CN104628958B - The hydrophilic modification method and material of polystyrene type or its copolymer material - Google Patents
The hydrophilic modification method and material of polystyrene type or its copolymer material Download PDFInfo
- Publication number
- CN104628958B CN104628958B CN201510061795.1A CN201510061795A CN104628958B CN 104628958 B CN104628958 B CN 104628958B CN 201510061795 A CN201510061795 A CN 201510061795A CN 104628958 B CN104628958 B CN 104628958B
- Authority
- CN
- China
- Prior art keywords
- polystyrene type
- hydrophilic
- copolymer material
- copolymer
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of polystyrene type or the hydrophilic modification methods and material of its copolymer material, including：1) by polystyrene type or its copolymer material, swelling treatment is carried out with organic solvent；2) under solvent existence condition, hydrophilic monomer is polymerize by the method initiation grafting of atom transfer radical polymerization to step 1) treated material surface, that is, completes the hydrophilic modifying to polystyrene type or its copolymer material.This method is easy to operate, reaction condition is mild, and obtained hydrophiling material settling out, coating is not easily to fall off, inhibits non-specific adsorption of the polymer microballoon to albumen well.Polystyrene type microballoon after hydrophilic modifying, hydrophilic layer can have prodigious application prospect directly or through other various functional groups are further derived as in biotechnology especially bio-chemistry separation field.
Description
Technical field
The present invention relates to polymer materials to be modified field more particularly to a kind of method of surface of polymer material hydrophily
And material obtained by this method, the especially surface hydrophilicity to super big hole polystyrene material.
Background technology
Polymer microballoon the advantage is that high mechanical strength, chemical property stabilization, acid-alkali-resistant degree as bio-chemistry separation medium
It is good, it can operate under high pressure, therefore have good foreground in the application field as chromatographic media.But polymer itself
Some features limit its application in terms of separation of biopolymer, as vinyl benzyl chloride and divinylbenzene are copolymerized (PCMS-
DVB) microballoon, microsphere surface carry a large amount of benzyl chloride group, are easy to be derived as various functions group, but since its surface has
Hydrophobicity, therefore be easy that hydrophobic effect occurs and the Irreversible Adsorption of albumen is caused even to be denaturalized between protein molecular.
Research shows that this hydrophobic effect is to cause albumen the main reason for non-specific adsorption occurs for material surface
(Journal of Colloid and Interface Science,1989,132:176-187) this way, is solved the problems, such as
One of diameter exactly increases the hydrophily of material surface.As CN103709274A discloses a kind of modified surface gathering containing Active Chlorine
The method of styrenic material, this method be by hydrophilic small molecules by occurring substitution reaction with the Active Chlorine of material surface
It is linked to material surface, to which material surface obtains certain hydrophily, but using Active Chlorine substitution reaction is occurring for this method
While, other side reactions are easily caused, the cross-linking reaction of material internal group is caused, destroy original aperture structure of microballoon.
In addition, we also once had studied the hydrophilic modifying (ZL 201210091582.X) of the material surface of polyacrylate, it will be hydrophilic
Property polysaccharide molecule is bonded to Polyacrylate materials surface by way of chemical coupling, certain to assign the material surface
Hydrophily, material surface after hydrophiling has abundant hydroxyl group, it is full can be further derived as various functions group
Sufficient bio-chemistry separation is for the needs of different clastotypes, but there is also certain limitations for this method, and mainly directly coupling is big
The hydrophilic polysaccharide molecule of molecular weight reacts steric hindrance, to be difficult to the uniform fold of hydrophilic coating due to existing.
Invention content
Based on the above existing technology problems, the present invention provides a kind of polystyrene type or its copolymer material
Hydrophilic modification method and material, modified side reaction is small, and the hydrophilic layer covering of modified material surface is uniform, solves because of hydrophily not
Good the problem of causing non-specific adsorption of the polystyrene material to albumen.
In order to solve the above technical problems, present invention offer is a kind of to carry out parent to polystyrene type or its copolymer material surface
The method that water is modified, includes the following steps：
1) by polystyrene type or its copolymer material, swelling treatment is carried out with organic solvent；
2) under solvent existence condition, hydrophilic monomer is gathered by the method initiation grafting of atom transfer radical polymerization
It is bonded to the step 1) treated material surface, that is, completes the hydrophilic modifying to polystyrene type or its copolymer material.
The above method further includes after step 2)：
3) under alkaline matter existence condition, the hydrophily for the material surface for being obtained the step 2) with derivative reagent is gathered
It closes object long-chain and carries out derivation function, obtain the polystyrene type or its copolymer material of functionalization.
In above method step 1), it is as follows to carry out swelling treatment process with organic solvent：By polystyrene type or its copolymerization
Object material, which is put into organic solvent, is sealed 2~5h of oscillation, and the organic solvent is that can carry out miscible organic solvent with water,
The volumetric usage of organic solvent is to wait for that the polystyrene type or its copolymer material exist by 10~20 times of swollen material quality
It in solvent after complete swelling, is filtered, organic solvent used is used in combination to be washed, filter clean solvent.
In the above method, polystyrene type or its copolymer material are：Polyvinyl benzyl chloride and divinyl benzene copolymer
Material or polyvinyl benzyl chloride material；
The organic solvent is selected from：One kind in dioxane, methanol, dimethyl sulfoxide (DMSO), dimethylformamide.
In above method step 2), the method initiation grafting that hydrophilic monomer is passed through into atom transfer radical polymerization
It polymerize to the process of the step 1) treated material surface and is：By hydrophilic monomer, catalyst and ligand system and described
The polystyrene type or its copolymer material that step 1) was swollen are put into reaction kettle, are thoroughly mixed in a solvent,
The reaction 12~for 24 hours at 30~60 DEG C, removes unreacted substance to get to surface grafting hydrophilic monomer after reaction
Polystyrene type or its copolymer material.
In above method step 2), hydrophilic monomer used is selected from：Sodium methacrylate (MANa), sodium acrylate
(ANa), hydroxyethyl methacrylate (HEMA), hydroxy propyl methacrylate (HPMA), methylacryoyloxyethyl trimethyl chlorine
Change the mixture of one or both of ammonium (DMC)；The hydrophilic monomer is polystyrene type or copolymer by quality dosage
1/3~3 times of quality of materials；
Solvent used is selected from：Butanone mixes with propyl alcohol, H2O, the mixture of one or both of DMSO；The solvent
Volumetric usage and the ratio of the step 1) treated quality of materials be 10：1~30：1(v/m)；
Catalyst and ligand system used is grouped as by two kinds of groups, respectively halide and containing n-donor ligand, wherein halogenation
Object is selected from：One or both of stannous chloride, cuprous bromide mixture；Containing n-donor ligand is selected from：2,2- bipyridines (Bpy),
Tetramethylethylenediamine (TMEDA), N, N, N, ' N, " N, " '-five methyl diethylentriamine (PMDETA) and 1, Isosorbide-5-Nitrae, 7,10,
One or more mixtures in 10 '-hexamethyl triens (HMETETA).
The halide of the catalyst and ligand system is as atom transfer radical polymerization initiator used, the halogenation
Object additional proportion is the 1~10% of the hydrophilic monomer molal quantity, and the molar ratio of the halide and the containing n-donor ligand is
1：1；
The graft polymerization reaction temperature is 30~80 DEG C, and the reaction time is 2~12h, and after graft reaction, decompression is taken out
Filter is used in combination deionized water to carry out washing and removes other soluble impurities.
In above method step 3), the hydrophilic polymer of the material surface obtained the step 2) with derivative reagent is long
Chain carry out derivation function process be：Derivative reagent, under alkaline condition, 20 is added in the material obtained to the step 2)
After reacting 3~10h at~50 DEG C, derivative products are washed, dry, obtain functional polystyrene class or its copolymer material.
In above method step 3), with derivative reagent by the hydrophilic polymer of the obtained material surface of the step 2)
Long-chain carries out derivation function：Function derivative is carried out to modified material of the grafting post-consumer polymer chain with hydroxyl；
Alkaline matter used is sodium hydroxide, one kind in dimethyl aminopyridine, alkaline matter a concentration of 1~
7mol/L；
Derivative reagent used is 2- lignocaine chloroethanes hydrochlorides or 2, and 3- epoxypropyltrimethylchloride chlorides are derivative
Reagent dosage is 2~10 times of step 2) the resulting materials quality.
The embodiment of the present invention also provides a kind of polystyrene type or the hydrophilic modifying material of its copolymer material, the material are
One layer of polymer long-chain for being rich in hydrophilic radical of chemical graft, shape in polystyrene type or its copolymer material surface and duct
At the hydrophilic modifying material that can be used as bio-chemistry separation medium directly or after derivative.
In above-mentioned material, polystyrene type or its copolymer material are：Polyvinyl benzyl chloride and divinyl benzene copolymer
Material or polyvinyl benzyl chloride material.
The present invention technique effect be：This method can uniformly be graft-polymerized one layer on polystyrene material surface
The hydrophilic layer covering of hydrophilic polymer long-chain molecule, modified material surface is uniform, and hydrophily greatly improves, can be notable
The non-specific adsorption amount to albumen is reduced, modified material directly or after derivative can be used as bio-chemistry separation medium.This method
The surface that can be applied to most polymers material is modified, and is not especially influencing aperture structure, poly- to super big hole
It closes object microballoon and carries out hydrophilic modifying, the polymer microballoon after hydrophilic modifying can be applied to biotechnology and chromatographic isolation field.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, other are can also be obtained according to these attached drawings
Attached drawing.
Fig. 1 is the hydrophiling PCMS-DVB microballoon schematic diagrames that the embodiment of the present invention one provides；
Fig. 2 be the gained of the embodiment of the present invention two polymer microballoon before modified after electronics surface sweeping microscope photo, wherein
A1 and A2 is microballoon before modified；B1 and B2 is modified microballoon；
Fig. 3 is the adsorbance measurement chart to albumen of the modified post-polymerization object microballoon obtained by the embodiment of the present invention, wherein ●
Represent chromatographic peak areas of the BSA without absorption when；■ represents chromatographic peak areas of the BSA after hydrophiling microballoon.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiment of the present invention, ordinary skill
The every other embodiment that personnel are obtained without making creative work, belongs to protection scope of the present invention.
The embodiment of the present invention provides a kind of polystyrene type or the hydrophilic modification method of its copolymer material, is to polyphenyl second
The method that alkenes or its copolymer material surface carry out hydrophilic modifying, can by hydrophilic vinyl monomer by atom transfer from
By base polymerization material table is covered in obtain hydrophilic polymer long-chain in material surface initiation grafting polymerisation
Face and channel surfaces, improve the non-specific adsorption that the hydrophily of material surface considerably reduces material to albumen, and by
There is abundant functional group in the side chain of polymer, can further be derivatized to various functions group, can be applied to biological big point
Son isolates and purifies.It can after method through the invention, polystyrene type or its copolymer microsphere material surface hydrophilic modifying
Albumen is effectively reduced in the non-specific adsorption on its surface, has the side of very high value through the invention in biologic applications field
Method after hydrophilic modifying, can continue to keep original macroporous structure, can be resistant to higher to super big hole PCMS-DVB microballoons
Pressure operation, while hydrophilic surface can further derive, and the bio-chemistry separation that may be used as under various clastotypes is used
Medium, therefore have good application prospect and advantage in bio-chemistry separation purification art.This method comprises the following steps：
Polystyrene type or its copolymer material are carried out swelling treatment by step 1) with organic solvent；
Step 2) is connect hydrophilic monomer molecule using atom transfer radical polymerization method under solvent existence condition
Branch is aggregated to the material surface that step 1) is handled well；
Step 3), the grafted polymer inside the material surface that step 2) is obtained and duct carry out derivation function.
In the above method, polystyrene material can be Polystyrene product, derivative products or graft copolymer
Equal materials.
Preferably, the swelling treatment process described in above method step 1) is as follows：By polystyrene type or its copolymer
Material, which is put into organic solvent, is sealed 2~5h of oscillation, waits for that polystyrene type or its copolymer material are completely molten in a solvent
It after swollen, is filtered, solvent used is used in combination to be washed, filter clean solvent.
Preferably, the organic solvent described in above method step 1) is selected from dioxane, methanol, dimethyl sulfoxide (DMSO), two
One or several kinds in methylformamide.Swelling solvent used in the present invention be not limited to it is above several, it is all can with water into
Other miscible polar organic solvents of row.The volumetric usage of organic solvent be preferably it is described by the 10 of swollen material quality~
20 times.That is microspheres quality：Solvent volume=1:10~20 (g/mL).
Swelling pretreatment step is important not omissible program in preparation process, and fully the microballoon after swelling is advantageous
In diffusing into inside microballoon completely for hydrophilic substance, conducive to the surface that the material that is modified is completely covered of hydrophilic substance.
Preferably, the graft polymerization described in above method step 2) is：Graft polymerization described in step 2)
Cheng Wei：Hydrophilic monomer molecule, catalyst and ligand system, the polystyrene type being swollen or its copolymer material are put into instead
Answer in kettle, be thoroughly mixed in a solvent, at 30~60 DEG C react 12~for 24 hours, remove unreacted after reaction
Substance, obtain the material of surface grafting hydrophilic substance.
Preferably, unreacting substance is removed in step 2) after reaction, program includes being filtered under diminished pressure, and filtering is same
When washed with deionized water.
Preferably, in above method step 2), after graft polymerization reaction, the washing of modified product, drying process
It is as follows：Decompression, which filters, to be simultaneously washed with water three times, is removed unreacted substance, is then dried in vacuo for 24 hours at 60 DEG C.In terms of mass method
The amount of the graft polymerization of every gram of microballoon is calculated, calculation formula is as follows：
Preferably, the derivation function process described in above method step 3) is：Add into the material obtained by step 2)
Enter derivative reagent, under alkaline condition, after reacting 3~10h at 20~50 DEG C, derivative products are washed, dry, obtain functionalization
Material.
Preferably, in the above method, polystyrene type or its copolymer material be cross-linking polyethylene benzyl chloride microballoon or
Plank or polyvinyl benzyl chloride and divinylbenzene copolymerization microsphere or plank.
Preferably, in above method step 2), hydrophilic monomer is selected from：Sodium methacrylate (MANa), sodium acrylate
(ANa), hydroxyethyl methacrylate (HEMA), hydroxy propyl methacrylate (HPMA), methylacryoyloxyethyl trimethyl chlorine
Change one or both of ammonium (DMC) mixture；Its further preferred quality dosage is polystyrene type or copolymer material matter
1/3~3 times of amount.
Preferably, solvent used in above method step 2) is selected from H2O, one in DMSO, butanone and propanol mixture
Kind or two kinds of mixtures, the ratio for the quality of materials that the volumetric usage of preferred solvent is handled well with step 1) is 10:1~30:1(v/
m)。
Preferably, the catalyst system in atom transfer radical polymerization method used in above method step 2) is by two
Kind group is grouped as, and respectively includes halide and containing n-donor ligand；Halide is selected from：One kind in stannous chloride, cuprous bromide or two
Kind mixture；Containing n-donor ligand includes：2,2- bipyridines (Bpy), tetramethylethylenediamine (TMEDA), N, N, N, ' N, " N, " '-five
Methyl diethylenetriamines (PMDETA) and 1, Isosorbide-5-Nitrae, one kind in 7,10,10 '-hexamethyl triens (HMETETA)
Or a variety of mixture；
In step 2), halide (such as stannous chloride, cuprous bromide) in atom transfer radical polymerization initiator plus
Enter 1~10% that ratio is the hydrophilic monomer molal quantity, and the halide (such as stannous chloride, cuprous bromide) and nitrogenous
The molar ratio of ligand is 1:1.
In step 2), graft polymerization reaction temperature is 30~80 DEG C, and the reaction time is 2~12h, after graft reaction,
Decompression filters, and is used in combination deionized water to be washed, removes other soluble impurities.
Preferably, the derivation function in above method step 3), mainly for grafting post-consumer polymer chain with hydroxyl
Modified material, the still more preferably modified material for graft polymerization hydroxyethyl methacrylate, alkaline matter used are hydrogen
One kind in sodium oxide molybdena (NaOH), dimethyl aminopyridine (DMAP), depending on the functional group different according to derivative, preferably its is dense
Spend ranging from 1~7mol/L；Derivative reagent used is 2- lignocaine chloroethanes hydrochlorides (DEAE) or 2,3- glycidyl
Trimethyl ammonium chloride (DTA), dosage are 2~10 times of step 2) resulting materials quality；
Preferably, solvent used in above-mentioned alkaline substance solution is H2O or H2O and DMSO (10:2, volume ratio) it is mixed
Close object, volumetric usage 10:1~30:The ratio of 1 (v/m), i.e. solvent volume and the quality of step 2) resulting materials；
Preferably, above-mentioned steps 3) in derivation functionization reaction temperature used be 30~70 DEG C, the reaction time is 2~
12h, after completion of the reaction, decompression filter gained functionalization material, and H is used in combination2O or DMSO are washed.
The embodiment of the present invention also provides a kind of polystyrene type of the hydrophilic modifying obtained by the above method or it is total
Polymer material, one layer of the material surface and microballoon inner surfaces of pores chemical coupling are poly- rich in hydroxyl or electrically charged hydrophily
Close object, the material can be directly used for or further it is modified be used for bio-chemistry separation.
Wherein, hydrophilic modifying polystyrene type or its copolymer material are preferably：The polyvinyl benzyl chloride material of hydrophilic modifying
Material or polyvinyl benzyl chloride and divinyl benzene copolymer material.
Examine after hydrophilic modifying microballoon to the inhibition of albumen non-specific adsorption by following manner, it will be modified micro-
Ball is packed into stainless steel gc column tube, and column tube specification is 4.6 × 50mm of φ, and the chromatographic column filled is connected to efficient liquid phase
Non-specific adsorption of the microballoon to protein B SA is tested in chromatography, specific experiment method is shown in embodiment part.The result shows that its BSA
Non-specific adsorption amount is close to 0.
The method of the hydrophilic modifying material surface of the present invention is that hydrophilic vinylic monomer is graft-polymerized to the material that is modified
The surface of material is modified especially for the surface of super big hole polystyrene type microballoon.
The method of the present invention on polystyrene material surface by can uniformly be graft-polymerized one layer of hydrophilic polymer
The hydrophily of object long-chain molecule, modified material surface greatly improves, and can significantly reduce the non-specific adsorption to albumen
Amount.And it is easy to operate, reaction condition is mild, obtained hydrophiling material settling out, coating is not easily to fall off.This method can be applied to
The surface of most polymers material is modified, especially super large pore polymer microsphere (such as polystyrene type microballoon), hydrophilic modifying
Inhibit non-specific adsorption of the polymer microballoon to albumen well afterwards, the polymer microballoon after hydrophilic modifying can directly or
Person is applied to biotechnology and chromatographic isolation field after being further derived as other various functional groups.
The method and material of the present invention are described further with reference to specific embodiment.
Embodiment one
1) super big hole PCMS-DVB microballoons pre-process in dioxane：
It accurately weighs PCMS-DVB microballoons 1.0g to be put into the conical flask of 50mL, dioxane 10mL is then added,
After vibrating 2h at room temperature in 120rpm oscillation shaking tables, is filtered, be used in combination the dioxane of same volume to be washed, after washing
Solvent is filtered to microsphere surface without apparent solvent.
2) PCMS-DVB microsphere surfaces graft polymerization Sodium methacrylate (MANa)：
It weighs 0.3g MANa (2.8mmol) to be put into 50mL there-necked flasks, 10mL H is then added thereto2O is as molten
The microballoon after step 1) swelling treatment in embodiment one is added to homogeneous solution is formed in agent, 120rpm mechanical agitations；Then it is added
Catalyst 0.03g CuCl (0.3mmol) and 0.05g Bpy (0.3mmol) ligand keep 30 DEG C of temperature, keep at this temperature
React 4h, after reaction while hot, decompression suction filtration carried out with G4 sand core funnels, at the same with 500mL deionized waters washed to
Microballoon is colourless.Microsphere surface and channel surfaces have sodium polymethacrylate long-chain molecule after grafting, due to the polymer lateral chain
With a large amount of-COO-Na+Group, therefore it can be directly used as cation exchange resin, the life being applied under ion exchange mode
Change separation, be not necessarily to subsequent derivation function group, poidometer calculates modified microballoon obtained above, and the grafting amount of PMANa is
102mg/g.Its non-specific adsorption amount is close to 0.The hydrophilic modification process signal of PCMS-DVB microballoons is as shown in Figure 1.
Embodiment two：
1) super big hole PCMS-DVB microballoons pre-process in DMSO：
It accurately weighs PCMS-DVB microballoons 1.0g to be put into the conical flask of 50mL, DMSO 20mL is then added, 120rpm shakes
Swing after vibrating 5h at room temperature in shaking table, filtered, the DMSO of same volume is used in combination to be washed, after washing by solvent filter to
Microsphere surface is without apparent solvent.
2) PCMS-DVB microsphere surfaces graft polymerization sodium acrylate (ANa)：
It weighs 3.0g ANa (31.9mmol) to be put into 50mL there-necked flasks, 30mL H is then added thereto2O is as molten
The microballoon after step 1) swelling treatment in embodiment two is added to homogeneous solution is formed in agent, 120rpm mechanical agitations；Then it is added
Catalyst 0.3g CuCl (3.2mmol) and 0.4g Bpy (3.2mmol) ligand increase temperature to 40 DEG C, keep at this temperature
React 2h, after reaction while hot, decompression suction filtration carried out with G4 sand core funnels, at the same with 500mL deionized waters washed to
Microballoon is colourless.Microsphere surface and channel surfaces have sodium polymethacrylate long-chain molecule after grafting, due to the polymer lateral chain
With a large amount of-COO-Na+Group, therefore it can be directly used as cation exchange resin, the life being applied under ion exchange mode
Change separation, be not necessarily to subsequent derivation function group, poidometer calculates modified microballoon obtained above, and the grafting amount of PANa is
240mg/g.Its non-specific adsorption amount is close to 0.Super big hole PCMS-DVB microballoons such as Fig. 2 institutes of the present embodiment hydrophilic modifying
Show, as can be seen that the super big hole of microsphere surface still remains after before modified from figure, maintains the good permeability of microballoon.
Embodiment three：
1) super big hole PCMS-DVB microballoons pre-process in DMF：
It accurately weighs PCMS-DVB microballoons 1.0g to be put into the conical flask of 50mL, DMF 15mL is then added, 120rpm shakes
Swing after vibrating 4h at room temperature in shaking table, filtered, the DMF of same volume is used in combination to be washed, after washing by solvent filter to
Microsphere surface is without apparent solvent.
2) PCMS-DVB microsphere surfaces graft polymerization hydroxyethyl methacrylate (HEMA)：
It weighs 2.0g HEMA (15.4mmol) to be put into 100mL there-necked flasks, 40mL butanone and positive third is then added thereto
The mixed solvent (by volume 3/7) of alcohol composition is used as solvent, 120rpm mechanical agitations that embodiment is added to homogeneous solution is formed
Microballoon in three after step 1) swelling treatment；Then catalyst 0.02g CuBr (0.2mmol) and 0.03g PMDETA are added
(0.2mmol) ligand increases temperature to 70 DEG C, reaction 2h is kept at this temperature, after reaction while hot, with G4 sand core funnels
Decompression suction filtration is carried out, while being washed with 500mL deionized waters colourless to microballoon.Microsphere surface and channel surfaces tool after grafting
There is poly hydroxy ethyl acrylate long-chain (PHEMA) molecule, since the polymer lateral chain carries a large amount of-OH groups, system
There is the microballoon obtained preferable hydrophily, poidometer to calculate modified microballoon obtained above, and the grafting amount of PHEMA is 201mg/g.
3) PCMS-DVB-PHEMA microballoons after derivation function graft modification：
It weighs 2.4g DEAE to be put into 50mL there-necked flasks, the NaOH aqueous solutions of 12mL 1.0mol, 120rpm is then added
Stirring is added the microballoon obtained by three step 2) of embodiment, reacts 2h at 30 DEG C after forming homogeneous solution, and reaction finishes, and uses
G4 sand core funnels carry out decompression suction filtration, and deionized water and ethyl alcohol is used in combination, and successively washing three times, removes unreacted substance.Washing is dry
Microballoon after net, constant weight is dried under vacuum at 50 DEG C.Microsphere surface and channel surfaces after derivation function carry weak anionic
Cation exchange groups-DEAE, may be used as weak anion exchange resin, be applied in bio-chemistry separation.Its non-specific adsorption amount is close
In 0.
Example IV：
1) super big hole PCMS-DVB microballoons pre-process in methyl alcohol：
It accurately weighs PCMS-DVB microballoons 1.0g to be put into the conical flask of 50mL, then addition methanol 20mL, 120rpm shake
Swing after vibrating 5h at room temperature in shaking table, filtered, the methanol of same volume is used in combination to be washed, after washing by solvent filter to
Microsphere surface is without apparent solvent.
2) PCMS-DVB microsphere surfaces graft polymerization hydroxyethyl methacrylate (HPMA)：
It weighs 3.0g HPMA (20.8mmol) to be put into 100mL there-necked flasks, 45mL H is then added thereto2O is as molten
The microballoon after step 1) swelling treatment in example IV is added to homogeneous solution is formed in agent, 120rpm mechanical agitations；Then it is added
Catalyst 0.15g CuBr (1.04mmol) and 0.24g HMETETA (1.04mmol) ligand, raising temperature are warm herein to 80 DEG C
Degree is lower to keep reaction 10h, after reaction while hot, decompression suction filtration is carried out with G4 sand core funnels, at the same with 500mL deionized waters into
Row washing is colourless to microballoon.Microsphere surface and channel surfaces are with polyhydroxypropyl methaciylate long-chain (PHPMA) point after grafting
Son, since the polymer lateral chain carries a large amount of-OH groups, microballoon obtained has preferable hydrophily, calculating of weighing
The grafting amount of modified microballoon obtained above, PHEMA is 241mg/g.
3) PCMS-DVB-PHPMA microballoons after derivation function graft modification：
It weighs 12.4g DTA to be put into 100mL there-necked flasks, the DMAP DMSO/H of 37mL 7.0mol is then added2O is mixed
(DMSO/H in solution2O volume ratios 2:8), 120rpm stirrings are added after forming homogeneous solution obtained by example IV step 2)
Microballoon, react 12h at 70 DEG C, reaction finishes, and decompression suction filtration is carried out with G4 sand core funnels, and deionized water and ethyl alcohol is used in combination successively
Washing three times, removes unreacted substance.Microballoon after washes clean is dried under vacuum to constant weight at 50 DEG C.After derivation function
Microsphere surface and channel surfaces carry strong anion cation exchange groups (quaternary ammonium salt), may be used as strong anion exchange resin, answer
For in bio-chemistry separation.Its non-specific adsorption amount is close to 0.
Embodiment five：
1) super big hole PCMS-DVB microballoons pre-process in DMSO：
It accurately weighs PCMS-DVB microballoons 1.0g to be put into the conical flask of 50mL, DMSO 20mL is then added, 120rpm shakes
Swing after vibrating 3h at room temperature in shaking table, filtered, the DMSO of same volume is used in combination to be washed, after washing by solvent filter to
Microsphere surface is without apparent solvent.
2) PCMS-DVB microsphere surfaces graft polymerization MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC)：
It weighs 1.0g DMC (5.2mmol) to be put into 50mL there-necked flasks, 30mL H is then added thereto2O as solvent,
The microballoon after step 1) swelling treatment in embodiment five is added to homogeneous solution is formed in 120rpm mechanical agitations；Then it is added and urges
Agent 0.05g CuCl (0.52mmol) and 0.09g PMDETA (0.52mmol) ligand increase temperature to 50 DEG C, in this temperature
Lower holding reaction 12h carries out decompression suction filtration, while being carried out with 500mL deionized waters with G4 sand core funnels after reaction while hot
Washing is colourless to microballoon.Microsphere surface and channel surfaces have polymethyl acyloxyethyl trimethyl ammonium chloride long-chain after grafting
Molecule can be directly used as strong anion exchange resin since the polymer lateral chain carries a large amount of quaternary ammonium group, apply
Bio-chemistry separation under ion exchange mode is not necessarily to subsequent derivation function group, and poidometer calculates modified microballoon obtained above,
The grafting amount of its PDMC is 140mg/g.
Embodiment six：
Non-specific adsorption measures fixed
1) modified microballoon is loaded
The modified microballoons of 1.0g are put in 50% ethanol waters of 20mL, after ultrasonic disperse 30min, are put in packing column machine
Homogenizer in, with 10MPa pressure fill column, duration 1h, column tube specification be 4.6 × 50mm of φ.
2) non-specific adsorption of modified microballoon is tested with BSA
By in embodiment six, the chromatographic column that step 1) is loaded is connected on liquid chromatograph, and chromatographic condition is as follows：Sample
The BSA solution of concentration 2mg/mL；200 μ L of applied sample amount；Flow velocity 1mL/min；Mobile phase A 1mol NaCl pH=7.0,50mM phosphorus
Acid buffering solution, B 1M NaOH aqueous solutions；Gradient condition 0-10min A phases；10.01-20min B phases；20.01-30A phases；Weight
Multiple sample introduction 5 times, record goes out peak area A every time1；B replaces chromatographic column, same chromatographic process test with connector, and record goes out every time
Peak area A2；C calculates the adsorbances of BSA on a column, and formula is as follows：
QBSA：The quality (mg/mL) of every milliliter of microballoon BSA adsorption；
V：The volume (mL) of microballoon in chromatographic column.
Hydrophilic modifying microballoon obtained by above example one to five, test b SA non-specific adsorption amounts, with above-mentioned spy
The test method that anisotropic adsorbance measures, Fig. 3 is three test results of embodiment.
The present invention causes hydrophilic small molecules monomer in polyphenyl second using the method for atom transfer radical polymerization (ATRP)
Alkenes material surface and internal channel surfaces are graft-polymerized, and the small molecule monomer reaction steric hindrance that this method uses is small, can
It diffuses to inside the duct of porous material, is solved the problems, such as since uneven coating caused by macromolecular steric hindrance is even completely；Simultaneously
ATRP is a kind of activity/controllable polymerization mode, can effectively control the grafting chain length of material surface, it is not easy to plugging material hole
Road；It selects vinyl hydrophilic monomer range extensively while realizing hydrophiling material surface, partly carries the monomer of functional group
It can realize that hydrophiling and functionalization, modified material may be directly applied in bio-chemistry separation purification art simultaneously with a step,
Remove the two steps operation that the first hydrophiling of the needs in previous hydrophilic modification method carries out functionalization again from.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (9)
1. the hydrophilic modification method of a kind of polystyrene type or its copolymer material, which is characterized in that include the following steps：
1) by polystyrene type or its copolymer material, swelling treatment is carried out with organic solvent；It is described carried out with organic solvent it is molten
Swollen processing procedure is as follows：Polystyrene type or its copolymer material are put into organic solvent and are sealed oscillation 2~5h, it is described
Organic solvent is that miscible organic solvent can be carried out with water, and the volumetric usage of organic solvent is by the 10~20 of swollen material quality
Times, it after the polystyrene type or its copolymer material in a solvent complete swelling, is filtered, is used in combination used organic molten
Agent is washed, and clean solvent is filtered；
2) under solvent existence condition, by hydrophilic monomer by the method initiation grafting of atom transfer radical polymerization polymerize to
The step 1) treated material surface, that is, complete the hydrophilic modifying to polystyrene type or its copolymer material.
2. the hydrophilic modification method of polystyrene type according to claim 1 or its copolymer material, which is characterized in that
Further include after step 2)：
3) under alkaline matter existence condition, with the hydrophilic polymer for the material surface that derivative reagent obtains the step 2)
Long-chain carries out derivation function, obtains the polystyrene type or its copolymer material of functionalization.
3. the hydrophilic modification method of polystyrene type according to claim 2 or its copolymer material, which is characterized in that institute
It states polystyrene type or its copolymer material is：Polyvinyl benzyl chloride and divinyl benzene copolymer material or polyvinyl benzyl
Cl material；
The organic solvent is selected from：One kind in dioxane, methanol, dimethyl sulfoxide (DMSO), dimethylformamide.
4. the hydrophilic modification method of polystyrene type according to claim 1 or its copolymer material, which is characterized in that institute
It states in step 2), it is described to polymerize hydrophilic monomer to the step by the method initiation grafting of atom transfer radical polymerization
1) process of treated material surface is：Hydrophilic monomer, catalyst and ligand system and the step 1) were swollen
Polystyrene type or its copolymer material are put into reaction kettle, are thoroughly mixed in a solvent, anti-at 30~60 DEG C
Answer 12~for 24 hours, remove after reaction unreacted substance to get to the polystyrene type of surface grafting hydrophilic monomer or its
Copolymer material.
5. the hydrophilic modification method of polystyrene type according to claim 1 or 4 or its copolymer material, feature exist
In in the step 2), hydrophilic monomer used is selected from：Sodium methacrylate (MANa), sodium acrylate (ANa), methyl-prop
In olefin(e) acid hydroxyl ethyl ester (HEMA), hydroxy propyl methacrylate (HPMA), MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC)
One or two kinds of mixtures；The hydrophilic monomer is by 1/3 that quality dosage is polystyrene type or copolymer material quality
~3 times；
Solvent used is selected from：Butanone mixes with propyl alcohol, H2O, the mixture of one or both of DMSO；The body of the solvent
The ratio of product dosage and the step 1) treated quality of materials is 10：1~30：1(v/m)；
Catalyst and ligand system used is grouped as by two kinds of groups, respectively halide and containing n-donor ligand, wherein halide selects
From：One or both of stannous chloride, cuprous bromide mixture；Containing n-donor ligand is selected from：2,2- bipyridines (Bpy), tetramethyl
Base ethylenediamine (TMEDA), N, N, N, ' N, " N, " '-five methyl diethylentriamine (PMDETA) and 1, Isosorbide-5-Nitrae, 7,10,10 '-six
One or more mixtures in methyl trien (HMETETA).
The halide of the catalyst and ligand system adds as atom transfer radical polymerization initiator used, the halide
It is the 1~10% of the hydrophilic monomer molal quantity to enter ratio, and the molar ratio of the halide and the containing n-donor ligand is 1：1；
The graft polymerization reaction temperature is 30~80 DEG C, and the reaction time is 2~12h, and after graft reaction, decompression filters,
It is used in combination deionized water to carry out washing and removes other soluble impurities.
6. the hydrophilic modification method of polystyrene type according to claim 2 or its copolymer material, in the step 3),
The process that the hydrophilic polymer long-chain for the material surface that the step 2) obtains is carried out to derivation function with derivative reagent is：
Derivative reagent is added in the material obtained to the step 2), it is under alkaline condition, derivative after reacting 3~10h at 20~50 DEG C
Product is washed, dry, obtains functional polystyrene class or its copolymer material.
7. the hydrophilic modification method of the polystyrene type or its copolymer material according to claim 2 or 6, feature exist
In in the step 3), the hydrophilic polymer long-chain of the obtained material surface of the step 2) is carried out with derivative reagent
Derivation function is：Function derivative is carried out to modified material of the grafting post-consumer polymer chain with hydroxyl；
Alkaline matter used is one kind in sodium hydroxide, dimethyl aminopyridine, a concentration of 1~7mol/ of alkaline matter
L；
Derivative reagent used is 2- lignocaine chloroethanes hydrochlorides or 2,3- epoxypropyltrimethylchloride chlorides, derivative reagent
Dosage is 2~10 times of step 2) the resulting materials quality.
8. the parent of a kind of polystyrene type prepared using claim 1 to 7 any one of them method or its copolymer material
Water modified material, which is characterized in that the material is the chemical graft in polystyrene type or its copolymer material surface and duct
One layer of polymer long-chain for being rich in hydrophilic radical, formation can change directly or after derivative as the hydrophilic of bio-chemistry separation medium
Property material.
9. the hydrophilic modifying material of polystyrene type according to claim 8 or its copolymer material, which is characterized in that institute
It states polystyrene type or its copolymer material is：Polyvinyl benzyl chloride and divinyl benzene copolymer material or polyvinyl benzyl
Cl material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510061795.1A CN104628958B (en) | 2015-02-05 | 2015-02-05 | The hydrophilic modification method and material of polystyrene type or its copolymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510061795.1A CN104628958B (en) | 2015-02-05 | 2015-02-05 | The hydrophilic modification method and material of polystyrene type or its copolymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104628958A CN104628958A (en) | 2015-05-20 |
| CN104628958B true CN104628958B (en) | 2018-08-10 |
Family
ID=53208232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510061795.1A Active CN104628958B (en) | 2015-02-05 | 2015-02-05 | The hydrophilic modification method and material of polystyrene type or its copolymer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104628958B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589201B (en) * | 2015-10-15 | 2019-03-19 | 中国科学院过程工程研究所 | A kind of hydrophilic modification method of polystyrene material and products thereof |
| CN105233807A (en) * | 2015-10-21 | 2016-01-13 | 北京石油化工学院 | Method for preparing high-loading affinity chromatographic medium |
| CN107694358A (en) * | 2017-09-22 | 2018-02-16 | 同济大学 | A kind of preparation method of the anti-bacterial and anti-fouling dyeing polymer seperation film based on surface grafting |
| CN108276526B (en) * | 2018-01-26 | 2020-01-17 | 北京石油化工学院 | High-load large-aperture polymer cation exchange chromatography medium and preparation thereof |
| CN109499555A (en) * | 2018-12-06 | 2019-03-22 | 苏州楚博生物技术有限公司 | A method of preparing the macropore affinity chromatography medium of high ligand density |
| CN109837545A (en) * | 2018-12-14 | 2019-06-04 | 华东理工大学 | A kind of anti-rotten and antifouling capacity method in the ocean of NB-IOT information module encapsulation protection stainless steel substrates |
| CN112871147B (en) * | 2020-12-30 | 2023-07-14 | 北京石油化工学院 | Preparation method of chromatography medium for removing multimers in monoclonal antibodies |
| CN114054006A (en) * | 2021-11-17 | 2022-02-18 | 苏州纳微科技股份有限公司 | Oligo-dT affinity chromatography filler |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101810888A (en) * | 2010-03-16 | 2010-08-25 | 武汉理工大学 | Preparation method for material with high density fixed biologically functional molecule |
| CN103709274A (en) * | 2013-12-11 | 2014-04-09 | 中国科学院过程工程研究所 | Hydrophilic modification method of polystyrene material, and product thereof |
| CN103923263A (en) * | 2014-04-10 | 2014-07-16 | 中国石油大学(华东) | Preparation method of thermosensitive super-macroporous bio-separation medium with high flow velocity |
-
2015
- 2015-02-05 CN CN201510061795.1A patent/CN104628958B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101810888A (en) * | 2010-03-16 | 2010-08-25 | 武汉理工大学 | Preparation method for material with high density fixed biologically functional molecule |
| CN103709274A (en) * | 2013-12-11 | 2014-04-09 | 中国科学院过程工程研究所 | Hydrophilic modification method of polystyrene material, and product thereof |
| CN103923263A (en) * | 2014-04-10 | 2014-07-16 | 中国石油大学(华东) | Preparation method of thermosensitive super-macroporous bio-separation medium with high flow velocity |
Non-Patent Citations (2)
| Title |
|---|
| Preparation of poly (ethylene glycol) acrylate grafted polystyrene resin for solid-phase peptide synthesis;Rongyue Zhang等;《Reactive & Functional Polymers》;20120626;第72卷;第773-780页 * |
| 超大孔聚合物微球的亲水改性及在快速生化分离中的应用;张荣月等;《主题B高分子材料结构和性能》;20141016;第230-232页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104628958A (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104628958B (en) | The hydrophilic modification method and material of polystyrene type or its copolymer material | |
| JP5475284B2 (en) | Hydrophilic cross-linked polymer | |
| CA1255827A (en) | Polysaccharide supports | |
| EP0172579B1 (en) | Modified siliceous supports | |
| US20140263011A1 (en) | Novel chromatographic media based on allylamine and its derivative for protein purification | |
| Savina et al. | Ion‐exchange macroporous hydrophilic gel monolith with grafted polymer brushes | |
| US8092682B2 (en) | Matrix for separation of polyethers and method of separation | |
| JP2001506364A (en) | Preformed polymer coating method and product | |
| WO2018217137A1 (en) | A polymeric sorbent, preparation and use thereof | |
| US11364480B2 (en) | Chromatography medium with bound microglobules and method for the preparation thereof | |
| CN106268703A (en) | DNA immunization adsorbent and preparation method thereof | |
| US5168104A (en) | Macroporous particles as biocompatible chromatographic supports | |
| CN108276526A (en) | A kind of high carrying capacity large aperture polymer cation displacement chromatography medium and its preparation | |
| JP5280604B2 (en) | Post-modification of porous support | |
| KR20120031869A (en) | Process for making improved chromatography media and method of use | |
| JP2005510593A5 (en) | ||
| KR101333577B1 (en) | Process for making improved chromatography media and method of use | |
| Arrua et al. | Preparation of macroporous monoliths based on epoxy-bearing hydrophilic terpolymers and applied for affinity separations | |
| JPS6361618B2 (en) | ||
| CN108837812A (en) | A kind of method of swellable poly ion liquid absorption and recycling coloring agent | |
| CN113000039B (en) | Preparation method of chromatographic medium for removing endotoxin in biological nano-particles | |
| JPS61141719A (en) | Modified polypeptide supporter | |
| CN112871147B (en) | Preparation method of chromatography medium for removing multimers in monoclonal antibodies | |
| CN113209949B (en) | Ion exchange resin doped adsorbent capable of being thermally regenerated and preparation method thereof | |
| JPS6392627A (en) | Hydrophilic porous particle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211102 Address after: 102401 No. 86, Wanxing Road, Changyang, Fangshan District, Beijing n1184 Patentee after: Beijing bosaipu Biotechnology Co.,Ltd. Address before: 102600 Beijing Daxing District Huangcun Qingyuan Road No. 19 Patentee before: BEIJING INSTITUTE OF PETROCHEMICAL TECHNOLOGY |
|
| TR01 | Transfer of patent right |