CN109569533A - A kind of polyurethane-graphite alkene chirality column material and preparation method thereof - Google Patents
A kind of polyurethane-graphite alkene chirality column material and preparation method thereof Download PDFInfo
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- CN109569533A CN109569533A CN201811254141.0A CN201811254141A CN109569533A CN 109569533 A CN109569533 A CN 109569533A CN 201811254141 A CN201811254141 A CN 201811254141A CN 109569533 A CN109569533 A CN 109569533A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
- B01D15/3833—Chiral chromatography
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
The invention discloses a kind of polyurethane-graphite alkene chirality column materials and preparation method thereof.Chiral monomer, isocyanates etc. and graphene are combined together by the polyurethane-graphite alkene chirality column material.Utilize the hydroxyl on graphene chiral material surface and reacting for isocyanates, polyurethane chemistry effectively can be bonded in graphene surface, the polyurethane-graphite alkene chiral separation column material of preparation, toughness, porosity, adsorption capacity and mechanical stability have all obtained greatly being promoted, with excellent swelling behavior, the promotion of toughness of material assigns its excellent processing performance, the defect for avoiding the layering of material and being unevenly distributed simultaneously.The chirality column material all has good fractionation effect to the enantiomer of phenylalanine, alanine, leucine, threonine.
Description
Technical field
The invention belongs to field of functional materials, be related to a kind of bonded type polyurethane graphene chirality column material of new chemical and
Preparation method.
Background technique
Chiral drug isolates and purifies, and plays very important effect to human health, chiral separation major gene its in chirality
Important application in terms of medical separation is widely regarded as one of the new material of most prospect.Chiral separation major gene stability is good,
The advantages that load capacity is strong, molecule dynamic delivery rate is fast, preparation cost is low and processing performance is good, in high performance liquid chromatography, core
It has been had been widely used in terms of the preparations of materials such as piece chromatography, capillary micro-extraction and Capillary Electrophoresis chromatography.Chirality point
Crosslinking inierpeneirating network structure unique from column and porous structure, make it possess biggish specific surface area and higher load capacity,
It in chiral drug separation, splits, the fields such as asymmetry catalysis have important application value, and chiral separation column prepares base at present
This is monopolized by overseas enterprise, and the price of chiral separation column is higher (being greater than 20,000 yuan/every).
Two-dimensional sheet graphene has high specific surface area (2630m2/ g), higher mechanical strength (130GPa) and excellent
Different thermal property, the research report in relation to graphene hybrid material are commonplace.But by it in conjunction with chipal compounds, preparation
Chiral column with medical separation ability, is but rarely reported, and causes toughness very poor this is because graphene chiral column intensity is excessively high,
It is easy to fracture in process, is crushed, pattern is difficult to maintain, and limits the preparation and application of splitter；And merely by chirality
The splitter of monomer preparation, material cost are high.The specific surface area of material is smaller simultaneously, causes material to the adsorbing separation of drug
Ability is poor.
Chiral column material has the separation of good chiral drug, asymmetric syntheses and catalytic performance, with chiral column material
Basic framework is the criteria for classifying, and chiral column material can be divided into two classes: (1) silica-base material, mainly using silica as basic framework
(Adv.Mater.,2006,18:3266-3270；J.Chromatogr.A,2014,1356:289-293)；(2) polymeric substrate
Material, mainly using polystyrene and polyacrylate as skeleton (J.Chromatogr.A, 2012,1267:144-155；Green
Chem.,2014,16:2798-2806).The chirality of the above chirality column material is mainly derived from the small molecules such as amino acid and protein
Equal natural macromoleculars.Research finds above-mentioned material there are specific surface areas that small, Swelling Capacity is low and bad mechanical property etc. lacks
Point has adverse effect on the service life and processing performance of material.
Summary of the invention
The object of the present invention is to provide a kind of polyurethane-graphite alkene chirality column material, large specific surface area, processing performance is good, hand
Property drug split ability it is strong.Flexibility improves, and cost significantly reduces.
It is a further object of the present invention to provide a kind of method for preparing polyurethane-graphite alkene chirality column material, processing step letters
It is single.
The invention is realized by the following technical scheme:
A kind of preparation method of polyurethane-graphite alkene chirality column material, comprising the following steps:
(1) preparation of Chiral functionalization graphene comprising the steps of: in the presence of an organic, catalyst A1's
Under catalysis, graphene oxide (GO) and chiral monomer separate product in 0 DEG C~100 DEG C preferably 30~80 DEG C reactions, dry,
It is made Chiral functionalization graphene (CFGO)；
(2) in the presence of an organic, under the catalysis of catalyst A2, CFGO, isocyanates and polyalcohol 0 DEG C~
100 DEG C of preferably 30~80 DEG C reactions, reaction time are preferably 3~6 hours 1~10 hour, are washed, dry.
Reaction equation is as follows:
Graphene oxide of the present invention is prepared using dilatometry well known in the art.
In step (1) of the present invention, the chiral monomer is selected from camphanic acid, camphor sulfonamide, isophorone diamine
It is one or more.
Chiral monomer of the invention has suitable big side group, provides enough steric hindrances, while also having stronger
Chiral radicals, the preferential of the property of can choose combine that configuration is identical therewith or similar chipal compounds, realize point of enantiomer
From, purifying.
In step (1) of the present invention, the mass ratio of GO and chiral monomer is 1:10~15:1.
It is sub- that organic solvent in step (1) of the present invention is selected from N,N-dimethylformamide, tetrahydrofuran, dimethyl
One of sulfone, acetone are a variety of.
Catalyst A1 in step (1) of the present invention includes that 4-dimethylaminopyridine (DMAP) and dicyclohexyl carbon two are sub-
Amine (DCC), wherein mass ratio=5:1~1:5 of GO and DMAP；It is preferred that mass ratio=1:1~1 of 3:1~1:2, GO and DCC:
15, preferably 1:1~1:10.
Any means well known in the art can be used in separation in step (1) of the present invention, it is preferred to use the side of centrifugation
Formula.
Dry temperature is 50~100 DEG C in step (1) of the present invention, and the time is 24~48 hours.
Preferably, step (2) of the present invention is the following steps are included: disperse CFGO in organic solvent, the side of dispersion
Any means well known in the art can be used in method, preferably ultrasonic；Isocyanates and polyalcohol are added in the dispersion liquid, mixed
It closes uniform；It is added dropwise to catalyst A2 in the dispersion liquid, after 30~80 DEG C are reacted 3~6 hours, washs, it is dry.
In step (2) of the present invention, isocyanates and polyalcohol and Chiral functionalization graphene oxide (CFGO)
In hydroxyl and/or amino reaction, formed macromolecules cross-linking structure.
It is sub- that organic solvent in step (2) of the present invention is selected from N,N-dimethylformamide, tetrahydrofuran, dimethyl
One of sulfone, acetone are a variety of.
In step (2) of the present invention, the mass ratio of isocyanates and CFGO are (1~3): 5；The matter of polyalcohol and CFGO
Amount is than being (10-20): 5.
In step (2) of the present invention, the catalyst A2 is selected from the C of leading chemical company, the U.S.6~C14Alkyl carboxylic acid
Zinc and/or bismuth carboxylate.
In step (2) of the present invention, the dosage of catalyst A2 is 0.2~1wt%, on the basis of the quality of isocyanates
It calculates.
In step (2) of the present invention, the time of the freeze-drying is 12~96 hours.
Isocyanates of the present invention includes but is not limited to one of following substance or a variety of: toluene di-isocyanate(TDI),
Isophorone diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, two isocyanide of hexa-methylene
Acid esters.
Polyalcohol of the present invention includes but is not limited to the one or more of following substance: polytetrahydrofuran polyol gathers
Ethylene glycol polyalcohol, polypropylene glycol polyalcohol, polyethylene glycol-propylene glycol polyalcohol.The number-average molecular weight of the polyalcohol is
500-4000, preferably 500-2000.
Polyurethane-graphite alkene chirality column material of the invention has regular layer structure, and toughness effectively improves, hand
Property column can maintain complete pattern.
Chiral separation column material of the invention, all has the enantiomer of phenylalanine, alanine, leucine, threonine
Good fractionation effect.
The present invention, can by the way that organic (chiral monomer, isocyanates etc.) and inorganic (graphene) component to be combined together
To prepare the organic and inorganic chirality column material for integrating a variety of advantages.And inorganic component (graphene) in chiral column material
Introducing, so that selectivity, toughness, service life and the mechanical performance of chiral column material is all effectively improved.Polyurethane is drawn
Enter above-mentioned system, it, can be effectively by polyurethane-reinforcement using the hydroxyl on graphene chiral material surface and reacting for isocyanates
Be bonded in graphene surface, the polyurethane-graphite alkene chiral separation column material of preparation, have the advantages that (1) toughness,
Porosity, adsorption capacity and mechanical stability have all obtained greatly being promoted, and have excellent swelling behavior, while toughness of material
Promotion assign its excellent processing performance, (2) chemical bonds, the defect for avoiding the layering of material and being unevenly distributed.
Detailed description of the invention
Fig. 1 is the photo in kind of the polyurethane-graphite alkene chiral separation column material of embodiment 1, and wherein A, B are respectively poly- ammonia
Picture before the swelling of ester graphene chirality column material and after swelling；
Fig. 2 is the infrared spectrum of the polyurethane-graphite alkene chiral separation column material of embodiment 1,
Wherein, A is the infrared spectrum of graphene oxide, and B is the infrared spectrum of Chiral functionalization graphene (CFGO), and C is
The infrared spectrum of polyurethane-graphite alkene chiral separation column material (CFGO).
Fig. 3 is the scanning electron microscope (SEM) photograph inside the polyurethane-graphite alkene chiral separation column material of embodiment 2；
Specific embodiment
Embodiment 1
The first step prepares Chiral functionalization graphene first, specific as follows: the GO (15g) that will be prepared is scattered in 50ml tetra-
In hydrogen furans, stirring a period of time, 1g camphor sulfonamide is added, then catalyst DCC (75g) is added in stirring to whole dissolutions
With DMAP (15g), 1h is reacted at room temperature, and product at reduced pressure filters, washed, is centrifuged with 100ml tetrahydrofuran, 70 DEG C of dryings for 24 hours, obtain
Chiral functionalization graphene CFGO.
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing CFGO (15g) and is scattered in and fills 50ml tetrahydro
In the test tube of furans, 3g toluene di-isocyanate(TDI) is added in Xiang Shangshu dispersion liquid, the poly- tetrahydro that 30g number-average molecular weight is about 1000
Furan polyols and 0.01g bismuth catalyst, under nitrogen protection, room temperature reaction 10h after reaction put chiral separation column
Enter in 50ml THF, washing removes uncrosslinked polyurethane, is freeze-dried 24 hours, obtains polyurethane-graphite alkene chiral column.
The comparison of A and B also illustrates that chiral column has stronger swelling energy to chiral column after taking out in test tube, while in Fig. 1
Power, swelling ratio 5, quality before swelling ratio=(quality before quality-swelling after swelling)/swelling.
Chiral column slice is when being bent 90 DEG C, the available holding of pattern, illustrates that chiral column is kept with good pattern
Ability is not susceptible to pattern and forgets oneself.
Chiral column material, specific surface area 4.329m are characterized using BET (BETA201A)2g-1, material internal is mostly nanometer
Hole aperture is about 18.8nm.
In Fig. 2, A is the infrared spectrum of graphene oxide, 1721cm-1Place be carboxyl in carbonyl absorption peak, illustrate by
Graphene oxide has successfully been prepared in graphene；B is the infrared spectrum of Chiral functionalization graphene (CFGO), appearance
1647cm-1And 1563cm-1The absorption peak at place shows that chiral monomer is bonded on graphene in a manner of chemical bond；C is poly-
The infrared spectrum of urethane graphene chiral separation column material (CFGO), 1715cm-1The absorption peak at place enhances.Illustrated by Fig. 2, is gathered
Urethane and Chiral functionalization graphene be in a manner of chemical bond it is bonded together.
Embodiment 2
The first step is prepared Chiral functionalization graphene (CFGO) first, specific as follows: the GO (5g) that will be prepared is scattered in
In 50ml tetrahydrofuran, stirring a period of time, 50g chiral monomer camphor sulfonamide is added, stirs to whole dissolutions, be then added
Catalyst DCC (25g) and DMAP (25g) reacts 1h at room temperature, and product at reduced pressure filters, washed, is centrifuged with 100ml tetrahydrofuran,
70 DEG C of dryings for 24 hours, obtain chirality function graphite alkene (CFGO).
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing Chiral functionalization graphene (CFGO) (15g)
It is scattered in the in the mixed solvent of 50ml tetrahydrofuran and acetone, 5g toluene di-isocyanate(TDI), 60g number is added in Xiang Shangshu dispersion liquid
The polytetrahydrofuran polyol and 0.01g bismuth catalyst that average molecular weight is about 2000 react at room temperature 2h under nitrogen protection, will
Chiral separation column is put into 80ml THF, and washing removes uncrosslinked polyurethane, is freeze-dried 24 hours, is obtained polyurethane-graphite
Alkene chiral column.
Inside SEM (Hitachi S-4700) analysis polyurethane-graphite alkene chiral separation column, Fig. 3, lamella are as a result seen
Structure is mainly made of graphene；Substance between lamella is mainly by cross-linked polymer group.
Embodiment 3
The first step prepares Chiral functionalization graphene first, specific as follows: the GO (15g) that will be prepared is scattered in 50ml
In n,N-Dimethylformamide, stirring a period of time, 2.5g camphanic acid is added, stirs to whole dissolutions, catalyst is then added
DCC (30g) and DMAP (3g) reacts 3h at room temperature, and product at reduced pressure filters, washed, is centrifuged with 100ml tetrahydrofuran, and 70 DEG C dry
It is dry for 24 hours, obtain chirality function graphite alkene CFGO.
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing CFGO (15g) and is scattered in 50ml N, N- bis-
5g dicyclohexyl methyl hydride diisocyanate is added in methylformamide, in Xiang Shangshu dispersion liquid, 40g number-average molecular weight is 2200
Chiral separation column is put by polyethylene glycol and 0.05g bismuth catalyst, under nitrogen protection, room temperature reaction 5h after reaction
In 100ml THF, washing removes uncrosslinked polyurethane, is freeze-dried 24 hours, obtains polyurethane-graphite alkene chiral column.
Embodiment 4
The first step is prepared Chiral functionalization graphene (CFGO) first, specific as follows: the GO (5g) that will be prepared is scattered in
In 50ml tetrahydrofuran, 2g chiral monomer isophorone diamine is added in stirring a period of time, stirring to whole dissolutions, then plus
Enter catalyst DCC (15g) and DMAP (1.5g), react 3h at room temperature, product at reduced pressure filters, washed with 100ml tetrahydrofuran, from
The heart, 70 DEG C of dryings for 24 hours, obtain chirality function graphite alkene (CFGO).
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing Chiral functionalization graphene (CFGO) (15g)
It is scattered in the in the mixed solvent of 50ml tetrahydrofuran and acetone, 5g toluene di-isocyanate(TDI), 35g number is added in Xiang Shangshu dispersion liquid
The polyethylene glycol polyalcohol and 0.03g bismuth catalyst that average molecular weight is 1200 react at room temperature 6h under nitrogen protection, will be chiral
Splitter is put into 100ml n,N-Dimethylformamide, and washing removes uncrosslinked polyurethane, is freeze-dried 48 hours, is obtained
Polyurethane-graphite alkene chiral column.
Embodiment 5
The first step prepares Chiral functionalization graphene first, specific as follows: the GO (15g) that will be prepared is scattered in 50ml tetra-
In hydrogen furans, stirring a period of time, 2.5g chiral monomer isophorone diamine is added, then stirring to whole dissolutions is added and urges
Agent DCC (30g) and DMAP (3g), reacts 5h at room temperature, and product at reduced pressure filters, washed, is centrifuged, 70 with 100ml tetrahydrofuran
It is DEG C dry for 24 hours, obtain chirality function graphite alkene CFGO.
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing CFGO (15g) and is scattered in 50ml tetrahydrofuran
In, 10g hexamethylene diisocyanate is added in Xiang Shangshu dispersion liquid, the polyethylene glycol-the third two that 60g number-average molecular weight is 2000
Chiral separation column is put by alcohol polyalcohol and 0.07g bismuth catalyst, under nitrogen protection, room temperature reaction 7h after reaction
In 100ml acetone, washing removes uncrosslinked polyurethane, is freeze-dried 72 hours, obtains polyurethane-graphite alkene chiral column.
Embodiment 6
The first step is prepared Chiral functionalization graphene (CFGO) first, specific as follows: the GO (5g) that will be prepared is scattered in
In 50ml dimethyl sulfoxide, stirring a period of time, 10g chiral monomer camphanic acid is added, then stirring to whole dissolutions is added and urges
Agent DCC (15g) and DMAP (1.5g) reacts 1h at room temperature, and product at reduced pressure filters, washed, is centrifuged with 100ml tetrahydrofuran,
70 DEG C of dry 48h, obtain chirality function graphite alkene (CFGO).
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing Chiral functionalization graphene (CFGO) (15g)
It is scattered in the in the mixed solvent of 50ml tetrahydrofuran and acetone, 5.6g toluene di-isocyanate(TDI), 30g is added in Xiang Shangshu dispersion liquid
The polyethylene glycol and 0.05g bismuth catalyst that number-average molecular weight is 4500 react at room temperature 2h, by chiral separation under nitrogen protection
Column is put into 100ml chloroform, and washing removes uncrosslinked polyurethane, is freeze-dried 24 hours, and it is chiral to obtain polyurethane-graphite alkene
Column.
Embodiment 7
The first step prepares Chiral functionalization graphene first, specific as follows: the GO (15g) that will be prepared is scattered in 50ml tetra-
In hydrogen furans, stirring a period of time, 5g camphor sulfonamide is added, then catalyst DCC (30g) is added in stirring to whole dissolutions
With DMAP (3g), 1h is reacted at room temperature, and product at reduced pressure filters, washed, is centrifuged with 100ml tetrahydrofuran, 70 DEG C of dryings for 24 hours, obtain
Chiral functionalization graphene CFGO.
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing CFGO (15g) and is scattered in 50ml N, N- bis-
7g dicyclohexyl methyl hydride diisocyanate is added in methylformamide, in Xiang Shangshu dispersion liquid, 55g number-average molecular weight is 3000
Polypropylene glycol polyalcohol and 0.02g bismuth catalyst react at room temperature 10h, after reaction, by chiral separation under nitrogen protection
Column is put into 100ml THF, and washing removes uncrosslinked polyurethane, is freeze-dried 24 hours, and it is chiral to obtain polyurethane-graphite alkene
Column.
Embodiment 8
The first step is prepared Chiral functionalization graphene (CFGO) first, specific as follows: the GO (5g) that will be prepared is scattered in
Stirring a period of time, 3g chiral monomer camphor sulphur is added in the in the mixed solvent of 50ml tetrahydrofuran and n,N-Dimethylformamide
Then amide, stirring to whole dissolutions are added catalyst DCC (20g) and DMAP (2.8g), react 1h, product at reduced pressure at room temperature
It filters, is washed, is centrifuged with excessive tetrahydrofuran, 70 DEG C of dryings for 24 hours, obtain chirality function graphite alkene (CFGO).
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing Chiral functionalization graphene (CFGO) (15g)
It is scattered in 50ml n,N-Dimethylformamide, 7g dicyclohexyl methyl hydride diisocyanate, 55g is added in Xiang Shangshu dispersion liquid
The polypropylene glycol polyalcohol and 0.05g bismuth catalyst that number-average molecular weight is 2000 react at room temperature 2h, by hand under nitrogen protection
Property splitter be put into 100ml THF, washing removes uncrosslinked polyurethane, is freeze-dried 24 hours, obtains polyurethane-graphite
Alkene chiral column.
Embodiment 9
The first step prepares Chiral functionalization graphene first, specific as follows: the GO (15g) that will be prepared is scattered in 50ml tetra-
In hydrogen furans, stirring a period of time, 5g chiral monomer camphanic acid is added, then catalyst DCC is added in stirring to whole dissolutions
(30g) and DMAP (3g) reacts 4h at room temperature, and product at reduced pressure filters, washed, is centrifuged with 500ml tetrahydrofuran, 70 DEG C of dryings
48h obtains chirality function graphite alkene CFGO.
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing CFGO (15g) and is scattered in 50ml tetrahydrofuran
In, 5g toluene di-isocyanate(TDI), 45g polytetrahydrofuran polyol and 0.05g bismuth catalyst are added in Xiang Shangshu dispersion liquid, in nitrogen
Under gas shielded, chiral separation column is put into 100ml THF by room temperature reaction 10h after reaction, and washing removes uncrosslinked
Polyurethane is freeze-dried 48 hours, obtains polyurethane-graphite alkene chiral column.
Embodiment 10
The first step is prepared Chiral functionalization graphene (CFGO) first, specific as follows: the GO (5g) that will be prepared is scattered in
In 50ml acetone, stirring a period of time, 5g chiral monomer camphor sulfonamide is added, then catalysis is added in stirring to whole dissolutions
Agent DCC (15g) and DMAP (1.5g), reacts 4.5h at room temperature, and product at reduced pressure is filtered, washed with excessive n,N-Dimethylformamide
It washs, be centrifuged, 70 DEG C of dryings for 24 hours, obtain chirality function graphite alkene (CFGO).
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing Chiral functionalization graphene (CFGO) (15g)
It is scattered in 50ml n,N-Dimethylformamide, 5g methyl diphenylene diisocyanate, 40g number is added in Xiang Shangshu dispersion liquid
Average molecular weight is that 1200 polyethylene glycol ester polyols and 0.04g bismuth catalyst react at room temperature 2h under nitrogen protection, will be chiral
Splitter is put into a large amount of n,N-Dimethylformamide, and washing removes uncrosslinked polyurethane, is freeze-dried 96 hours, is obtained
Polyurethane-graphite alkene chiral column.
Embodiment 11
The first step prepares Chiral functionalization graphene first, specific as follows: the GO (15g) that will be prepared is scattered in 50ml tetra-
In hydrogen furans, stirring a period of time, 5g chiral monomer camphanic acid is added, then catalyst DCC is added in stirring to whole dissolutions
(20g) and DMAP (1g) reacts 5h at room temperature, and product at reduced pressure filters, washed, is centrifuged with 100ml tetrahydrofuran, 70 DEG C of dryings
36h obtains chirality function graphite alkene CFGO.
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing CFGO (15g) and is scattered in 50ml tetrahydrofuran
In, 5g methyl diphenylene diisocyanate is added in Xiang Shangshu dispersion liquid, the polyethylene glycol-the third that 60g number-average molecular weight is 2000
Glycol polyalcohol and 0.01g bismuth catalyst, under nitrogen protection, room temperature reaction 10h after reaction put chiral separation column
Enter in 70ml THF, washing removes uncrosslinked polyurethane, is freeze-dried 24 hours, obtains polyurethane-graphite alkene chiral column.
For the chiral column slice of embodiment 2-11 when being bent 90 DEG C, it is good to illustrate that chiral column has for the available holding of pattern
Good pattern holding capacity, is not susceptible to pattern and forgets oneself.
Comparative example 1:
The first step prepares Chiral functionalization graphene first, specific as follows: the GO (1g) that will be prepared is scattered in 100ml tetra-
In hydrogen furans, stirring a period of time, 50g chiral monomer camphanic acid is added, then catalyst DCC is added in stirring to whole dissolutions
(20g) and DMAP (3g) reacts 5h at room temperature, and product at reduced pressure filters, washed, is centrifuged with 100ml tetrahydrofuran, 70 DEG C of dryings
For 24 hours, chirality function graphite alkene CFGO is obtained.
Second step prepares polyurethane-graphite alkene chiral column, specific as follows: weighing CFGO (15g) and is scattered in 100ml tetrahydro furan
30g methyl diphenylene diisocyanate is added in muttering, in Xiang Shangshu dispersion liquid, the polyethylene glycol-that 30g number-average molecular weight is 2000
Propylene glycol polyalcohol and 0.1g bismuth catalyst, under nitrogen protection, room temperature reaction 10h after reaction put chiral separation column
Enter in 200ml THF, washing removes uncrosslinked polyurethane, is freeze-dried 24 hours, obtains polyurethane-graphite alkene chiral column.
Graphene dosage is less in the program, to a certain extent increases the number of perforations of material, but increase it is unobvious, together
When graphene content it is less when, the intensity of material is not significantly improved, and the more crisp easy fragmentation of material cannot keep shape
Looks.
The drug of material splits experiment:
Application example 1: the chiral column material (20g) in above-described embodiment 1 is put into bag filter, raceme is subsequently placed in
In phenylalanine saturated solution.Timing take quantitative raffinate, with etc. quality pH=2 perchloric acid solution dilute, utilize HPLC
Measure the e.e. value of the surplus solution after chiral separation column material is split.The chiral column is torn open racemic phenylalanine solution
In point, chiral column material can realize racemic phenylalanine drug with the L-phenylalanine in Preferential adsorption racemic drug
It splits, chiral resolution efficiency is up to 87%.
Above-mentioned other embodiments and comparative example chiral separation column material imitate the fractionation application of phenylalanine racemization liquid solution
Fruit is summarized as follows table 1:
Table 1
| Embodiment | Sample quality | Phenylalanine raceme (35 DEG C) | Chiral resolution efficiency (e.e.) |
| 1 | 20 | 0.5g/mL | 87% |
| 2 | 20 | 0.5g/mL | 83% |
| 3 | 20 | 0.5g/mL | 83% |
| 4 | 20 | 0.5g/mL | 91% |
| 5 | 20 | 0.5g/mL | 88% |
| 6 | 20 | 0.5g/mL | 82% |
| 7 | 20 | 0.5g/mL | 89% |
| 8 | 20 | 0.5g/mL | 78% |
| 9 | 20 | 0.5g/mL | 83% |
| 10 | 20 | 0.5g/mL | 79% |
| 11 | 20 | 0.5g/mL | 86% |
| Comparative example 1 | 20 | 0.5g/mL | 67% |
Claims (10)
1. a kind of preparation method of polyurethane-graphite alkene chirality column material, comprising the following steps:
(1) preparation of Chiral functionalization graphene comprising the steps of: in the presence of an organic, in the catalysis of catalyst A1
Under, graphene oxide and chiral monomer separate product in 0 DEG C~100 DEG C preferably 30~80 DEG C reactions, and it is dry, chirality is made
Functionalization graphene；
(2) in the presence of an organic, under the catalysis of catalyst A2, Chiral functionalization graphene, isocyanates and polyalcohol
In 0 DEG C~100 DEG C preferably 30~80 DEG C reactions, the reaction time is preferably 3~6 hours 1~10 hour, is washed, dry.
2. the method according to claim 1, wherein the step (2) is the following steps are included: by Chiral functionalization
Graphene dispersion is in organic solvent；Isocyanates and polyalcohol are added in the dispersion liquid, are uniformly mixed；By catalyst
A2 is added dropwise in the dispersion liquid, after 30~80 DEG C are reacted 3~6 hours, is washed, dry.
3. method according to claim 1 or 2, which is characterized in that the chiral monomer of the step (1) be selected from camphanic acid,
Camphor sulfonamide, isophorone diamine it is one or more.
4. method according to claim 1-3, which is characterized in that in the step (1), graphene oxide and hand
Property monomer mass ratio be 1:10~15:1.
5. method according to claim 1-4, it is characterised in that, the catalyst A1 in the step (1) includes
4-dimethylaminopyridine and dicyclohexylcarbodiimide, wherein mass ratio=5:1 of graphene oxide and 4-dimethylaminopyridine
~1:5；It is preferred that mass ratio=1:1~1:15 of 3:1~1:2, graphene oxide and dicyclohexylcarbodiimide, preferably 1:1~
1:10。
6. method according to claim 1-5, which is characterized in that in the step (2), isocyanates and chirality
The mass ratio of functionalization graphene is (1~3): 5；The mass ratio of polyalcohol and Chiral functionalization graphene is (10-20): 5.
7. method according to claim 1-6, which is characterized in that the isocyanates is selected from toluene diisocynate
Ester, isophorone diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and hexa-methylene two
One of isocyanates is a variety of.
8. method according to claim 1-7, which is characterized in that it is polynary that the polyalcohol is selected from polytetrahydrofuran
Alcohol, polyethylene glycol polyalcohol, polypropylene glycol polyalcohol, polyethylene glycol-propylene glycol polyalcohol.
9. method according to claim 1-8, which is characterized in that the number-average molecular weight of the polyalcohol is 500-
4000, preferably 500-2000.
10. a kind of polyurethane-graphite alkene chirality column material of -9 described in any item method preparations according to claim 1.
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