CN103709274A - Hydrophilic modification method of polystyrene material, and product thereof - Google Patents
Hydrophilic modification method of polystyrene material, and product thereof Download PDFInfo
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Abstract
The invention discloses a hydrophilic modification method of a polystyrene material with the surface containing active chlorine, and a hydrophilic modification product thereof. The method comprises the following steps: 1, swelling the polystyrene material with the surface containing active chlorine by using an organic solvent; 2, carrying out a hydrophilic function group and the active chlorine on the surface of the polystyrene material in the presence of an alkaline substance to make the hydrophilic function group cross-linked to the surface of the material processed in step 1. The hydrophilic modification method has the advantages of simple operation, mild reaction condition, stable hydrophilic material, difficult shedding of a coating group, and great reduction of the hydrophobicity of the polystyrene skeleton. Additionally, the active chlorine on the surface of the polystyrene material can covalently graft different function groups through a substitution reaction to obtain a functional medium product suitable for different separation modes in order to satisfy the special needs of the biochemical separation field.
Description
Technical field
The present invention relates to polymer materials modification technology field, relate in particular to a kind of surface containing hydrophilic modification method and the product obtained by this method of the polystyrene type material of reactive chlorine.
Background technology
Polystyrene (PSt) class material has the advantages such as stable chemical nature, pH tolerance, pressure tolerance, is widely used in the separation and purification process of biochemical molecular.Yet the own characteristic of unmodified PSt material has seriously limited its Application Areas, for example PSt microballoon, can not be directly as chromatographic media isolated protein biomacromolecule except for reverse-phase chromatography.Its reason is that PSt microsphere surface lacks functional group, is difficult to the hydrophilic aglucon of direct coupling; In addition the strong hydrophobic interaction between PSt microsphere surface and protein molecule often can cause the even sex change of protein irreversible adsorption.Overcoming these problems need to carry out hydrophilic modifying to PSt microballoon, need to cover with hydrophilic radical its hydrophobic surface, and then on hydrophilic radical the specific aglucon of coupling to meet different clastotype requirements.How to address this problem become in recent years study hotspot of biochemical separation field (Journal of Chromatography A, 2009,1216:6511-6516).
At present, p-poly-phenyl vinyl microballoon carries out hydrophilic modification method and mainly contains three kinds:
(1) physical adsorption coating process.This method research is the most extensive, by directly adsorbing the hydrophilic polymer of one deck at microsphere surface, then with linking agent, adsorption layer is cross-linked to increase the stability of coating, microballoon specific surface energy is reduced, thereby reach the effect that reduces protein non-specific adsorption ability.
Different according to adsorption, physical adsorption hydrophilic layer mainly contains following three kinds of methods: a. electrostatic adsorption: make it electronegative microsphere surface sulfonation/carboxylation with chlorsulfonic acid/chromic acid, then utilize electrostatic force that large hydrophilic molecular is adsorbed onto to polystyrene type microsphere surface, coating is cross-linked and fixedly obtains Ion Exchange Medium; B. adsorb hydrophilic monomer repolymerization: the hydrophilic monomer that contains crosslinking kinetic energy based group is adsorbed onto to Surfaces of Polystyrene Microparticles, and then carries out polyreaction; C. hydrophobic interaction absorption: due to polystyrene type microballoon performance strong-hydrophobicity, can utilize hydrophobic interaction at microsphere surface absorption hydrophilic/hydrophobic amphipathic nature polyalcohol, PSt surface is pressed close to by the hydrophobic portion branch of polymkeric substance, hydrophilic segment abduction, thus realize hydrophilic modifying.But these methods all exist finally need to coating, be cross-linked again fixing, and coating hold caducous problem (Industrial & Engineering Chemistry Research, 2001,40:1624-1632).
(2) chemical coupling coating process.Compare physisorphtion, the report of chemical coupling method grafting hydrophilic macromolecule is less, and in existing document, more is the report of Surfaces of Polystyrene Microparticles grafting PEG.Chemical modification method carries out conventionally in two steps, and the phenyl ring that first will lack on surface functional group connects can be for the active small molecules group of functionalization (as-NH
2,-OH ,-COOH ,-CH
2cl etc.), further coupling hydrophilic macromolecule then, reaches the object (U.S.Pat.5466758,1995) of surface modification.But the factor that affects chemical plating is a lot, relate to the physico-chemical property of temperature, catalyzer, grafting agent type and consumption, type of solvent and consumption, blank microballoon as particle diameter, aperture, degree of crosslinking etc.High-crosslinking-degree PSt microballoon particularly, because be difficult to swelling and space steric effect, on phenyl ring, the position of substitution of Friedel-Crafts reaction only can carry out at microsphere surface, modify with further grafting and be difficult to be deep into microballoon inside, hydrophilic modifying (the Journal of Molecular Catalysis A:Chemical that has difficulties, 2013,370:56-63).
(3) functional nucleocapsid structure complex microsphere.Nucleocapsid structure polymeric particles is the polymer particle that a class has bilayer or multilayered structure, and the inside and outside enrichment heterogeneity respectively of particle, demonstrates special bilayer or multilayered structure, and core, shell have respectively different functions.The common feature of this class microballoon is to have hydrophobic polystyrene core and hydrophilic shell.The method of preparing polystyrene series nucleocapsid structure microballoon of bibliographical information is a lot, take seeding polymerization method as main.In addition, block and grafting parents multipolymer can form the character of stablizing nucleocapsid structure and also cause people's interest widely in the aqueous solution.In addition, the dispersion copolymerization that macromonomer participates in is the polymerization system that a kind of new development is got up, it has avoided the problem of conventional emulsion polymerization, the required emulsifying agent of dispersion polymerization or stablizer when preparing polymer microballoon, operate also relatively simply, simultaneously the molecular structure on polymer microballoon surface can design according to purposes.Therefore adopt in recent years macromonomer technology to prepare polymer microballoon and present the trend increasing year by year.In the dispersion copolymerization participating at macromonomer, the formation of polymer microballoon is proceed step by step: before reaction, monomer, macromonomer and initiator are dissolved in medium completely, along with the decomposition of initiator causes polymerization in homogeneous phase and generates a large amount of line style oligopolymer and graftomer; When these molecular chains reach after certain critical chain length, polymer chain coagulation from medium out forms micronucleus, and the grafted chain being formed by macromonomer is in the outside stabilization that rises of micronucleus; Monomer diffuses in micronucleus and carries out transfer reaction, finally obtain stable polymer microballoon (Polymer Bulletin, 2012,411:40-49).
For physical adsorption coating and chemical coupling coating, bibliographical information mainly concentrates on modifies PSt emulsion particle, atresia PSt microballoon and conventional PSt porous microsphere.What physics coating or chemical plating were used is all superpolymer, being carried out to coating modification, conventional porous PSt microballoon also there is following problem: 1) because aperture is little, it is inner that large hydrophilic molecular is difficult to enter microballoon duct, at PSt microsphere surface, has clustering phenomena; 2), because aperture is little, large hydrophilic molecular can exist and stop up duct phenomenon, and PSt microballoon aperture is obviously diminished.For functional nucleocapsid structure complex microsphere, because method restriction also cannot modified porous PSt microballoon.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of the invention is to propose a kind of hydrophilic modification method of showing polystyrene type material, polystyrene type material for surface containing reactive chlorine, wetting ability functional group is linked to its surface by the reactive chlorine on substituted polystyrene class material surface; Polystyrene type material hydrophobicity after hydrophilic modifying reduces greatly, and can keep original structure, can tolerate higher pressure operation and extreme acid or alkali environment, hydrophilic surface can further derive simultaneously, can be used as the biochemistry separation medium under multiple clastotype, in biochemical separation and purification field, have good application prospect and advantage.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of effects on surface and containing the polystyrene type material of reactive chlorine, carries out the method for hydrophilic modifying, it is characterized in that, comprising:
(1) the polystyrene type material that surface is contained to reactive chlorine carries out swelling treatment with organic solvent;
(2), under alkaline matter existence condition, wetting ability functional group is linked to by the reactive chlorine generation substitution reaction with described polystyrene type material surface the material surface that step (1) gained is handled well.
As preferably, the described surface of step (1) is prepared and is obtained by copolymerization by styrene monomer and the styrene monomer containing chloro alkyl containing the polystyrene type material of reactive chlorine;
Further preferably, described styrene monomer is selected from the styrene monomer containing olefin functionalities; Still more preferably, described styrene monomer is any one or a few in vinylbenzene, vinyl toluene, ethyl styrene or Vinylstyrene;
Further preferably, the described styrene monomer containing chloro alkyl is any one or a few in p-chloromethyl styrene, a 1-chloro-4-methyl-benzene or trichlorine ethyl styrene;
Further preferably, the mass ratio of described styrene monomer and the described styrene monomer containing chloro alkyl is (1:100)～(100:1), more preferably (50:100)～(100:50).
As preferably, the described organic solvent of step (1) be for carrying out miscible polar organic solvent with water, more preferably any one or a few in dioxane, ethanol, dimethyl sulfoxide (DMSO), dimethyl formamide, methylene dichloride, trichloromethane, dithiocarbonic anhydride, toluene or dimethyl formamide.
As preferably, by g/ml, the described surface of step (1) is 1:(1-100 containing the polystyrene type material of reactive chlorine and the mass volume ratio of described organic solvent), be preferably 1:(5-50), 1:(10-20 more preferably);
Preferably, the time of the described swelling of step (1) is 0.1-24 hour, 1-24 hour more preferably.
As preferably, the described alkaline matter of step (2) be in sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus any one or several, described alkaline matter preferably adopts the alkaline substance solution of 0.01-5mol/L;
Preferably, the mass ratio of described alkaline matter and described wetting ability functional group is (0.01-1): 1, more preferably (0.01-0.5): 1.
As preferably, the donor of the described wetting ability functional group of step (2) be in amino-contained compound or derivatives thereof, poly glycol monomethyl ether salt or polyethylene polyamine any one or multiple;
Further preferably, described amino-contained compound or derivatives thereof is Trimethylamine 99;
The poly glycol monomethyl ether salt that described poly glycol monomethyl ether salt is various molecular weight, more preferably poly glycol monomethyl ether sodium salt;
Further preferably, described polyethylene polyamine is tetraethylene pentamine, triethylene tetramine or diethylenetriamine;
In step (2), by g/ml, the material that step (1) gained is handled well and the mass volume ratio of described wetting ability functional group donor are preferably 1:(1-100), 1:(1-50 more preferably);
In step (2), described crosslinked temperature is preferably 0～200 ℃, more preferably 30～80 ℃, most preferably is 50～80 ℃;
In step (2), described cross-linking reaction time is preferably 1～48 hour, more preferably 5～24 hours, most preferably be 5～18 hours.
Above-mentioned hydrophilic modification method, not restriction of structure for described surface containing the polystyrene type material of reactive chlorine, the microballoon of the various structures such as, micropore solid such as thinking, aperture, macropore, oversized hole, hollow, depression, and the controlled microballoon of preparation size homogeneous such as binding film emulsifying technology, fast film emulsifying technology, seed swelling polymerization technology, microflow control technique; Also can be other structures such as film.
In addition, described method of modifying is also applicable to take the material that polystyrene is matrix.
Also not restriction of preparation method for described surface containing the polystyrene type material of reactive chlorine, can be in conjunction with the preparation method of existing polymer microballoon.
Second aspect, the invention provides a kind of preparation method of polystyrene type material of hydrophilic modifying, and the method comprises the following steps:
(1 ') contains styrene monomer and the styrene monomer copolymerization preparation surface containing chloro alkyl the polystyrene type material of reactive chlorine;
(2 ') obtains step (1 ') gained surface containing hydrophilic modification method modification described in the polystyrene type materials'use first aspect of reactive chlorine.
As preferably, in step (1 '), described styrene monomer is selected from the styrene monomer containing olefin functionalities; Further preferably, described styrene monomer is any one or a few in vinylbenzene, vinyl toluene, ethyl styrene or Vinylstyrene;
As preferably, in step (1 '), the described styrene monomer containing chloro alkyl is any one or a few in p-chloromethyl styrene, a 1-chloro-4-methyl-benzene or trichlorine ethyl styrene;
As preferably, in step (1 '), the mass ratio of described styrene monomer and the described styrene monomer containing chloro alkyl is 1:100～100:1,50:100～100:50 more preferably.
In embodiment, above-mentioned preparation method's step (1 ') specifically comprises the steps:
(i) using styrene monomer, mix and be dissolved in solvent as disperse phase containing chloro alkyl styrene monomer and additive; Described additive comprises initiator, optionally comprises any one or a few in linking agent, pore-creating agent or cosurfactant; Described " optionally comprising ", meaning can be added as required;
Preferably, described initiator is any one or a few in benzoyl peroxide, dilauroyl peroxide, peroxy dicarbonate ethylhexyl, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile);
Preferably, described linking agent is any one or a few in divinylbenzene monomer, vulcabond or N,N methylene bis acrylamide;
Preferably, described pore-creating agent is any one or a few the mixture in hydrophobic C4-C22 alkanes, C4-C22 alkane chain alcohols, saturated aromatics or linear styrene's oligopolymer;
Preferably, described cosurfactant is any one or a few in lauryl alcohol, hexanol or enanthol;
Preferably, described solvent is any one or a few the mixture in deionized water, gelatin, Mierocrystalline cellulose, hydroxy alkyl cellulose, polyvinylpyrrolidone, anhydrous sodium sulphate, sodium lauryl sulphate or sodium laurylsulfonate, and more preferably two kinds of solvents are with 1: 100-100: the mixed solvent that 1 volume ratio is mixed;
(ii) dispersion agent or emulsifying agent and optional stopper are mixed and be dissolved in deionized water as external phase;
Preferably, described dispersion agent and emulsifying agent are any one or a few in polyvinyl alcohol, gelatin, Mierocrystalline cellulose, hydroxy alkyl cellulose, polyvinylpyrrolidone, anhydrous sodium sulphate, sodium lauryl sulphate or sodium laurylsulfonate;
Preferably, described stopper is Resorcinol; Described stopper can add as required, and its effect is to prevent secondary nucleation;
By step (i) gained disperse phase be dispersed in step (ii) in gained external phase, form the oil/water type emulsion of homogeneous;
By step (iii) gained oil/water type emulsion move in the reactor with prolong, stirring rod, nitrogen conduit, after logical nitrogen replacement oxygen, at 30-150 ℃, preferably 50-120 ℃, more preferably polyreaction 1-48 hour, preferably 5-35 hour, more preferably 5-28 hour at 60-100 ℃, obtain polystyrene type microsphere suspension liquid;
To step (iv) gained polystyrene type microsphere suspension liquid carry out suction filtration or centrifugal, to the solid matter after suction filtration or centrifugal after throw out wash, dry, obtain surface containing the polystyrene type microballoon of reactive chlorine.
In embodiment, above-mentioned steps concrete operations are (v): use Büchner funnel suction filtration or centrifugation to obtain polystyrene type microballoon, with after deionized water and ethanol repetitive scrubbing microballoon, put into vacuum drying oven inner drying, make surface containing the polystyrene type microballoon of reactive chlorine.Thus obtained microsphere particle diameter is controlled at 0.1～1000 μ m, and aperture is controlled at 0～1000nm, and degree of crosslinking, 2%～80% controlled, is preferably more than 40%, and specific surface area is 20～1000m
2/ g, pore volume is 100～1000mm
3/ g; The forms such as that micro-sphere structure can be is solid, porous, macropore, hollow, simple eye or depression.
In embodiment, above-mentioned steps (1 ') thus obtained microsphere is put into organic solvent and seal vibration, until microballoon, in solvent, after complete swelling, carry out suction filtration, and wash with solvent used, the clean solvent of suction filtration; Then in the microballoon after swelling treatment, add wetting ability functional group, under alkaline condition, make the active chlorine atom of wetting ability functional group and microsphere surface carry out substitution reaction, reaction product, through washing, dry, obtains the polystyrene type microspheres product of described hydrophilic modifying.
The third aspect, the invention provides a kind of polystyrene type material of hydrophilic modifying, is made, or made by preparation method described in second aspect by the hydrophilic modification method described in first aspect.
Hydrophilic modification method of the present invention, easy and simple to handle, reaction conditions is gentle; Gained hydrophilization material settling out, coating group difficult drop-off, has greatly reduced the hydrophobicity of polystyrene skeleton.In addition, the reactive chlorine that polystyrene type material surface is rich in, can obtain being applicable to the function medium product of different clastotypes by the different functional group of substitution reaction covalence graft, to meet the special requirement of biochemical separation field.
Accompanying drawing explanation
Fig. 1 is the synthetic schematic diagram of high-crosslinking-degree PSt-Cl porous microsphere.
Fig. 2 is PSt-Cl amination reaction and PEGization reaction schematic diagram.
Fig. 3 A is that the made microballoon of embodiment 3 (being microballoon before modification) amplifies the SEM photo of 800 times.
Fig. 3 B is that after embodiment 5 modification gained modifications, microballoon amplifies 500 times of SEM photos.
Fig. 3 C is that after embodiment 5 modification gained modifications, microballoon amplifies the SEM photo of 10000 times.
Fig. 4 is the pressure flow velocity graphic representation of microballoon packed column after the modification of embodiment 5 gained.
Fig. 5 A is the laser co-focusing image after commercially available PSt microballoon absorption FITC-BSA.
Fig. 5 B is the laser co-focusing image after microballoon PSt-TMA absorption FITC-BSA after embodiment 5 gained modifications.
Embodiment
Below in conjunction with embodiment, further illustrate technical scheme of the present invention.
embodiment 1?
surface is containing the preparation of polystyrene type (PSt-Cl) microballoon of reactive chlorine
After 5g vinyl toluene (MST) and 0.1g trichlorine ethyl styrene, 1g Vinylstyrene (DVB) mix, as monomer phase, add perforating agent 5g normal heptane (HP), 0.3g dibenzoyl peroxide (BPO), after dissolving as disperse phase.After adding 2g polyvinyl alcohol (PVA) and 0.0015g dodecyl sulphate (SDS) to dissolve in 100ml deionized water as external phase.Utilize conventional film emulsifying technology (fenestras of 3.5 μ m) disperse phase to be dispersed in to the oil/water type emulsion that forms homogeneous in external phase.Then the emulsion preparing is moved in the reactor with prolong, stirring rod, nitrogen conduit, after logical nitrogen replacement oxygen, at 70 ℃, after polyreaction 10h, obtain microballoon polymeric suspensions.After polymerization finishes, with Büchner funnel suction filtration, obtain microspheres product.Product, after deionized water and ethanol repetitive scrubbing, is put into vacuum drying oven inner drying, and the final surface that obtains is containing the PSt-Cl porous microsphere of reactive chlorine.The median size of thus obtained microsphere is that 23 μ m, surface apertures are 80nm after tested, and specific surface area is 475m
2/ g.
Take after 1-chloro-4-methyl-benzene between 10g ethyl styrene (EST), 10g, 0.5g Potassium Persulphate (KPS) mixed dissolution as oil phase; At 150ml deionized water, add 1.8g PVA, 0.0004g SDS and 0.0045g Na
2sO
4after dissolving completely as water.Utilize fast film emulsifying technology (fenestras of 2.8 μ m) the fast ram compression of profit phase mixed solution to be crossed to the emulsion that obtains homogeneous after microporous membrane pipe circulating emulsion 5 times.Then the emulsion preparing is moved in the reactor with prolong, stirring rod, nitrogen conduit, after logical nitrogen replacement oxygen, at 85 ℃, after polyreaction 16h, obtain microballoon polymeric suspensions.After polymerization finishes, with whizzer centrifugal microspheres product that obtains under 3000rpm.Product repeatedly after centrifuge washing, is put into vacuum drying oven inner drying through deionized water and ethanol, and the final surface that obtains is containing the PSt-Cl solid microsphere of reactive chlorine.The median size of thus obtained microsphere is that 2.2 μ m, size distribution coefficient S pan value are 0.71 after tested, productive rate 92%.
embodiment 3?
surface is containing the preparation of polystyrene type (PSt-Cl) microballoon of reactive chlorine
Take after 1g vinylbenzene (St), 7g p-chloromethyl styrene (cMSt), 1g DVB and 0.42g azo amidine (V65), 3g n-Hexadecane (HD) and 3g n-hexyl alcohol (HA) mixed dissolution as oil phase; At 300ml deionized water, add 3.5g PVA, 0.0008g SDS and 0.009g Na
2sO
4after dissolving completely as water.Utilize conventional film emulsifying technology (fenestras of 5.2 μ m) oil phase to be dispersed in to the oil/water type emulsion that forms homogeneous in water.Then the emulsion preparing is moved in the reactor with prolong, stirring rod, nitrogen conduit, after logical nitrogen replacement oxygen, at 80 ℃, after polyreaction 20h, obtain microballoon polymeric suspensions.After polymerization finishes, with Büchner funnel suction filtration, obtain microspheres product.Product, after deionized water and ethanol repetitive scrubbing, is put into vacuum drying oven inner drying, and the final surface that obtains is containing the PSt-Cl porous microsphere of reactive chlorine.The median size of thus obtained microsphere is that 30 μ m, surface apertures are 600nm after tested, and specific surface area is 356m
2/ g, pore volume is 582mm
3/ g.Fig. 3 A is that this microballoon amplifies the SEM photo of 800 times.
The surface of above embodiment 1～3 containing the synthetic schematic diagram of polystyrene type (PSt-Cl) microballoon of reactive chlorine as shown in Figure 1.
As shown in Figure 2, get the prepared PSt-Cl microballoon 0.5g of embodiment 3, with 30mL1,4-dioxane swelling 2h, adds 5mL poly glycol monomethyl ether sodium salt, more than back flow reaction 20h, until detect on microballoon without chlorion.Then Isosorbide-5-Nitrae-dioxane, deionized water, the dehydrated alcohol repetitive scrubbing final vacuum for method by centrifugal-redispersion is dried, and can obtain PSt-PEG microballoon, surface hydrophilic degree > 90%.
embodiment 5?
embodiment 3 gained PSt-Cl porous microspheres quaternary ammoniated
As shown in Figure 2, in there-necked flask, add successively after the prepared PSt-Cl microballoon of 0.4g embodiment 3 and 20mL dimethyl formamide swelling 3h, in flask, drip Trimethylamine 99 (TMA) and alkali lye, at 50 ℃, after polyreaction 8h, be cooled to room temperature.Then reacted microballoon product suction filtration is isolated and first with deionized water, is washed till neutrality, then uses ethanol filter wash 3 times vacuum-drying to constant weight, obtains PSt-TMA microballoon.Microsphere surface hydrophilicity > 90% after modification after testing.Fig. 3 B, 3C are respectively scanning electron microscope (SEM) photo that microballoon after modification amplifies respectively 500 times and 10000 times.
Gained PSt-TMA microballoon is carried out to anion-exchange capacity mensuration, and measuring method is as follows:
Pack in exchange column PSt-TMA microballoon into slowly sedimentation, with deionized water, flow through till cylinder do not develop the color to phenolphthalein to flowing liquid.First with acid buret, accurately measuring 25ml concentration is that the hydrochloric acid soln of 0.01mol/L carries out drip washing and collects in 250ml triangular flask; With the sodium chloride solution of 1mol/L, being added dropwise to cylinder again carries out drip washing and collects equally in 250ml triangular flask.In collecting liquid, add 3 phenolphthalein indicators, with the sodium hydroxide solution of 0.01mol/L, be titrated to and collect liquid and present blush and keep colour-fast for eventually in 15S, record consume alkali lye volume.The loading capacity of this PSt-TMA microsphere medium product is calculated according to the following formula:
Wherein, C
1for the concentration of 0.01mol/L hydrochloric acid soln, V
1consumption volume (ml) for hydrochloric acid soln; C
2for the concentration of 0.01mol/L sodium hydroxide solution, V
2consumption volume (ml) for sodium hydroxide solution; V is the volume of cylinder medium.
Press said determination and method of calculation, the anion-exchange capacity of the present embodiment gained PSt-TMA microballoon is the dry medium of 0.319mmol/g.
Use embodiment 5 gained PSt-TMA microballoon sample separation bovine serum albumins (BSA), Shimadzu high performance liquid phase instrument detects detach Spline.
Elution requirement (detecting wavelength 280nm): 0-10min, B phase, PBS, 100%; 10.01-40min, A phase, 2M NaCl+PBS, 100%(is B phase, 0%); 40.01-55min, B phase, PBS, 100%; 55.01-85min, A phase, 1M NaOH+PBS, 100%(is B phase, 0%); 85.01-100min, B phase, PBS, 100%.
Mobile phase A 1(10.01-40min) be 2M NaCl+PBS, Mobile phase B is pH=7.0,50mM PBS;
Mobile phase A 2(55.01-85min) be 1M NaOH+PBS, Mobile phase B is pH=7.0,50mM PB.
Stainless steel column length is 25cm, and filling microballoon is the prepared PSt-TMA microballoon of embodiment 5.
Column volume V=4.15ml, sample size is 20 μ L, flow velocity 1ml/min.
Experiment finds that BSA can be retained on chromatography media by ion exchange completely, adopts A1 moving phase can realize 100% albumen wash-out completely, appearance time < 1min, resolution R > 1.5.Fig. 4 is the pressure flow velocity graphic representation of chromatographic separation process.
embodiment 7?
the protein adsorption comparison of modification microballoon of the present invention and unmodified microballoon
In order to contrast the protein adsorption situation of modification microballoon of the present invention and commercially available unmodified polystyrene microsphere, utilize laser confocal microscope to carry out contrast sign to embodiment 5 gained modification microballoon PSt-TMA and commercially available PSt microballoon (Archon) adhesion protein situation, under 488nm, excite, observed the fluorescence situation within the scope of 520-550nm.
Concrete operation method: first by fluorescein isothiocyanate for BSA (FITC) mark, be made into the FITC-BSA solution (pH7.4) of 10mg/ml.In the tool plug triangular flask of 25ml, accurately take microballoon 0.05g, add FITC-BSA solution 5ml, put into water bath chader, rotating speed 120rpm, keeps 25 ℃ of water temperatures, after absorption 24h, uses whizzer centrifugation; And then adding the damping fluid 5ml of pH7.4, centrifugation after water-bath vibration 1h, with damping fluid repeated washing 1 time again, to wash away the FITC-BSA that microsphere surface adheres to.The sample that takes a morsel is put into sample table at laser capture microdissection Microscopic observation, utilizes laser excitation FITC fluorescence imaging; Laser co-focusing image after commercially available PSt microballoon and embodiment 5 gained modification microballoon PSt-TMA absorption FITC-BSA is respectively as shown in Fig. 5 A, Fig. 5 B.
From Fig. 5 A, Fig. 5 B result, can obtain: compare with commercially available PSt microballoon, the fluorescence intensity of modification microballoon PSt-TMA of the present invention obviously reduces, illustrate that modification microballoon declines to the adsorptive capacity of albumen, the hydrophobic surface of microballoon has obtained effectively covering, and wetting ability obviously strengthens.
Applicant statement, the present invention illustrates technical scheme of the present invention by above-described embodiment, but the present invention is not limited to above-described embodiment, does not mean that the technical qualification that the present invention must rely on above-described embodiment could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of the selected raw material of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. effects on surface carries out a method for hydrophilic modifying containing the polystyrene type material of reactive chlorine, it is characterized in that, comprising:
(1) the polystyrene type material that surface is contained to reactive chlorine carries out swelling treatment with organic solvent;
(2), under alkaline matter existence condition, wetting ability functional group is linked to by the reactive chlorine generation substitution reaction with described polystyrene type material surface the material surface that step (1) gained is handled well.
2. method according to claim 1, it is characterized in that, the described surface of step (1) is prepared and is obtained by copolymerization by styrene monomer and the styrene monomer containing chloro alkyl containing the polystyrene type material of reactive chlorine, is preferably surface containing the polystyrene type microballoon of reactive chlorine;
Preferably, described styrene monomer is selected from the styrene monomer containing olefin functionalities; Further preferably, described styrene monomer is any one or a few in vinylbenzene, vinyl toluene, ethyl styrene or Vinylstyrene;
Preferably, the described styrene monomer containing chloro alkyl is any one or a few in p-chloromethyl styrene, a 1-chloro-4-methyl-benzene or trichlorine ethyl styrene;
Preferably, the mass ratio of described styrene monomer and the described styrene monomer containing chloro alkyl is (1:100)～(100:1), more preferably (50:100)～(100:50).
3. method according to claim 1 and 2, it is characterized in that, the described organic solvent of step (1) be for carrying out miscible polar organic solvent with water, is preferably any one or a few in dioxane, ethanol, dimethyl sulfoxide (DMSO), dimethyl formamide, methylene dichloride, trichloromethane, dithiocarbonic anhydride, toluene or dimethyl formamide.
4. according to the method described in claim 1-3 any one, it is characterized in that, by g/ml, the described surface of step (1) is 1:(1-100 containing the polystyrene type material of reactive chlorine and the mass volume ratio of described organic solvent), be preferably 1:(5-50), 1:(10-20 more preferably);
Preferably, the time of described swelling is 0.1-24 hour, 1-24 hour more preferably.
5. according to the method described in claim 1-4 any one, it is characterized in that, the described alkaline matter of step (2) be in sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus any one or several, preferably adopt the alkaline substance solution of 0.01-5mol/L;
Preferably, the mass ratio of described alkaline matter and described wetting ability functional group is (0.01-1): 1, more preferably (0.01-0.5): 1.
6. according to the method described in claim 1-5 any one, it is characterized in that, the donor of the described wetting ability functional group of step (2) be in amino-contained compound or derivatives thereof, poly glycol monomethyl ether salt, polyethylene polyamine any one or multiple;
Preferably, described amino-contained compound or derivatives thereof is Trimethylamine 99;
Preferably, the poly glycol monomethyl ether salt that described poly glycol monomethyl ether salt is various molecular weight, more preferably poly glycol monomethyl ether sodium salt;
Preferably, described polyethylene polyamine is tetraethylene pentamine, triethylene tetramine or diethylenetriamine;
Preferably, by g/ml, the material that step (1) gained is handled well and the mass volume ratio of described wetting ability functional group donor are 1:(1-100), 1:(1-50 more preferably);
Preferably, described crosslinked temperature is 0～200 ℃, more preferably 30～80 ℃, most preferably is 50-80 ℃;
Preferably, described cross-linking reaction time is 1～48 hour, more preferably 5～24 hours, most preferably is 5-18 hour.
7. a preparation method for the polystyrene type material of hydrophilic modifying, is characterized in that, comprises the following steps:
(1 ') contains styrene monomer and the styrene monomer copolymerization preparation surface containing chloro alkyl the polystyrene type material of reactive chlorine;
(2 ') obtains step (1 ') gained surface containing hydrophilic modification method modification described in the polystyrene type materials'use claim 1-6 any one of reactive chlorine.
8. preparation method according to claim 7, is characterized in that, in step (1 '), described styrene monomer is selected from the styrene monomer containing olefin functionalities; Preferably, described styrene monomer is any one or a few in vinylbenzene, vinyl toluene, ethyl styrene or Vinylstyrene;
Preferably, the described styrene monomer containing chloro alkyl is any one or a few in p-chloromethyl styrene, a 1-chloro-4-methyl-benzene or trichlorine ethyl styrene;
Preferably, the mass ratio of described styrene monomer and the described styrene monomer containing chloro alkyl is (1:100)～(100:1), more preferably (50:100)～(100:50).
9. according to the preparation method described in claim 7 or 8, it is characterized in that, step (1 ') comprises the steps:
(i) using styrene monomer, mix and be dissolved in solvent as disperse phase containing chloro alkyl styrene monomer and additive; Described additive comprises initiator, optionally comprises any one or a few in linking agent, pore-creating agent or cosurfactant;
Preferably, described initiator is any one or a few in benzoyl peroxide, dilauroyl peroxide, peroxy dicarbonate ethylhexyl, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile);
Preferably, described linking agent is any one or a few in divinylbenzene monomer, vulcabond or N,N methylene bis acrylamide;
Preferably, described pore-creating agent is any one or a few the mixture in hydrophobic C4-C22 alkanes, C4-C22 alkane chain alcohols, saturated aromatics or linear styrene's oligopolymer;
Preferably, described cosurfactant is any one or a few in lauryl alcohol, hexanol or enanthol;
Preferably, described solvent is any one or a few the mixture in deionized water, gelatin, Mierocrystalline cellulose, hydroxy alkyl cellulose, polyvinylpyrrolidone, anhydrous sodium sulphate, sodium lauryl sulphate or sodium laurylsulfonate, and more preferably two kinds of solvents are with 1: 100-100: the mixed solvent that 1 volume ratio is mixed;
(ii) dispersion agent or emulsifying agent and optional stopper are mixed and be dissolved in deionized water as external phase;
Preferably, described dispersion agent and emulsifying agent are any one or a few in polyvinyl alcohol, gelatin, Mierocrystalline cellulose, hydroxy alkyl cellulose, polyvinylpyrrolidone, anhydrous sodium sulphate, sodium lauryl sulphate or sodium laurylsulfonate;
Preferably, described stopper is Resorcinol;
By step (i) gained disperse phase be dispersed in step (ii) in gained external phase, form the oil/water type emulsion of homogeneous;
By step (iii) gained oil/water type emulsion move in the reactor with prolong, stirring rod, nitrogen conduit, after logical nitrogen replacement oxygen, at 30-150 ℃, preferably 50-120 ℃, more preferably polyreaction 1-48 hour, preferably 5-35 hour, more preferably 5-28 hour at 60-100 ℃, obtain polystyrene type microsphere suspension liquid;
To step (iv) gained polystyrene type microsphere suspension liquid carry out suction filtration or centrifugal, to the solid matter after suction filtration or centrifugal after throw out wash, dry, obtain surface containing the polystyrene type microballoon of reactive chlorine.
10. a polystyrene type material for hydrophilic modifying, is made by the hydrophilic modification method described in claim 1-6 any one, or is made by preparation method described in claim 7-9 any one.
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