, and CD is beta-cyclodextrin, and A is hydrophobic segment; B represents block; P(NIPAAm-co-CD) be hydrophilic segment;
The polymkeric substance forming described hydrophobic segment is the one in following polymkeric substance: PBA-C ≡ CH, PMBA-C ≡ CH, PMA-C ≡ CH, PMMA-C ≡ CH and (CH
2)
n-C ≡ CH, wherein n=8 ~ 16;
The polymkeric substance forming described hydrophilic segment is P(NIPAAm-co-CD)-N
3.
2. the preparation method of Thermo-sensitive chiral separation additive according to claim 1, is characterized in that comprising following steps:
(1) synthesis of hydrophobic segment polymkeric substance;
(2) synthesis of hydrophilic segment polymkeric substance;
(3) the click chemistry grafting of hydrophobe segmented polymer: the hydrophilic segment polymkeric substance described in step (2) getting 100 molar part, the hydrophobic segment polymkeric substance described in step (1) of 100 molar part, adds the CuSO of 1 molar part
4, the sodium ascorbate of 1 molar part, the dimethyl formamide of 500 molar part carries out click chemistry.
3. the preparation method of Thermo-sensitive chiral separation additive according to claim 2, is characterized in that:
Hydrophobic segment polymkeric substance described in step (1) is the one in following polymkeric substance: PBA-C ≡ CH, PMBA-C ≡ CH, PMA-C ≡ CH, PMMA-C ≡ CH and (CH
2)
n-C ≡ CH, wherein n=8 ~ 16;
Hydrophilic segment polymkeric substance described in step (2) is P(NIPAAm-co-CD)-N
3.
4. the preparation method of Thermo-sensitive chiral separation additive according to claim 3, is characterized in that:
The synthetic method of described PBA-C ≡ CH comprises following steps: the PMDETA getting the bromo acid propynyl ester initiator of 3 ~ 10 molar part, the n-butyl acrylate of 300 ~ 1000 molar part, the toluene of 300 ~ 1000 molar part, the CuBr of 3 ~ 10 molar part and 3 ~ 10 molar part, 90 DEG C are carried out ATRP reaction under nitrogen protection, obtain the PBA-C ≡ CH that the polymerization degree is 33 ~ 100;
The synthetic method of described PMBA-C ≡ CH comprises following steps: the PMDETA getting the bromo acid propynyl ester initiator of 3 ~ 10 molar part, the n-BMA of 300 ~ 1000 molar part, the toluene of 300 ~ 1000 molar part, the CuBr of 3 ~ 10 molar part and 3 ~ 10 molar part, 90 DEG C are carried out ATRP reaction under nitrogen protection, obtain the PMBA-C ≡ CH that the polymerization degree is 33 ~ 100;
The synthetic method of described PMA-C ≡ CH comprises following steps: the PMDETA getting the bromo acid propynyl ester initiator of 3 ~ 10 molar part, the methyl acrylate of 300 ~ 1000 molar part, the phenyl ether of 300 ~ 1000 molar part, the CuBr of 3 ~ 10 molar part and 3 ~ 10 molar part, 90 DEG C are carried out ATRP reaction under nitrogen protection, obtain the PMA-C ≡ CH that the polymerization degree is 33 ~ 100;
The synthetic method of described PMMA-C ≡ CH comprises following steps: the PMDETA getting the bromo acid propynyl ester initiator of 3 ~ 10 molar part, the methyl methacrylate of 300 ~ 1000 molar part, the phenyl ether of 300 ~ 1000 molar part, the CuBr of 3 ~ 10 molar part and 3 ~ 10 molar part, 90 DEG C are carried out ATRP reaction under nitrogen protection, obtain the PMMA-C ≡ CH that the polymerization degree is 33 ~ 100;
Described (CH
2)
nthe synthetic method of-C ≡ CH comprises following steps: (the CH getting 50 ~ 100 molar part
2)
nthe propiolic alcohol of-COOH, 80 ~ 120 molar part, be dissolved in the dioxane of 500 ~ 800 molar part, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride of 80 ~ 120 molar part, the Dimethylamino pyridine of 1 ~ 3 molar part, stirred at ambient temperature 24 hours, by revolving steaming, dichloromethane extraction, obtains (CH
2)
n-C ≡ CH; Wherein n=8 ~ 16.
5. the preparation method of Thermo-sensitive chiral separation additive according to claim 3, is characterized in that:
Described P(NIPAAm-co-CD) synthetic method of-N3 comprises following steps: the bromo acid nitrine ethyl ester getting 3 ~ 10 molar part; the NIPAAm of 300 ~ 500 molar part; the mono-vinyl cyclodextrin monomer of 150 ~ 250 molar part; the Virahol of 500 ~ 1000 molar part, the water of 500 ~ 1000 molar part; the CuCl of 3 ~ 10 molar part and three (2-methylaminoethyl) amine of 3 ~ 10 molar part; 25 DEG C are carried out ATRP reaction under nitrogen protection, obtain the P(NIPAAm-co-CD that the polymerization degree is 38 ~ 92)-N
3.
6. a Thermo-sensitive polysulfones chiral separation film, is characterized in that adopting Thermo-sensitive chiral separation additive according to claim 1 to prepare.
7. the preparation method of Thermo-sensitive polysulfones chiral separation film according to claim 6, is characterized in that comprising following steps:
(1) the Thermo-sensitive chiral separation additive of 1 ~ 10 mass parts is dissolved in the solvent orange 2 A of 1000 mass parts;
(2) add the water of 500 ~ 4000 mass parts in the solution obtained in step (1) with the speed of 5 ~ 10mL/min, and constantly stir the reaction heat discharged wherein;
(3) finished product polysulfone membrane is soaked into the solution in step (2), keeps soaking solution temperature to be 5 ~ 30 DEG C, soak 1 ~ 4 day;
(4) taken out by the film soaked, put into water and continue immersion 4 days, taking-up nitrogen dries up afterwards.
8. the preparation method of Thermo-sensitive polysulfones chiral separation film according to claim 7, is characterized in that:
Solvent orange 2 A described in step (1) is the one in dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF).
9. the application of Thermo-sensitive polysulfones chiral separation film according to claim 6 in functional polymer technical field.
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| CN108559265A (en) * | 2018-04-18 | 2018-09-21 | 苏州科技大学 | A kind of Thermo-sensitive polysulfones graft copolymer and Thermo-sensitive PS membrane |
| CN115253696B (en) * | 2021-04-29 | 2023-09-22 | 天津膜天膜科技股份有限公司 | Chiral separation membrane and preparation method thereof |
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| JPH05239157A (en) * | 1991-12-20 | 1993-09-17 | W R Grace & Co | Thermosensitive cyclodextrin |
| CN1788832A (en) * | 2004-12-17 | 2006-06-21 | 李连超 | Intelligent molecular blotting affinity membrane for chiral resolution and its preparation method |
| CN100480291C (en) * | 2007-06-15 | 2009-04-22 | 北京化工大学 | Method for preparing temperature sensitive hydrogel with supramolecular structure |
| CN102775564A (en) * | 2012-08-15 | 2012-11-14 | 西北工业大学 | Preparation method of temperature sensitive type monolithic column with chiral molecule recognition function |
| CN103007774A (en) * | 2012-12-19 | 2013-04-03 | 天津工业大学 | Flat sheet membrane for chiral separation of amino acid and preparation method thereof |
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| JPH05239157A (en) * | 1991-12-20 | 1993-09-17 | W R Grace & Co | Thermosensitive cyclodextrin |
| CN1788832A (en) * | 2004-12-17 | 2006-06-21 | 李连超 | Intelligent molecular blotting affinity membrane for chiral resolution and its preparation method |
| CN100480291C (en) * | 2007-06-15 | 2009-04-22 | 北京化工大学 | Method for preparing temperature sensitive hydrogel with supramolecular structure |
| CN102775564A (en) * | 2012-08-15 | 2012-11-14 | 西北工业大学 | Preparation method of temperature sensitive type monolithic column with chiral molecule recognition function |
| CN103007774A (en) * | 2012-12-19 | 2013-04-03 | 天津工业大学 | Flat sheet membrane for chiral separation of amino acid and preparation method thereof |
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