CN102617869B - Polyacrylic ester and polyacrylic ester copolymer material hydrophilic modification products and hydrophilic modification method of polyacrylic ester - Google Patents
Polyacrylic ester and polyacrylic ester copolymer material hydrophilic modification products and hydrophilic modification method of polyacrylic ester Download PDFInfo
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Abstract
The invention discloses a method for hydrophilically modifying a polyacrylic ester or polyacrylic ester copolymer material and a product prepared with the method. The modification method comprises the following steps of: (1) performing swelling pretreatment on microspheres by using an organic solvent; (2) under the action of an alkaline catalyst, catalyzing ring opening of an epoxy group for reacting with hydroxy groups of polysaccharides to generate a stable ester bond, and chemically bonding hydrophilic polysaccharide molecules on the surfaces of the microspheres; and (3) under an alkaline condition, crosslinking and reinforcing the polysaccharide molecules bonded on the surfaces of the microspheres by using a bifunctional crosslinking agent. The method provided by the invention is easy and convenient to operate, and has mild reaction conditions; and an obtained hydrophilic material is stable, a coating is prevented from falling easily, and nonspecific adsorption of polymer microspheres on proteins is well suppressed. According to hydrophilically-modified polyacrylic ester microspheres, rich hydroxy groups contained in a hydrophilic layer can be further derived into other various functional groups; and the microspheres have great application prospects in the field of biotechnology, particularly in the field of biochemical separation.
Description
Technical field
The present invention relates to polymer materials modification field, relate in particular to a kind of method and product obtained by this method, the particularly surface hydrophilicity to oversized hole polyacrylate(s) material of surface of polymer material wetting ability.
Background technology
Polymer microballoon is as biochemical separating medium, and its advantage is that physical strength is high, stable chemical nature, acid-alkali-resistant degree are good, can under high pressure operate etc., therefore in the Application Areas as chromatographic media, has good prospect.But the Some features of polymkeric substance itself has limited its application aspect separation of biopolymer, as polymethyl acrylic acid glycidyl ether and Vinylstyrene copolymerization (PGMA-DVB) microballoon, its microsphere surface is with a large amount of epoxy group(ing), be easy to derive for various functional groups, therefore easily and between protein molecular, hydrophobic interaction occurs and cause the even sex change of irreversible adsorption of albumen but because its surface has hydrophobicity.
Research shows that this hydrophobic interaction is to cause that albumen is at major cause (the Journal of Colloid and Interface Science of material surface generation non-specific adsorption, 1989,132:176-187), one of approach addressing this problem, increases the wetting ability of material surface exactly.As CN 101011645A discloses the hydrophilic modification method of a kind of amphipathic molecule to polypropylene porous membrane surface, the method is to using the amphipathic molecule of block structure as hydrophilic modifying agent, first polypropylene porous film be impregnated in the swelling agent that is dissolved with amphipathic molecule and carry out surface treatment, finally by the method for vacuum extraction swelling agent, carry out surperficial deswelling; Employing has the close and distant water amphipathic molecule of block structure as surface treatment agent, wherein hydrophobic segment and polyacrylic consistency are better, the effect of " grappling " is easily provided with the polypropylene molecule chain combination of surperficial swollen region, hydrophilic segment is owing to being separated or orientation effect stretches to the outside on film surface, and gives the wetting ability of polypropylene porous membrane surface.
PGMA-DVB microballoon more easily carries out surface chemical modification as the more traditional polystyrene of separating medium and Vinylstyrene (PSt-DVB) microballoon, and the hydrophobicity of its skeletal matrix compared with PSt matrix a little less than, so be more suitable for as biochemical separating medium.The PGMA-DVB microsphere surface hydrophilic modifying of bibliographical information mostly is and surperficial epoxy group(ing) is hydrolyzed under acidity or alkaline condition to two hydroxyls, the polarity on strongthener surface is to obtaining good wetting ability (Chem Commun, 2007,4614-4616), as shown in Figure 1a; Or in this laboratory patented technology in early stage, by material surface coupling large hydrophilic molecular polyoxyethylene glycol (PEG) (CN100487011C) as shown in Figure 1 b, the PGMA microballoon after modification can be applied to the separation and purification of biomacromolecule under hydrophobic interaction chromatograph pattern.
Summary of the invention
The object of the invention is to develop a kind of method of surface of polymer material hydrophilization, the mode by hydrophilic polysaccharide molecule with chemical coupling, at surface of polymer material, then utilizes the hydroxyl that enriches on polysaccharide surface to carry out further chemically derived its coating.Material surface after modification and duct surface bond one deck hydroaropic substance, thereby significantly reduced the non-specific adsorption of material to albumen, surface after modification, owing to can being further derivatized to various functional groups, can be applied to the separation and purification of biomacromolecule.
After polyacrylate(s) or its copolymer microsphere material surface hydrophilic modifying, can effectively reduce albumen in its surperficial non-specific adsorption, in biologic applications field, have very high value; Oversized hole PGMA-DVB microballoon in the present invention is after hydrophilic modifying, can continue to keep original macroporous structure, can tolerate higher pressure operation, hydrophilic surface can further derive simultaneously, can, as the biochemistry separation medium under various clastotypes, therefore in biochemical separation and purification field, there be good application prospect and advantage.
For reaching this object, method of polyacrylate(s) or its copolymer material surface being carried out to hydrophilic modifying of the present invention, comprises the steps:
1) by polyacrylate(s) or its copolymer material, with organic solvent, carry out swelling treatment;
2), under alkaline matter existence condition, wetting ability polysaccharide molecule is chemically bonded to step 1 by covalent linkage under solvent exists) material surface handled well;
3) under alkaline matter existence condition, with linking agent by step 2) the hydrophilic polysaccharide of resulting material surface is cross-linked reinforcing.
Polyacrylate(s) material can be the materials such as polyacrylate modified product, derived products or graft copolymer.
As optimal technical scheme, step 1) the swelling treatment process described in is as follows: polyacrylate(s) or its copolymer material are put into organic solvent and seal vibration 1～4h, until polyacrylate(s) or its copolymer material in solvent after complete swelling, carry out suction filtration, and with solvent used, wash the clean solvent of suction filtration.
Swelling pretreatment step is important not omissible program in preparation process, and what fully the microballoon after swelling was conducive to hydrophilic substance diffuses into microballoon inside completely, and what be beneficial to hydrophilic substance covers the surface of the material that is modified completely.
As optimal technical scheme, step 2) bonding process described in is: the bonding process step 2) is: the polyacrylate(s) that wetting ability polysaccharide, alkaline matter, swelling are crossed or its copolymer material are put into reactor, in solvent, be fully uniformly mixed, at 30～80 ℃, react 12～24h, reaction finishes the unreacted material of rear removal, obtains the material of surface bond hydrophilic substance.
Preferably, described reaction finishes rear removal unreacting substance, and its program comprises carries out filtration under diminished pressure, filters and with hot deionized water, washs simultaneously, and the temperature of the deionized water of described heat is preferably 40～80 ℃.
As optimal technical scheme, step 3) the crosslinked reinforcing process described in is: to step 2) add linking agent in the material of gained, under alkaline condition, 20～50 ℃ are cross-linked after 12～24h hydrophilic coating, cross-linking products, through washing, dry, obtains hydrophilic modifying material.
Preferably, after crosslinking reaction finishes, washing, the drying process of cross-linking products are as follows: decompress filter water and ethanol successively wash three times, remove unreacted material, then vacuum-drying 24h at 50 ℃.The coating amount of calculating every gram of microballoon with mass method, calculation formula is as follows:
As optimal technical scheme, described polyacrylate(s) or its copolymer material are polymethyl acrylic acid glycidyl ether microballoon or sheet material or polymethyl acrylic acid glycidyl ether and Vinylstyrene copolymerization microsphere or sheet material.
As optimal technical scheme, step 1) described in organic solvent be selected from one or several in dioxane, ethanol, dimethyl sulfoxide (DMSO), dimethyl formamide.Swelling solvent used is not limited to above severally in the present invention, allly can carry out other miscible polar organic solvents with water and all can.
Preferably, the volumetric usage of described organic solvent is described 10～20 times by swollen material quality.Be microspheres quality: solvent volume=1: 10～20 (g/mL).
As optimal technical scheme, step 2) in, described alkaline matter is selected from one or several in sodium hydroxide, ammoniacal liquor, triethylamine, dimethyl aminopyridine, and preferably its consumption is 4～32% of polysaccharide quality.
Preferably, described wetting ability polysaccharide is agarose or dextran; Preferably agarose weight average molecular weight range is 10～30W, and dextran weight average molecular weight range is 5K～7W; Further preferred its quality consumption is polymethacrylate or copolymer material quality 1/3～3 times.
Preferably, described solvent is H
2o, DMSO or its mixture, preferred its mixture, further preferably DMSO and H
2o mixes with the ratio of 1: 10～1: 1 (v/v); Particularly preferably volumetric usage and the step 1 of solvent) ratio of quality of materials before untreated is 30: 1～50: 1 (v/m).DMSO adds the swelling that is conducive to polymer materials.
As optimal technical scheme, step 3) described in alkaline matter be sodium hydroxide or/and potassium hydroxide, preferably its concentration range is 1～7mol/L;
Preferably, in described alkaline substance solution, solvent used is H
2the mixture of O and DMSO, preferably DMSO and H
2the volume ratio of O is 1: 10～1: 1 (v/v);
Preferably, described linking agent is selected from one or several in ethylene glycol diglycidylether, epoxy chloropropane, two polyethyleneglycol diglycidylethers; Preferably its consumption is to be crosslinked 1～10 times of quality of materials.
One of object of the present invention is also to provide a kind of hydrophilic modifying polyacrylate(s) making according to preparation method provided by the present invention or its copolymer material, described material surface comprise the internal surface chemical coupling of microballoon duct one deck be rich in wetting ability agarose or the dextran molecule of hydroxyl, can be used for further modification or derivative.
As optimal technical scheme, the polymethyl acrylic acid glycidyl ether material that described hydrophilic modifying polyacrylate(s) or its copolymer material are hydrophilic modifying or polymethyl acrylic acid glycidyl ether and divinyl benzene copolymer material.
For the inhibition of microballoon to albumen non-specific adsorption after check hydrophilic modifying, the microballoon of modification is packed in stainless steel chromatogram column jecket, column jecket specification is φ 4.6 * 50mm, the chromatographic column filling is connected on high performance liquid chromatography and tests the non-specific adsorption of microballoon to protein B SA, and specific experiment method is shown in embodiment part.Result shows that its BSA non-specific adsorption amount is close to 0.
The method of hydrophilic modifying material surface of the present invention is, polyose molecular chemistry is coupled to the surface of the material that is modified, particularly for the surface modification of oversized hole polymethyl acrylic acid Racemic glycidol ethers microballoon.
The technique effect that the present invention produces is, at the enough uniform bonding one deck wetting ability polysaccharide molecule of polymethyl acrylic acid Racemic glycidol ethers material surface energy, the wetting ability of the material surface after modification improves greatly, can significantly reduce the non-specific adsorption amount to albumen.
Method of the present invention, can be applied to surface modification, the especially super large pore polymer microsphere of most polymers material, and the polymer microballoon after hydrophilic modifying can be applied to biotechnology and chromatographic separation field.
Accompanying drawing explanation
Fig. 1 is PGMA-DVB microballoon hydrophilization schematic diagram.
Fig. 2 is the electronics surface sweeping microphotograph of the polymer microballoon modification front and back of embodiment bis-gained, and wherein A is the microballoon before modification; B is the microballoon after modification.
Fig. 3 is the adsorptive capacity mensuration figure to albumen of the modification post polymerization thing microballoon of embodiment tri-gained, ● the chromatographic peak area while representing BSA without absorption; ■ represents the chromatographic peak area of BSA after hydrophilization microballoon.
Embodiment
Below in conjunction with accompanying drawing and by embodiment, further illustrate technical scheme of the present invention.
Embodiment mono-
1) oversized hole PGMA-DVB microballoon pre-treatment in dioxane
Accurately take the Erlenmeyer flask that PGMA-DVB microballoon 1.0g puts into 50mL, then add dioxane 10mL, in 120rpm vibration shaking table, under room temperature, vibrate after 2h, carry out suction filtration, and with the dioxane of same volume, wash, after washing by solvent suction filtration to microsphere surface without obvious solvent.
2) PGMA-DVB microsphere surface bonding agarose (Mw=13W)
Take 1.0g agarose (Mw=13W), 0.32g NaOH puts into 100mL there-necked flask, then adds wherein 50mL DMSO/H2O (1: 5; V/v) mixed solvent, under 120rpm mechanical stirring, adds step 1 in embodiment mono-) microballoon after swelling treatment, be warming up to 70 ℃, at this temperature, keep reaction 24h, after reaction finishes while hot, with G4 sand core funnel, carry out decompress filter, with 80 ℃ of hot water of 500mL, wash simultaneously.
3) with the crosslinked PGMA-DVB microsphere surface bonding agarose of reinforcing of EDGE
By step 2 in case study on implementation one) microballoon that makes is transferred in tri-mouthfuls of reaction flasks of 100mL, then to reaction flask, adds 10g NaOH pressed powder, adds 50mL DMSO/H under 120rpm mechanical stirring
2o (1: 5, v/v) mixed solvent, then by constant pressure funnel, slowly drip the EDGE of 3.5mL, control rate of addition, at 20 ℃, in 4h, EDGE is dropwised, keep reaction 12h, react complete, with G4 sand core funnel, carry out decompress filter, and successively wash three times with deionized water and ethanol, remove unreacted material.Microballoon after washes clean, to constant weight, characterizes coating with Fourier's infrared spectra (FTIR) 50 ℃ of vacuum-dryings, shows at 3432cm
-1the hydroxyl absorption peak at place is obviously strengthened, simultaneously at 1071cm
-1near also occurred the stretching vibration peak of the C-O-C of agarose, the appearance of these characteristic peaks show agarose successful coating to PGMA-DVB microballoon.Poidometer is counted in and is stated the modification microballoon making, and its agarose coating amount is 110mg/g.
Embodiment bis-
1) oversized hole PGMA-DVB microballoon pre-treatment in DMSO
Accurately take the Erlenmeyer flask that PGMA-DVB microballoon 1.0g puts into 50mL, then add DMSO20mL, in 120rpm vibration shaking table, under room temperature, vibrate after 2h, carry out suction filtration, and with the DMSO of same volume, wash, after washing by solvent suction filtration to microsphere surface without obvious solvent.
2) PGMA-DVB microsphere surface bonding dextran (Mw=2W)
Take 1.0g dextran (Mw=2W), 0.32g NaOH puts into 100mL there-necked flask, then adds wherein 50mL DMSO/H
2o (1: 5, v/v) mixed solvent, under 120rpm mechanical stirring, add step 1 in embodiment bis-) microballoon after swelling treatment, be warming up to 37 ℃, at this temperature, keep reaction 20h, after reaction finishes, with G4 sand core funnel, carry out decompress filter while hot, with 40 ℃ of deionized waters of 500mL, wash simultaneously.
3) by the crosslinked PGMA-DVB microsphere surface bonding dextran of reinforcing of EPCl
By step 2 in case study on implementation two) microballoon that makes is transferred in tri-mouthfuls of reaction flasks of 100mL, then to reaction flask, adds 10g NaOH pressed powder, adds 50mL DMSO/H under 120rpm mechanical stirring
2o (1: 5, v/v) mixed solvent, then be warming up to 35 ℃ of EPCl that slowly drip 4.5mL by constant pressure funnel, control rate of addition, under room temperature, in 4h, EPCl is dropwised, keep reaction 24h, react complete, with G4 sand core funnel, carry out decompress filter, and successively wash three times with deionized water and ethanol, remove unreacted material.Microballoon after washes clean, to constant weight, observes the microballoon of modification front and back 50 ℃ of vacuum-dryings with scanning electron microscope, its pattern, without considerable change, as shown in Figure 2, shows that surface hydrophilic modification reaction does not destroy the original pore passage structure of microballoon.After above-mentioned modification, the coating amount of microballoon is 116mg/g.
Embodiment tri-
1) oversized hole PGMA-DVB microballoon pre-treatment in DMF
Accurately take the Erlenmeyer flask that PGMA-DVB microballoon 1.0g puts into 50mL, then add DMF15mL, in 120rpm vibration shaking table, under room temperature, vibrate after 2h, carry out suction filtration, and with the DMF of same volume, wash, after washing by solvent suction filtration to microsphere surface without obvious solvent.
2) PGMA-DVB microsphere surface bonding dextran (Mw=5W)
Take 1.0g dextran (Mw=5W), 0.32g NaOH puts into 100mL there-necked flask, then add wherein 50mL DMSO/H2O (1: 5, v/v) mixed solvent, under 120rpm mechanical stirring, add step 1 in embodiment tri-) microballoon after swelling treatment, be warming up to 47 ℃, at this temperature, keep reaction 24h, after reaction finishes, with G4 sand core funnel, carry out decompress filter while hot, and wash with 50 ℃ of deionized waters of 500mL.
3) by the crosslinked PGMA-DVB microsphere surface bonding dextran (Mw=5W) of reinforcing of EDGE
By step 2 in case study on implementation three) microballoon that makes is transferred in tri-mouthfuls of reaction flasks of 100mL, then to reaction flask, adds 10g NaOH pressed powder, adds 50mL DMSO/H under 120rpm mechanical stirring
2o (1: 5, v/v) mixed solvent, then be warming up to 40 ℃, by constant pressure funnel, slowly drip the EDGE of 3.5mL, control rate of addition, in 4h, EDGE is dropwised, keep reaction 24h, after completion of the reaction, with G4 sand core funnel, carry out decompress filter, and successively wash three times with deionized water and ethanol, remove unreacted material.Microballoon after washes clean, 50 ℃ of vacuum-dryings, to constant weight, coating amount is 120mg/g.After modification, microballoon is usingd bovine serum albumin (BSA) as model protein, measures its albumen non-specific adsorption, shows that its BSA non-specific adsorption amount is close to 0, and measured value is 0.004mg/mL, and its test result as shown in Figure 3.
Embodiment tetra-
1) oversized hole PGMA-DVB microballoon pre-treatment in DMSO
Accurately take the Erlenmeyer flask that PGMA-DVB microballoon 1.0g puts into 50mL, then add DMSO15mL, in 120rpm vibration shaking table, under room temperature, vibrate after 3h, carry out suction filtration, and with the DMSO of same volume, wash, after washing by solvent suction filtration to microsphere surface without obvious solvent.
2) PGMA-DVB microsphere surface bonding dextran (Mw=5W)
Take 1.0g dextran (Mw=5W), 0.32g DMAP puts into 100mL there-necked flask, then add wherein 50mL DMSO/H2O (1: 3, v/v) mixed solvent, under 120rpm mechanical stirring, add step 1 in embodiment tetra-) microballoon after swelling treatment, be warming up to 37 ℃, at this temperature, keep reaction 24h, after reaction finishes, with G4 sand core funnel, carry out decompress filter while hot, with 40 ℃ of deionized waters of 500mL, wash simultaneously.
3) by the crosslinked PGMA-DVB microsphere surface bonding dextran (Mw=5W) of reinforcing of DEDGE
By step 2 in case study on implementation four) microballoon that makes is transferred in tri-mouthfuls of reaction flasks of 100mL, then to reaction flask, add 10g NaOH pressed powder, under 120rpm mechanical stirring, add 50mL DMSO/H2O (1: 5, v/v) mixed solvent, then be warming up to 50 ℃, by constant pressure funnel, slowly drip the DEDGE of 3.5mL, control rate of addition, in 4h, DEDGE is dropwised, keep reaction 24h, react complete, with G4 sand core funnel, carry out decompress filter, and successively wash three times with deionized water and ethanol, remove unreacted material.Microballoon after washes clean, 50 ℃ of vacuum-dryings to constant weight.The above-mentioned microballoon coating amount making is 116mg/g, and BSA non-specific adsorption amount is 0.01mg/mL.
Embodiment five
1) oversized hole PGMA-DVB microballoon pre-treatment in DMSO
Accurately take the Erlenmeyer flask that PGMA-DVB microballoon 1.0g puts into 50mL, then add DMSO15mL, in 120rpm vibration shaking table, under room temperature, vibrate after 2h, carry out suction filtration, and with the DMSO of same volume, wash, after washing by solvent suction filtration to microsphere surface without obvious solvent.
2) PGMA-DVB microsphere surface bonding dextran (Mw=1W)
Take 2.0g dextran (Mw=1W), 0.24g triethylamine is put into 100mL there-necked flask, then add wherein 50mL DMSO/H2O (1: 3, v/v) mixed solvent, under 120rpm mechanical stirring, add step 1 in embodiment five) microballoon after swelling treatment, be warming up to 60 ℃, at this temperature, keep reaction 24h, after reaction finishes, with G4 sand core funnel, carry out decompress filter while hot, with 70 ℃ of deionized waters of 500mL, wash simultaneously.
3) by the crosslinked PGMA-DVB microsphere surface bonding dextran (Mw=1W) of reinforcing of EDGE
By step 2 in embodiment five) microballoon that makes is transferred in tri-mouthfuls of reaction flasks of 100mL, then to reaction flask, add 14g NaOH pressed powder, under 120rpm mechanical stirring, add 50mL DMSO/H2O (1: 10, v/v) mixed solvent, then be warming up to 35 ℃ of EDGE that slowly drip 6.5mL by constant pressure funnel, control rate of addition, in 4h, EDGE is dropwised, keep reaction 24h, react complete, with G4 sand core funnel, carry out decompress filter, and successively wash three times with deionized water and ethanol, remove unreacted material.Microballoon after washes clean, 50 ℃ of vacuum-dryings, to constant weight, coating amount is 126mg/g, and BSA non-specific adsorption amount is 0.02mg/mL microballoon, and its non-specific adsorption amount is also close to 0.
Embodiment six
1) oversized hole PGMA-DVB microballoon pre-treatment in DMSO
Accurately take the Erlenmeyer flask that PGMA-DVB microballoon 1.0g puts into 50mL, then add DMSO15mL, in 120rpm vibration shaking table, under room temperature, vibrate after 2h, carry out suction filtration, and with the DMSO of same volume, wash, after washing by solvent suction filtration to microsphere surface without obvious solvent.
2) PGMA-DVB microsphere surface bonding dextran (Mw=4W)
Take 2.0g dextran (Mw=4W), 0.24g DMAP puts into 100mL there-necked flask, then adds wherein 50mL DMSO/H
2o (1: 4, v/v) mixed solvent, under 120rpm mechanical stirring, add step 1 in embodiment six) microballoon after swelling treatment, be warming up to 47 ℃, at this temperature, keep reaction 24h, after reaction finishes, with G4 sand core funnel, carry out decompress filter while hot, with 50 ℃ of deionized waters of 500mL, wash simultaneously.
3) by the crosslinked PGMA-DVB microsphere surface bonding dextran (Mw=4W) of reinforcing of DEDGE
By step 2 in embodiment six) microballoon that makes is transferred in tri-mouthfuls of reaction flasks of 100mL, then to reaction flask, adds 14g KOH pressed powder, adds 50mL DMSO/H under 120rpm mechanical stirring
2o (1: 10, v/v) mixed solvent, then by constant pressure funnel, slowly drip the DEDGE of 10mL, control rate of addition, under room temperature, in 4h, EDGE is dropwised, keep reaction 24h, react complete, with G4 sand core funnel, carry out decompress filter, and successively wash three times with deionized water and ethanol, remove unreacted material.Microballoon after washes clean, 50 ℃ of vacuum-dryings, to constant weight, coating amount is 123mg/g, BSA non-specific adsorption amount is close to 0.
Non-specific adsorption flow measurement
1) microballoon after filling modification
Microballoon after 1.0g modification is put in 20mL 50% aqueous ethanolic solution, after ultrasonic dispersion 30min, is put in the homogenizer of packing column machine, with 10MPa pressure dress post, time length 1h, column jecket specification is φ 4.6 * 50mm.
2) with the non-specific adsorption of microballoon after BSA test modification
A is in embodiment seven, step 1) chromatographic column of loading is connected on liquid chromatograph, and chromatographic condition is as follows: the BSA solution of sample concentration 2mg/mL; Applied sample amount 200 μ L; Flow velocity 1mL/min; Mobile phase A pH=7.0,50mM phosphate buffer solution, the B 1M NaOH aqueous solution; Gradient condition 0-10minA phase; 10.01-20min B phase; 20.01-30A phase; Repeat sample introduction 5 times, record goes out peak area A1 at every turn; B replaces chromatographic column with connecting joint, same chromatographic process test, and record goes out peak area A at every turn
2; C calculates the adsorptive capacity of BSA in chromatographic column, and formula is as follows:
Q
bSA: the quality of every milliliter of microballoon BSA adsorption (mg/mL);
V: the volume of microballoon (mL) in chromatographic column.
The prepared hydrophilic modifying microballoon of above embodiment 1-6, test b SA non-specific adsorption amount, all uses the testing method of above-mentioned specific adsorption flow measurement, and Fig. 3 is tri-test results of embodiment.
Claims (25)
1. polyacrylate(s) or its copolymer material surface are carried out to a method for hydrophilic modifying, comprise the steps:
1) by polyacrylate(s) or its copolymer material, with organic solvent, carry out swelling treatment;
2), under alkaline matter existence condition, wetting ability polysaccharide molecule is chemically bonded to step 1 by covalent linkage under solvent exists) material surface handled well;
3) under alkaline matter existence condition, with linking agent by step 2) the hydrophilic polysaccharide of resulting material surface is cross-linked reinforcing;
Step 2), in, described alkaline matter consumption is 4～32% of polysaccharide quality; Polysaccharide quality consumption is polymethacrylate or copolymer material quality 1/3～3 times.
2. method according to claim 1, it is characterized in that, step 1) the swelling treatment process described in is as follows: polyacrylate(s) or its copolymer material are put into organic solvent and seal vibration 1～4h, until polyacrylate(s) or its copolymer material in solvent after complete swelling, carry out suction filtration, and with solvent used, wash the clean solvent of suction filtration.
3. method according to claim 1, it is characterized in that, step 2) bonding process described in is: the polyacrylate(s) that wetting ability polysaccharide, alkaline matter, swelling are crossed or its copolymer material are put into reactor, in solvent, be fully uniformly mixed, at 30～80 ℃, react 12～24h, reaction finishes the unreacted material of rear removal, obtains the material of surface bond hydrophilic substance.
4. method according to claim 3, is characterized in that, described reaction finishes rear removal unreacting substance, and its program comprises carries out filtration under diminished pressure, filters and with hot deionized water, washs simultaneously, and the temperature of the deionized water of described heat is preferably 40～80 ℃.
5. method according to claim 1, it is characterized in that, step 3) the crosslinked reinforcing process described in is: to step 2) add linking agent in the material of gained, under alkaline condition, 20～50 ℃ are cross-linked after 12～24h hydrophilic coating, cross-linking products, through washing, dry, obtains hydrophilic modifying material.
6. method according to claim 5, is characterized in that, after crosslinking reaction finishes, washing, the drying process of cross-linking products are as follows: decompress filter water and ethanol successively wash three times, remove unreacted material, then vacuum-drying 24h at 50 ℃.
7. method according to claim 1, is characterized in that, described polyacrylate(s) or its copolymer material are polymethyl acrylic acid glycidyl ether microballoon or sheet material or polymethyl acrylic acid glycidyl ether and Vinylstyrene copolymerization microsphere or sheet material.
8. method according to claim 1, is characterized in that step 1) described in organic solvent be selected from one or several in dioxane, ethanol, dimethyl sulfoxide (DMSO), dimethyl formamide.
9. according to the method described in claim 1-8 any one, it is characterized in that step 1) described in the volumetric usage of organic solvent be described 10～20 times by swollen material quality.
10. according to the method described in claim 1～8 any one, it is characterized in that step 2) described in alkaline matter be selected from one or several in sodium hydroxide, ammoniacal liquor, triethylamine, dimethyl aminopyridine.
11. according to the method described in claim 1～8 any one, it is characterized in that step 2) described in wetting ability polysaccharide be agarose or dextran.
12. methods according to claim 11, is characterized in that, agarose weight average molecular weight range is 10～300,000, and dextran weight average molecular weight range is 5,000～70,000.
13. according to the method described in claim 1～8 any one, it is characterized in that step 2) described in solvent be H
2o, DMSO or its mixture.
14. methods according to claim 13, is characterized in that, described solvent is H
2o and DMSO mixture.
15. methods according to claim 14, is characterized in that, described solvent is DMSO and H
2o mixes with the ratio of volume ratio 1:10～1:1.
16. according to the method described in claim 1-8 any one, it is characterized in that step 2) in the ratio of the volumetric usage of solvent and the quality of materials of step 1) before untreated be 30:1～50:1.
17. methods according to claim 1, is characterized in that step 3) described in alkaline matter be that sodium hydroxide is or/and potassium hydroxide.
18. methods according to claim 17, is characterized in that, alkaline matter concentration range is 1～7mol/L.
19. according to the method described in claim 1-8 any one, it is characterized in that step 3) described in alkaline substance solution solvent used be H
2the mixture of O and DMSO.
20. methods according to claim 19, is characterized in that, solvent used is DMSO and H
2the volume ratio of O is 1:10～1:1.
21. according to the method described in claim 1-8 any one, it is characterized in that step 3) described in linking agent be selected from one or several in ethylene glycol diglycidylether, epoxy chloropropane, two polyethyleneglycol diglycidylethers.
22. according to the method described in claim 1-8 any one, it is characterized in that step 3) described in dosage of crosslinking agent be to be crosslinked 1～10 times of quality of materials.
23. methods according to claim 21, is characterized in that, described dosage of crosslinking agent is to be crosslinked 1～10 times of quality of materials.
The 24. hydrophilic modifying polyacrylate(s) making according to the method described in claim 1～23 any one or its copolymer materials, it is characterized in that, material surface comprise the internal surface chemical coupling of microballoon duct one deck be rich in wetting ability agarose or the dextran molecule of hydroxyl, can be used for further modification or derivative.
25. hydrophilic modifying polyacrylate(s) according to claim 24 or its copolymer materials, it is characterized in that the polymethyl acrylic acid glycidyl ether material that described hydrophilic modifying polyacrylate(s) or its copolymer material are hydrophilic modifying or polymethyl acrylic acid glycidyl ether and divinyl benzene copolymer material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210091582.XA CN102617869B (en) | 2012-03-30 | 2012-03-30 | Polyacrylic ester and polyacrylic ester copolymer material hydrophilic modification products and hydrophilic modification method of polyacrylic ester |
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| CN103611512A (en) * | 2013-12-05 | 2014-03-05 | 苏州博进生物技术有限公司 | Hydrophilic high mechanical strength chromatography medium and preparation method thereof |
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| CN107365422B (en) * | 2016-05-11 | 2020-12-01 | 中国科学院过程工程研究所 | Hydrophilic modification method of polyglycidyl methacrylate or copolymer thereof and modified material |
| CN106582578B (en) * | 2016-12-22 | 2019-06-14 | 苏州楚博生物技术有限公司 | High pressure resistant affinity chromatography medium |
| CN108235666B (en) * | 2018-02-11 | 2024-03-01 | 中国科学院工程热物理研究所 | Surface-regulated flexible micro-groove group heat sink, heat dissipation device and method |
| CN109647361A (en) * | 2019-02-22 | 2019-04-19 | 北京石油化工学院 | A kind of preparation method of composite polymer chromatography media |
| CN112341663B (en) * | 2020-10-28 | 2022-02-22 | 苏州纳微科技股份有限公司 | Protein A affinity chromatography medium of PMMA matrix and preparation method and application thereof |
| CN112808250B (en) * | 2020-12-25 | 2022-01-11 | 同济大学 | Hollow microsphere, preparation method and water treatment application |
| 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 |
| CN114113414B (en) * | 2021-12-23 | 2023-12-01 | 宁波市疾病预防控制中心 | Polymer composite microsphere for extracting and purifying triphenyl metabolite in urine, preparation method, kit and extraction method |
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