CN103752180B - A kind of HP-β-CD chiral composite membrane and application thereof - Google Patents
A kind of HP-β-CD chiral composite membrane and application thereof Download PDFInfo
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- CN103752180B CN103752180B CN201310680500.XA CN201310680500A CN103752180B CN 103752180 B CN103752180 B CN 103752180B CN 201310680500 A CN201310680500 A CN 201310680500A CN 103752180 B CN103752180 B CN 103752180B
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- composite membrane
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- phpg
- chiral composite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a kind of hydroxypropyl beta cyclodextrin chiral composite membrane and application thereof.Polysulfone membrane deionized water is soaked two days, vertically dries, put into and take out and vertically dry after 0.02g/mL hydroxypropyl beta cyclodextrin solution soaks, then with 0.012g/mL1,6 hexamethylene diisocyanate solution carry out interfacial polymerization.After taking-up, dry after being washed with deionized water only after surface reagent volatilizees, obtain required chiral composite membrane.Being loaded by composite membrane in conventional electrodialysis apparatus, under concentration difference drives, split D-pHPG racemic modification solution, permeate D-pHPG enantiomeric purity is more than 55%.The present invention obtain enantiomeric purity is of a relatively high, low cost, energy-saving and environmental protection, be prone to continuous operation and large-scale industrial production.
Description
Technical field
The invention belongs to polymeric membrane chiral separation technical field, be specifically related to a kind of hydroxy propyl-Beta-ring
Dextrin chiral composite membrane.Meanwhile, the invention still further relates to this chiral composite membrane disappear outside D-pHPG
Application in rotation body fractionation.
Background technology
After chiral drug refers to introduce chiral centre in drug molecular structure, a pair obtained mirror image each other
Enantiomer, owing in chiral drug, the pharmaco-kinetic processes of two enantiomer is different, so chirality
Two enantiomer pharmacologically active, metabolic process, metabolic rate and toxicity the most in vivo in medicine
Etc. there is significant difference, it is understood that there may be following several situations: a kind of enantiomer in two enantiomer
There is pharmacologically active, and another kind is without significant pharmacological action；In two enantiomer one active, and another
One can occur antagonism；In two enantiomer one active, another does not only have activity on the contrary
Toxic side effect；Two enantiomer have equivalent or close pharmacologically active, and two enantiomer have sometimes
Close activity, but single enantiomer is the most preferably selected from overall balance；Two enantiomer have entirely different
Physiologically active, such as one of which enantiomer is appetite suppressant, and another kind is then revitalizer.
Owing to the deficiency of the most chiral medicine understanding causes many bitter lessons, these make people more increase the weight of
Depending on the enantiomer in chiral drug.
The production of chipal compounds typically has asymmetric synthesis and the big approach of chiral separation two.But pass through at present
The medicine that asymmetric synthesis obtains is relatively costly, and Enantiomer excess value (e.e.%) is relatively low, overall use
Scope is narrower；Chiral separation technology has again physical separation, chemical resolution method, molecularly imprinted polymer to tear open
Point-score, Chromatographic resolution method and film Split Method etc., but size of synthesis production, energy-saving and environmental protection, low cost etc.
Advantage surely belongs to chiral polymer film Split Method.
D-pHPG is mainly used in synthesizing broad ectrum antibiotic amoxicillin and cephalo-type antibiosis
Element medicine, such as amoxicillin, cefadroxil azoles etc..Owing to such medicine has disease resisting effect work good, secondary
By the feature such as little, therefore it is widely used.China is big to this type of pharmaceutical requirements amount, its medical market prospect
Wide.D-pHPG has optical activity, and they are left-handed different from dextrorotation, for medicine and agriculture
The mainly dextrorotation D-pHPG of medicine.
So far, there is not yet HP-β-CD composite membrane and at D-pHPG racemic modification
The open report of application in fractionation.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that a kind of with HP-β-CD
The chiral composite membrane prepared for raw material.
The present invention also aims to provide described HP-β-CD chiral composite membrane to hydroxyl
Application in phenylglycine racemate resolution.
The purpose of the present invention is achieved by the following technical programs.
Except as otherwise noted, percent of the present invention is mass percent.
A kind of HP-β-CD chiral composite membrane, it is characterised in that: use HP-β-CD
Soak basement membrane, obtain after then carrying out interfacial polymerization with function groups compound.
Specifically prepared by following methods:
(1) using polysulfone membrane as basement membrane, first soak two days with deionized water, vertically dry, then put
Enter immersion 3h in 0.02g/mL HP-β-CD aqueous solution, take out and vertically dry；
(2) interfacial polymerization, polymerization time 10s are carried out again with function groups compound；
(3) take out the basement membrane being polymerized, treat that surface reagent volatilizees, put in 110 DEG C of drying baker, heat
Process 20min；
(4) film after heat treatment is washed with deionized water only, i.e. obtains required HP-β-CD
Chiral composite membrane.
Described function groups compound is in multicomponent isocyanate, polynary acyl chlorides or multi-anhydride
Kind, or contain the functional group of plural isocyanates, acyl chlorides or anhydride simultaneously.Because hydroxypropyl
Effective body of-beta-schardinger dextrin-crosslinking chiral film is HP-β-CD, but HP-β-CD
Molecular structure in have substantial amounts of hydroxyl, therefore, with multicomponent isocyanate, polynary acyl chlorides or polyprotic acid,
Or contain the functional group of plural isocyanates, acyl chlorides or anhydride as cross-linking agent simultaneously, permissible
Reach same chiral separation effect.
It is molten that described function groups compound is preferably 0.012g/mL1,6-hexamethylene diisocyanate normal heptane
Liquid.
Described HP-β-CD chiral composite membrane is in D-pHPG racemate resolution
Application.
Particularly as follows: described HP-β-CD chiral composite membrane is loaded in conventional electrodialysis apparatus,
Under 0～0.5mg/mL concentration difference drives, split D-pHPG racemic modification aqueous solution.
Compared with prior art, it is an advantage of the current invention that:
1, the HP-β-CD chiral composite membrane of the application present invention splits outside D-pHPG
Raceme gained enantiomeric purity (e.e.%) can reach more than 55%, can realize enantiomer higher degree
Separation；
2, film splits and carries out at normal temperatures, and not undergoing phase transition, energy consumption is low；
3, film split process is without new chemical reagent, environmental protection, low cost；
4, membrance separation is prone to continuous operation, easily carries out large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the molecular structural formula of HP-β-CD；
Fig. 2 is the detection spectrogram that the chiral high performance liquid chromatography of film liquid crossed by enantiomer sample.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, present disclosure is described in further detail.But accompanying drawing
It is not limited to the technical solution with embodiment.
Embodiment 1
Commodity polysulfone membrane, as basement membrane, is soaked two days with deionized water, is vertically dried, put into 0.02g/mL
HP-β-CD solution soaking 3h, takes out and vertically dries.With oneself two isocyanides of 0.012g/mL1,6-
Acid esters n-heptane solution carries out interfacial polymerization, polymerization time 10s.Take out polysulfone membrane, treat that surface reagent volatilizees,
Put in 110 DEG C of drying baker, heat treatment 20min.Polysulfone composite membrane is washed with deionized water only, i.e. obtains
Required HP-β-CD chiral composite membrane.
Application Example 1
HP-β-CD chiral composite membrane embodiment 1 prepared loads conventional electrodialysis apparatus
In, under 0.5mg/mL difference drives, split the D-pHPG racemic modification that concentration is 0.5mg/mL
Solution.
Test result indicate that: utilize HP-β-CD chiral composite membrane of the present invention to split para hydroxybenzene
Glycine racemic modification, the D-pHPG enantiomer sample obtained after crossing film is through efficient liquid phase
Chromatogram shows that its purity is more than 55%.The separation of enantiomer higher degree can be realized；Owing to film splits
Carrying out at normal temperatures, not undergoing phase transition, therefore energy consumption is low；Owing to film split process is without new change
Learn reagent, therefore environmental protection, low cost；Membrance separation is prone to continuous operation, easily carries out large-scale industrial production.
Chiral separation effect is as shown in Figure 2.The raw material that chiral film splits is racemic compound, disappears outside
In rotation compound, the enantiomer concentration of left and right rotation is equal, if therefore with not having chiral separation energy
When the film of power removes resolution of racemic body, reflection should be the peak of two area equation in fig. 2.And we
It can be seen that the area at two peaks exists obvious difference from Fig. 2, therefore the hydroxypropyl of the present invention is described
-beta-schardinger dextrin-chirality cross linking membrane has obvious selectivity to the enantiomer of left and right rotation.Obtain after crossing film
D-pHPG enantiomer sample through high-efficient liquid phase chromatogram show its purity 55% with
On, the separation of high antimer purity can be realized.
Embodiment 2
Commodity polysulfone membrane, as basement membrane, is soaked two days with deionized water, is vertically dried, put into 0.02g/mL
HP-β-CD solution soaking 3h, takes out vertical 0.5h.With 0.021g/mL1,3,5-mesitylene
Formyl chloride n-heptane solution carries out interfacial polymerization, polymerization time 20s.Take out polysulfone membrane, treat that surface reagent is waved
Send out, put in 110 DEG C of drying baker, heat treatment 25min.Polysulfone composite membrane is washed with deionized water only, i.e.
Obtain required HP-β-CD chiral composite membrane.
Application Example 2
HP-β-CD chiral composite membrane embodiment 2 prepared loads conventional electrodialysis apparatus
In, under 0.2mg/mL difference drives, split the D-pHPG racemic modification that concentration is 0.2mg/mL
Solution.
Test result indicate that: utilize HP-β-CD chiral composite membrane of the present invention to split para hydroxybenzene
Glycine racemic modification, the D-pHPG enantiomer sample obtained after crossing film is through efficient liquid phase
Chromatogram shows that its purity is more than 50%.The separation of enantiomer higher degree can be realized；Owing to film splits
Carrying out at normal temperatures, not undergoing phase transition, therefore energy consumption is low；Owing to film split process is without new change
Learn reagent, therefore environmental protection, low cost；Membrance separation is prone to continuous operation, easily carries out large-scale industrial production.
Claims (2)
1. a HP-β-CD chiral composite membrane, it is characterised in that specifically by following methods
Prepare:
(1) using polysulfone membrane as basement membrane, first soak two days with deionized water, vertically dry, then put
Enter immersion 3h in 0.02g/mL HP-β-CD aqueous solution, take out and vertically dry；
(2) interfacial polymerization, polymerization time 10s are carried out again with function groups compound；Described many merits
Can dough compound be 0.012g/mL hexamethylene diisocyanate n-heptane solution；
(3) take out the basement membrane being polymerized, treat that surface reagent volatilizees, put in 110 DEG C of drying baker, heat
Process 20min；
(4) film after heat treatment is washed with deionized water only, i.e. obtains required HP-β-CD
Chiral composite membrane.
2. the HP-β-CD chiral composite membrane described in claim 1 is at D-pHPG
Application in racemate resolution, particularly as follows: by described HP-β-CD chiral composite membrane dress
Enter in conventional electrodialysis apparatus, under 0～0.5mg/mL concentration difference drives, split outside D-pHPG
Raceme aqueous solution.
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| CN103752180B true CN103752180B (en) | 2016-11-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104826506B (en) * | 2015-05-18 | 2017-02-22 | 天津工业大学 | Beta-cyclodextrin grafted polymer chiral separation membrane and preparation method thereof |
| CN111359455B (en) * | 2020-02-27 | 2021-05-18 | 华中科技大学 | Cyclodextrin modified polyamide thin film composite membrane, preparation and application thereof |
| CN113457468B (en) * | 2021-06-24 | 2022-10-28 | 北京工业大学 | Tannin-hydroxypropyl beta cyclodextrin composite nanofiltration membrane and preparation method thereof |
| CN114100379B (en) * | 2021-11-09 | 2023-10-03 | 天津大学 | Method for preparing high-flux reverse osmosis composite membrane by 4-dimethylaminopyridine-assisted cyclodextrin surface grafting |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357279A (en) * | 2013-07-30 | 2013-10-23 | 云南师范大学 | Teicoplanin chiral conposite membrane and its application in separation of D,L-p-hydroxyphenylglycine racemates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103357279A (en) * | 2013-07-30 | 2013-10-23 | 云南师范大学 | Teicoplanin chiral conposite membrane and its application in separation of D,L-p-hydroxyphenylglycine racemates |
Non-Patent Citations (2)
| Title |
|---|
| 环糊精及其衍生物作手性选择剂;傅若农等;《色谱分析概论》;化工工业出版社;20050331;第245页 * |
| 膜分离拆分对映异构体的研究进展;赵磊等;《河北工业科技》;20090131;第26卷(第1期);第55页 * |
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