CN105885082A - Method for preparing surface glycosyl modified porous material by utilizing highly-introverted emulsion template method - Google Patents
Method for preparing surface glycosyl modified porous material by utilizing highly-introverted emulsion template method Download PDFInfo
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- CN105885082A CN105885082A CN201610249463.0A CN201610249463A CN105885082A CN 105885082 A CN105885082 A CN 105885082A CN 201610249463 A CN201610249463 A CN 201610249463A CN 105885082 A CN105885082 A CN 105885082A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention belongs to the fields of high polymer materials, environment functional materials and biomedical materials and particularly relates to a method for preparing a surface glycosyl modified porous material by utilizing a highly-introverted emulsion template method. The preparation method comprises the steps that a non-ionic surfactant is utilized to stabilize a highly-introverted emulsion, water is used as a dispersion phase, a styrene monomer and a crosslinking agent divinyl benzene serve as continuous phases, 4-vinyl phenmethyl phthalimide is mixed in the continuous phases, and a porous foam material is prepared in the presence of an initiator by adopting the highly-introverted emulsion template method; a bromine group is introduced to the surface of the foam material through surface modification, the surface bromine group is used as an initiator to conduct atom transfer radical polymerization on a sugar monomer methylacrylic acid-2-(N-glucosamide) ethyl ester, and finally the surface glycosyl modified porous material is obtained. The product obtained by means of the method not only contains rich channel structures and functional groups and also has the effect of repeated usage, and a glucosamide structure polymer on the surface can effectively adsorb a trace amount of boron elements, sword bean protein lectin and the like.
Description
Technical field
The invention belongs to macromolecular material and environment functional material preparation field, be specifically related to a kind of method utilizing High Internal Phase Emulsion masterplate method to prepare the glycosyl modified porous material in surface.
Background technology
High Internal Phase Emulsion masterplate method is prepared gained porous material because of it and is had low-density and highly porous, can relatively conveniently process and chemical modification.Prepare compared with the method for porous material with other, this method has and is accurately controlled the size in hole and channel diameter and the advantage of distribution and becomes and prepare one of maximally efficient method of polymer porous material.This kind of method is suitably used as preparing adsorbing material, prepared material adsorption efficiency not to the utmost height and recoverable, material can be made to have good Selective adsorption by hole wall modification simultaneously.
Andreas Heise et al. (F. Audouin, A. Heise, et al.Biomacromolecules.,
2012,13,3787-3794) High Internal Phase Emulsion polymer is carried out amino functional surface modification, and then by its bromination, cause atom transferred free radical initiator polymerization (ATRP).ATRP initiator composition merit Atom Transfer Radical Polymerization on High Internal Phase Emulsion polymer surfaces, (methyl) acrylic monomers that polymer is intensive on High Internal Phase Emulsion polymer surface coating is polymerized, such as methyl methacrylate (MMA), tert-butyl acrylate (TBA) etc., the High Internal Phase Emulsion polymer obtaining high functionalization connects an acrylic acid, separation of small molecuies is included, it is provided that new thinking for bio-molecular separation.
Material containing Cis-hydroxyl groups and boron compound generation exchange reaction, form the boron ester type compound of tetrahedral structure.Around this principle, (B.F. Senkal, the N. Bicak such as SenkalReact.
&Funct. Polym., 2003,55:27-33) it is prepared for the boron adsorbent resin containing N-methyl glucose osamine, its main functional group is tertiary amine and hydroxyl, and for tertiary amine functional group, its protonation can promote the formation of boron tetrahedral complexes, prevent pH value from reducing, it is possible to be effectively prevented the hydrolysis of boron ester compounds.
It is known that there is interaction between glycosyl and protein, but this effect is also not only to occur between single glycan molecule and target protein so simple, fact proved that this effect is by the multivalence effect between the complex containing a large amount of glycosyls and protein.Dong Changming etc. (X.H. Dai, C.M. Dong,Journal of Polymer Science, Part A: Polymer Chemistry,2008, 46(3):
817 ~ 829) by PCL macromole evocating agent, cause methacrylic acid-2-(N-glucose amide) the acetate monomer polymerization containing unsaturated glycosyl, obtain sugary amphipathic nature block polymer, then investigate this sugar-containing polymer recognition performance for Con A Concanavalin (ConA).After result shows to add certain density ConA in this polymer nano-particle aqueous solution, muddy degree substantially strengthens, and uv absorption is significantly increased.In DLS test simultaneously, the nano-particle solution particle diameter of addition ConA is compared and is significantly increased with simple nano-particle solution.These results have all convincingly demonstrated the sugar-containing polymer of its synthesis and have had recognition reaction for ConA.
Utilize methacrylic acid-2-(N-glucose amide) ethyl ester as monomer (R. Narain,
S.P. Armes.Biomacromolecules, 2003,
4:1746-1758.), carry out atom transfer radical polymerization, by porous foam surface modification, introduce a large amount of glycosyl group, it is possible to achieve the effect of selective absorption.
High Internal Phase Emulsion is utilized to prepare the advantage of porous material structure, polymerization in conjunction with this advanced person of atom transfer radical polymerization, a large amount of Cis-hydroxyl groups segments are introduced on porous foam surface, synthetic product does not contain only abundant pore passage structure and function group, glycosyl modified energy active adsorption trace B element, the canavaline agglutinin etc. on surface, and there is reusable usefulness, all it is with a wide range of applications in environment functional material, technical field of biological material.
Summary of the invention
It is an object of the invention to provide a kind of method utilizing High Internal Phase Emulsion masterplate method to prepare the glycosyl modified porous material in surface.
It is an object of the invention to the sugar monomer methacrylic acid-2-(N-glucose amide containing great amount of hydroxy group) ethyl ester is incorporated on High Internal Phase Emulsion polymer surfaces as side chain, makes obtained product have low-density, highly porous, good Selective adsorption, high adsorption efficiency and repeatable usability simultaneously.Present invention styrene/divinylbenzene High Internal Phase Emulsion masterplate the law system of research maturation the most, use atom transfer radical polymerization method, prepare poly-(methacrylic acid-2-(N-glucose amide) ethyl ester of a series of different chain length) surface modify perforated foams.
The preparation method of the glycosyl modified porous material in surface that the present invention proposes, specifically comprises the following steps that
(1) Span80 is utilized to stablize high interior to emulsion, styrene monomer and cross-linker divinylbenzene are continuous phase, it is mixed into 4-vinyl benzyl group phthalimide in continuous phase, wherein: styrene, divinylbenzene, the mass ratio of Span80,4-vinyl four kinds of materials of benzyl group phthalimide are 1:(0.3 ~ 0.5): (0.3 ~ 0.6): (0.2 ~ 0.3), with water as dispersion phase, under potassium peroxydisulfate causes, the mass percent that aqueous phase accounts for emulsion overall is 70%～90%, obtains perforated foams by High Internal Phase Emulsion masterplate legal system；By product in the tert-butyl catechol solution of ethanol condensing reflux, wash, be dried, and with 2-bromo isobutyryl bromine reaction, by surface amino groups bromination, through surname extraction 10 ~ 48 hours, vacuum drying, obtain the white porosity foam that end group is bromine；
(2) step (1) is obtained the white porosity foam thing block that end group is bromine and add in solvent orange 2 A; it is subsequently adding sugar monomer methacrylic acid-2-(N-glucose amide) ethyl ester; sugar monomer methacrylic acid-2-(N-glucose amide) addition of ethyl ester determines by designed molecular weight and performance thereof; add catalyst B; system is reacted under argon or nitrogen are protected; reaction temperature is 50 ~ 90 DEG C, reacts 1～5 hour；Products therefrom, respectively with oxolane and acetone as washing liquid, through surname extraction 10 ~ 48 hours, vacuum drying, i.e. obtains required product.
In the present invention, described solvent orange 2 A is oxolane, DMF, N, one or more in N-diethylformamide or N,N-dimethylacetamide.
In the present invention, described catalyst B is one or more in Cu-lyt ./bipyridyl, cuprous bromide/bipyridyl, Cu-lyt ./pentamethyl-diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, Cu-lyt ./hexamethyl trien or cuprous bromide/hexamethyl trien.
It is an advantage of the current invention that: raw material sources are extensive, used styrene monomer, divinylbenzene, solvent, emulsifying agent, catalyst etc. all can industrialized production, 4-vinyl benzyl group phthalimide, methacrylic acid-2-(N-glucose amide) ethyl ester is relatively easily-synthesized, and whole preparation process method is simple.High Internal Phase Emulsion masterplate method is accurately controlled hole and the size of channel diameter and distribution.The glycosyl modified perforated foams in synthesized surface has low-density, highly porous, the glycosyl modified polymer energy active adsorption trace B element on surface, canavaline agglutinin etc. simultaneously, and has reusable usefulness.
Accompanying drawing explanation
Fig. 1: surface poly-(methacrylic acid-2-(N-glucose amide) ethyl ester of preparation in the present invention) structural representation of the terminal modified porous material of chain.
Fig. 2: the electron scanning micrograph of the porous foam material that the surface of preparation is glycosyl modified in the present invention.
Detailed description of the invention
Following example are to further illustrate the present invention rather than limit the scope of the present invention.
Porous foam structure pattern Fourier transform infrared spectrometer (FTIR) and scanning electron microscope (SEM) that this surface is glycosyl modified measure.
Embodiment 1
By Span80 0.8g, styrene monomer 1.7g, cross-linker divinylbenzene 0.7g, 4-vinyl benzyl group phthalimide 0.4g mixing, the most dropwise dropping potassium persulfate solution 17ml, obtains perforated foams by High Internal Phase Emulsion masterplate legal system；By product in the tert-butyl catechol solution of ethanol condensing reflux, wash, be dried, and with 2-bromo isobutyryl bromine reaction, by surface amino groups bromination, through surname extraction 24 hours, vacuum drying, obtain the white porosity foam that end group is bromine；Take product thing block 0.12g to add in DMF, be subsequently adding sugar monomer methacrylic acid-2-(N-glucose amide) ethyl ester 2g; Cu-lyt ./pentamethyl-diethylenetriamine is catalyst system and catalyzing; reacting under nitrogen protection, reaction temperature is 65 DEG C, reacts 4 hours；Products therefrom, respectively with oxolane and acetone as washing liquid, through surname extraction 24 hours, vacuum drying, i.e. obtains required product.
Embodiment 2
By Span80 0.8g, styrene monomer 1.7g, cross-linker divinylbenzene 0.7g, 4-vinyl benzyl group phthalimide 0.4g mixing, the most dropwise dropping potassium persulfate solution 17ml, obtains perforated foams by High Internal Phase Emulsion masterplate legal system；By product in the tert-butyl catechol solution of ethanol condensing reflux, wash, be dried, and with 2-bromo isobutyryl bromine reaction, by surface amino groups bromination, through surname extraction 10 hours, vacuum drying, obtain the white porosity foam that end group is bromine；Take product thing block 0.2g to add in oxolane, be subsequently adding sugar monomer methacrylic acid-2-(N-glucose amide) ethyl ester 2.5g, cuprous bromide/bipyridyl is catalyst system and catalyzing, reacts under nitrogen protection, and reaction temperature is 80 DEG C, reacts 2.5 hours；Products therefrom, respectively with oxolane and acetone as washing liquid, through surname extraction 10 hours, vacuum drying, i.e. obtains required product.
Embodiment 3
By Span80 0.8g, styrene monomer 1.7g, cross-linker divinylbenzene 0.7g, 4-vinyl benzyl group phthalimide 0.4g mixing, the most dropwise dropping potassium persulfate solution 17ml, obtains perforated foams by High Internal Phase Emulsion masterplate legal system；By product in the tert-butyl catechol solution of ethanol condensing reflux, wash, be dried, and with 2-bromo isobutyryl bromine reaction, by surface amino groups bromination, through surname extraction 24 hours, vacuum drying, obtain the white porosity foam that end group is bromine；Take product thing block 0.09g to add in N,N-dimethylacetamide, be subsequently adding sugar monomer methacrylic acid-2-(N-glucose amide) ethyl ester 2.5g; Cu-lyt ./hexamethyl trien is catalyst system and catalyzing; reacting under nitrogen protection, reaction temperature is 40 DEG C, reacts 5 hours；Products therefrom, respectively with oxolane and acetone as washing liquid, through surname extraction 24 hours, vacuum drying, i.e. obtains required product.
Claims (3)
1. one kind utilizes the method that High Internal Phase Emulsion masterplate method prepares the glycosyl modified porous material in surface, it is characterised in that specifically comprise the following steps that
(1) Span80 is utilized to stablize high interior to emulsion, with styrene monomer and cross-linker divinylbenzene as continuous phase, 4-vinyl benzyl group phthalimide it is mixed in continuous phase, wherein: styrene, divinylbenzene, the mass ratio of Span80,4-vinyl four kinds of materials of benzyl group phthalimide are 1:(0.3 ~ 0.5): (0.3 ~ 0.6): (0.2 ~ 0.3), with water as dispersion phase, the mass percent that aqueous phase accounts for emulsion overall is 70%～90%, under potassium peroxydisulfate causes, obtain perforated foams by High Internal Phase Emulsion masterplate legal system；By gained perforated foams in the tert-butyl catechol solution of ethanol condensing reflux, wash, be dried, and with 2-bromo isobutyryl bromine reaction, by surface amino groups bromination, through surname extraction 10 ~ 48 hours, vacuum drying, obtains the white porosity foam thing block that end group is bromine；
(2) step (1) is obtained the white porosity foam thing block that end group is bromine and join in solvent orange 2 A; it is subsequently adding sugar monomer methacrylic acid-2-(N-glucose amide) ethyl ester; sugar monomer methacrylic acid-2-(N-glucose amide) addition of ethyl ester determines by designed molecular weight and performance thereof; add catalyst B; system is reacted under argon or nitrogen are protected; reaction temperature is 50 ~ 90 DEG C, reacts 1～5 hour；Products therefrom, respectively with oxolane and acetone as washing liquid, through surname extraction 10 ~ 48 hours, vacuum drying, i.e. obtains required product.
A kind of method utilizing High Internal Phase Emulsion masterplate method to prepare the glycosyl modified porous adsorbing material in surface the most according to claim 1, it is characterized in that described solvent orange 2 A is oxolane, N, dinethylformamide, N, one or more in N-diethylformamide or N,N-dimethylacetamide.
A kind of method utilizing High Internal Phase Emulsion masterplate method to prepare the glycosyl modified porous adsorbing material in surface the most according to claim 1, is characterized in that described catalyst B is one or more in Cu-lyt ./bipyridyl, cuprous bromide/bipyridyl, Cu-lyt ./pentamethyl-diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, Cu-lyt ./hexamethyl trien or cuprous bromide/hexamethyl trien.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106552606A (en) * | 2016-12-02 | 2017-04-05 | 华东理工大学 | A kind of method that porous ion-exchange resin is prepared based on click chemistry reaction |
| CN106905533A (en) * | 2017-02-24 | 2017-06-30 | 同济大学 | A kind of method that utilization High Internal Phase Emulsion masterplate method prepares the porous adsorbing material of surface beta cyclodextrin modification |
Citations (2)
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| CN1858074A (en) * | 2006-04-17 | 2006-11-08 | 江南大学 | Process for preparing surface functional crosslinking polystyrene micro ball |
| CN102516435A (en) * | 2011-11-21 | 2012-06-27 | 浙江大学 | Method for preparing porous material by reversible addition fragmentation chain transfer polymerization of high internal phase emulsion |
-
2016
- 2016-04-21 CN CN201610249463.0A patent/CN105885082A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858074A (en) * | 2006-04-17 | 2006-11-08 | 江南大学 | Process for preparing surface functional crosslinking polystyrene micro ball |
| CN102516435A (en) * | 2011-11-21 | 2012-06-27 | 浙江大学 | Method for preparing porous material by reversible addition fragmentation chain transfer polymerization of high internal phase emulsion |
Non-Patent Citations (2)
| Title |
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| FABRICE AUDOUIN ET AL.: "Protein Immobilization onto Poly(acrylic acid) Functional Macroporous PolyHIPE Obtained by Surface-Initiated ARGET ATRP", 《BIOMACROMOLECULES》 * |
| RAVIN NARAIN ET AL.: "Synthesis and Aqueous Solution Properties of Novel Sugar Methacrylate-Based Homopolymers and Block Copolymers", 《BIOMACROMOLECULES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106552606A (en) * | 2016-12-02 | 2017-04-05 | 华东理工大学 | A kind of method that porous ion-exchange resin is prepared based on click chemistry reaction |
| CN106552606B (en) * | 2016-12-02 | 2019-01-11 | 华东理工大学 | A method of porous ion-exchange resin is prepared based on click chemistry reaction |
| CN106905533A (en) * | 2017-02-24 | 2017-06-30 | 同济大学 | A kind of method that utilization High Internal Phase Emulsion masterplate method prepares the porous adsorbing material of surface beta cyclodextrin modification |
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