CN101440168B - Method for surface hydrophilic modification of polystyrene material and product - Google Patents
Method for surface hydrophilic modification of polystyrene material and product Download PDFInfo
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 87
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 26
- 230000004048 modification Effects 0.000 title claims abstract description 22
- 238000012986 modification Methods 0.000 title claims abstract description 22
- 239000004005 microsphere Substances 0.000 claims abstract description 27
- 230000008878 coupling Effects 0.000 claims abstract description 26
- 238000010168 coupling process Methods 0.000 claims abstract description 26
- 238000005859 coupling reaction Methods 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 monochloromethyl Chemical group 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- KCMZYCFSSYXEQR-UHFFFAOYSA-N CCCC[K] Chemical group CCCC[K] KCMZYCFSSYXEQR-UHFFFAOYSA-N 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000012501 chromatography medium Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 45
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 45
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 238000013375 chromatographic separation Methods 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 3
- 230000021736 acetylation Effects 0.000 abstract description 3
- 238000006640 acetylation reaction Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000006266 etherification reaction Methods 0.000 abstract description 2
- 230000011987 methylation Effects 0.000 abstract 1
- 238000007069 methylation reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002202 Polyethylene glycol Substances 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000001464 adherent effect Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920000858 Cyclodextrin Polymers 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000001116 FEMA 4028 Substances 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 3
- 229960004853 betadex Drugs 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- YKSNHLNTLVRITE-UHFFFAOYSA-N [Br].CC(Br)=O Chemical compound [Br].CC(Br)=O YKSNHLNTLVRITE-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000012412 chemical coupling Methods 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 241001566735 Archon Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229940106780 human fibrinogen Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a method for preparing surface hydrophilic modified polystyrene materials, and a product thereof, and the method is characterized by grafting and coupling the surface of polystyrene with a layer of hydrophilic macromolecular polyvinyl alcohol (PVA) through a stable chemical bond, particularly performing hydrophilic modification on the surfaces of super-macroporous polystyrene microspheres. The method comprises the following concrete steps: (1) benzene ring of polystyrene is subjected to halogen acetylation or halogen methylation in an organic solvent under the action of acidic catalysts through Friedel-Crafts reaction, and is added to active radical halogen acetyl or halogen methyl; and (2) under alkaline conditions and the action of phase transfer catalyst, Williamson etherification is utilized to couple the hydrophilic PVA to the surface of polystyrene through ether linkage. The method has the advantages of simple operation and mild conditions. A hydrophilic coating is stable, not easy to fall off and rich in hydroxyl. The method has great application potential in biotechnology, particularly the chromatographic separation field.
Description
Technical field
The present invention relates to a kind of method and product of surface hydrophilic modification polystyrene material.Particularly to oversized hole polystyrene microsphere surface hydrophilic modification, the product feature that obtains is the inner high-intensity hydrophobic stephanoporate framework that is, surface (comprising the duct internal surface) coupling one deck is rich in the wetting ability macromole polyvinyl alcohol (PVA) of hydroxyl, the perfusion chromatographic media of back as the sharp separation protein and other of further deriving.Belong to the function modified field of polymer microsphere.
Background technology
In a lot of biotechnology applications, all exist the non-specific adsorption problem of protein and other at hydrophobic surface.Can cause accuracy of detection to descend such as antibody and antigen in the solid phase diagnosis in the absorption of 96 orifice plates, the non-specific adsorption of albumen on medium can cause bands of a spectrum to broaden and (Analytical Biochemistry such as sample loss in the chromatographic separation, 1980,105:375～383; Journal of Chromatography, 1988,445:1～11).In addition, cell, bacterium and higher organism also are the major causes of biological pollution at material surface absorption formation egg white layer.Hydrophobic interaction be hydrophobic material to the main factor of albumen non-specific adsorption (Journal of colloid and interface Science, 1989,132:176-187), the wetting ability that increases material will reduce proteic adsorptive capacity greatly.Therefore hydrophobic material being carried out surface hydrophilic modification is a kind of Perfected process that reduces the albumen non-specific adsorption..
Polystyrene material is because its favorable mechanical performance and chemical stability, behind the hydrophilic modifying in biology and analytical separation field extensive application.Method of modifying commonly used has two kinds: physical adsorption coating hydrophilic material and chemical coupling coating hydrophilic material.Physical adsorption coating is normally at polystyrene material surface adsorption one deck hydrophilic/hydrophobic amphipathic nature polyalcohol, carries out crosslinkedly then, and adsorpting type belongs to the Langmuir type more.Amphipathic nature polyalcohol mainly contains PVA, hydrophobically modified polysaccharide, polyoxyethylene-poly-oxypropylene polyoxyethylene inlay and break copolymer etc.Though the wetting ability of material surface effectively improves behind the physical adsorption coating, suppressed proteic non-specific adsorption.But coating comes off easily, and when particularly being in the middle of the protein solution, this has limited the recycling number of times of material, and influence is very big during particularly as chromatography separation media.
Compare physisorphtion, the report of chemical coupling method grafting hydrophilic macromolecule is less, and in the existing document, more is the report of polystyrene microsphere surface conjugated polyethylene glycol (PEG).The polystyrene modification at first will be reflected at by Friedel-Crafts and connect reactive group (CH on the benzene ring of polystyrene
2C1 ,-OH ,-COOH ,-COCH
2Cl ,-NH
2Deng), and then utilize the further modification of these reactive groups.Lee Yoon-Sik (U.S.Patent 5,466,758 (1995) .) etc. the people invented the short-cut method that a kind of preparation has β hydroxyl polystyrene (PS-PO), and prepare the polystyrene microsphere of grafting PEG on this basis.Synthetic route is as follows:
People such as Holmberg have studied the polystyrene of grafting branching type PEG and line style PEG to reducing the influence (Journal of biomedical materials research, 1992,26:779～790) of human fibrinogen's adsorptive power.The result shows, branching type and line style PEG (molecular weight is 1500～20000) can both obviously reduce proteic adsorptive capacity, branching type PEG compares clear superiority in the not anticipation with linear PEG, the author has proved that with Size Exclusion Chromatograph SEC the exclusion volume of branching type and line style PEG does not have different in water.The reaction synoptic diagram is as follows:
Above-mentioned two methods all belong at polystyrene surface grafting PEG, can effectively reduce proteinic non-specific adsorption effect.But a PEG chain only contains a hydroxyl after the grafting, if the further modification of material require meeting is restricted, further is derivatized to ion-exchange chromatography, media for affinity chromatography etc. such as microballoon after the modification.
(functional polymer journal such as Mao Luyuan, 1997,10:205～212) prepared the polystyrene microsphere of the immobilized cyclodextrin in a kind of surface, with DMF is solvent, potassiumiodide and four butyl bromation amine are cooked phase-transfer catalyst (Phasetransfer catalyst, PTC), make beta-cyclodextrin in the presence of sodium hydroxide or sodium hydride with chloromethyl polystyrene microsphere generation nucleophilic substitution reaction.Reaction scheme is as follows:
The first step: change reaction scheme with carrying
Second step: graft reaction route
They have investigated the inclusion recognition performance of beta-cyclodextrin multipolymer Pyrogentisinic Acid, para-chlorophenol, ortho chloro phenol, and the result shows clathration contraposition＞ortho position＞phenol.This beta-cyclodextrin multipolymer belongs to oligopolymer, can not effectively cover the hydrophobic surface of polystyrene, is not suitable as the biomacromolecule isolation medium.
The invention provides a kind of method and product of effective surface hydrophilic modification polystyrene material, in previous work (ion-exchange and absorption, 2005,21 (4): 289～296; Chengdu Univ. of Science ﹠ Technology's journal; 1993; 76 (6): on the basis 44～50) (polystyrene halomethylation or halogen acetylize); wetting ability macromole polyvinyl alcohol successfully is coupled to oversized hole polystyrene microsphere surface; not only effectively reduce proteinic non-specific adsorption; and the microballoon after the modification is rich in hydroxyl, can further adopt traditional method to be derivatized to various chromatography separation medias.
Summary of the invention
The present invention utilizes Williamson etherification reaction principle, and purpose is at the even coupling one deck of polystyrene surface hydroaropic substance.Can effectively reduce absorption of proteins behind the ordinary polystyrene material modification, very big value is arranged in the biologic applications field; Be a kind of good biomacromolecule chromatographic separation matrix after the modification of oversized hole polystyrene microsphere, the back of further deriving has very big potentiality and advantage in Fast Separation of Proteins purifying field.
The present invention proposes a kind of method and product of surface hydrophilic modification polystyrene material, comprise the steps:
A, under an acidic catalyst effect, utilize Friedel-Crafts reaction with acetylize of benzene ring of polystyrene halogen or halomethylation, obtain possessing the substance A of following general formula:
Wherein R can be C=O, H, and X can be Cl, Br.The functional group RCHX of A is halogen ethanoyl or monochloromethyl, preferred chloracetyl or chloromethyl.
B, under the alkaline matter existence condition, the A of gained and an amount of PTC are joined in the organic solvent that is dissolved with PVA, make PVA and polystyrene pass through the ehter bond coupling.Chemical equation is as follows when alkaline matter is sodium hydroxide:
Polystyrene among the step a of modified-reaction of the present invention is a crosslinked polystyrene, is preferably crosslinked polystyrene microsphere or polystyrene board.
When step a finishes, with reaction solution suction filtration under anhydrous state, separate the solid matter obtain and pour into rapidly in the cryosel acid and stir, filter once more and be washed till neutrality with deionized water, filter with absolute ethanol washing more at last, in vacuum drying oven, carry out the reaction of second step after the drying.
The step b of modified-reaction of the present invention is committed step.If control badly, both may cause dewatering between the polyvinyl alcohol molecular chain, crosslinkedly be wrapped in polystyrene surface after agglomerating, may cause also that PVA coupling amount is too low can't fully to cover the polystyrene hydrophobic surface.The coupling amount of ideal PVA is at 0.8～1.0mg/m
2In the scope.
PVA is a kind of critical material among the modified-reaction step b of the present invention, and PVA2K that mentions in the literary composition and PVA22K alcoholysis degree are respectively 75% and 87～89%, purchases the company in Acros Organics; PVA9k～10k and PVA13K～23K alcoholysis degree is respectively 80% and 87～89%, purchases the company in Sigma-Aldrich.The digitized representation molecular weight of PVA back represents that as 2K molecular weight is 2000.
The present invention is not limited to given several critical materials source, and the PVA molecular weight ranges can be 2k～95K, is preferably 5-25K.
Used organic solvent is N among the step b of modified-reaction of the present invention, and dinethylformamide (DMF) and dimethyl sulfoxide (DMSO) (DMSO) must be handled through drying and dehydrating before using, otherwise can have a strong impact on reaction effect.
Used alkaline matter is to be selected from a kind of in tertiary butyl potassium alcoholate, butyllithium, sodium amide, potassium hydroxide, sodium hydroxide, potassium hydride KH and the sodium hydride among the step b of the present invention, preferred potassium hydroxide and sodium hydroxide.The amount of substance ratio of X is 1～20 in alkali number and the substance A, preferred 5-10.
Used phase-transfer catalyst is Tetrabutyl amonium bromide (TBAB), cetyl trimethylammonium bromide (CTMAB), palmityl trimethyl ammonium chloride (CTMAC), 4-butyl ammonium hydrogen sulfate (TBSB), tetrabutylammonium iodide (TBAI) among the step b of modified-reaction of the present invention.The consumption mol ratio of X and phase-transfer catalyst is 0.01～1 in the substance A, is preferably 0.1～0.5.
The concentration range of used PVA is 1～50mg/ml among the step b of modified-reaction of the present invention, and optimum range is 8～15mg/ml.
Required reaction time range 1～100h among the step b of modified-reaction of the present invention is for guaranteeing halogen ethanoyl/monochloromethyl sufficient reacting, preferred reaction time 24～36h; 0～100 ℃ of temperature of reaction, preferred 50～70 ℃.
The PVA molecular chain is connected with ehter bond with halogen acetylize/halomethylation polystyrene among the step b of modified-reaction of the present invention, and the coupling mode is different with end group grafting PEG in the document, belongs to the side chain graft coupling, helps forming homogeneous coating.
When step b finishes, reacting liquor while hot is filtered, then solid matter is used a large amount of hot washes, remove the PVA of modified polystyrene surface adhesion, filter then and vacuum-drying.
Solid product of the present invention be the surface grafting coupling crosslinked polystyrene of PVA, the oversized hole polystyrene microsphere of particularly surperficial coupling PVA.
The technique effect that the present invention produces: in the even coupling of polystyrene surface one deck PVA polymer, coating connects by stable chemical bond, and the hydrophilicity of polystyrene surface is improved greatly, and proteic non-specific adsorption ability is obtained very big reduction.
Polystyrene material hydrophilic modification method of the present invention, it is material modified to obtain a kind of new polystyrene, has important use and be worth in biotechnology and chromatographic separation.
Embodiment
Embodiment one
The chlorine acetylation of A polystyrene
Add 0.8g ordinary polystyrene plate in the 50ml flask, the 20ml methylene dichloride, aluminum trichloride (anhydrous) 1.2g, magneton stirs, the solution becomes yellowly,, drip chloroacetyl chloride 0.8ml then, 30 ℃ of oil bath reaction 5h.With reaction solution suction filtration under anhydrous state, separate the solid matter obtain and pour into rapidly in the cryosel acid and stir, filter once more and be washed till neutrality with deionized water, filter with absolute ethanol washing more at last, dry in vacuum drying oven.
Dried chloroacetylation polystyrene is measured cl content with the sodium hydroxide scorification, and infrared spectra (FTIR) analysis revealed is compared at 1683cm before sample and the reaction
-1The strong carbonylic stretching vibration absorption peak that links to each other with the benzene evil idea appears, at 645cm
-1A very strong chlorine atom (Cl) stretching vibration peak has appearred in the place.B chloroacetylation polystyrene coupling PVA
With 5mlDMF the above-mentioned chloroacetylation polystyrene 0.6g swelling that obtains is spent the night; the DMF solution that adds 35ml PVA2K guarantees that PVA concentration is 20mg/ml in the reaction system, adds Tetrabutyl amonium bromide 0.4g under whipped state successively; sodium hydroxide 0.8g, 70 ℃ of oil bath reaction 24h.Reacting liquor while hot is filtered, then solid matter is used a large amount of hot washes, remove the PVA of modified polystyrene surface adhesion, filter then and vacuum-drying.The FTIR analysis revealed is at 3433cm
-1The very strong hydroxyl absorption peak of appearance at place; At 1114cm
-1The asymmetric stretching vibration absorption peak of C-O-C has appearred in the place; 645cm in chloroacetylation polystyrene infrared spectra
-1Locate very strong C-Cl stretching vibration peak and disappear, above-mentioned this three places variation shows that all PVA successfully is coupled on the polystyrene microsphere.
Embodiment two
The chlorine acetylation of A polystyrene
Add the 0.8g polystyrene microsphere in the 50ml flask, 24ml dithiocarbonic anhydride, aluminum trichloride (anhydrous) 1.06g, magneton stirs, the solution becomes yellowly,, drip chloroacetyl chloride 0.3ml then, 50 ℃ of oil bath reaction 3h.With reaction solution suction filtration under anhydrous state, separate the solid matter obtain and pour into rapidly in the cryosel acid and stir, filter once more and be washed till neutrality with deionized water, filter with absolute ethanol washing more at last, dry in vacuum drying oven.The microballoon cl content is 12.02% after the modification.
B chloroacetylation polystyrene coupling PVA
With 5mlDMF the above-mentioned chloroacetylation polystyrene microsphere 1.0g swelling that obtains is spent the night; the DMF solution that adds 35mlPVA9K～10K; guarantee that PVA concentration is 20mg/ml in the reaction system; under the stirring arm whipped state, add tetrabutylammonium iodide 0.76g successively; potassium hydroxide 1.15g, 70 ℃ of oil bath reaction 24h.Reacting liquor while hot is filtered, then solid matter is used a large amount of hot washes, remove the adherent PVA of modified polystyrene microsphere surface, filter then and vacuum-drying, the microballoon hydroxy radical content 4.212mmol/g dry bulb that obtains, PVA coupling amount is 0.59mg/m
2Dry bulb.
Embodiment three
The acetobrom reaction of A polystyrene
Add the 1g polystyrene microsphere in the 50ml flask, 24ml dithiocarbonic anhydride, aluminum trichloride (anhydrous) 1.5g, magneton stirs, the solution becomes yellowly,, dripping bromine acetyl bromide 0.4ml then, 50 ℃ of oil baths reaction 3h.With reaction solution suction filtration under anhydrous state, separate the solid matter obtain and pour into rapidly in the cryosel acid and stir, filter once more and be washed till neutrality with deionized water, filter with absolute ethanol washing more at last, dry in vacuum drying oven.The microballoon bromine content is 25.54% after the modification.
B acetobrom polystyrene coupling PVA
With 5mlDMF the above-mentioned acetobrom polystyrene microsphere 0.6g swelling that obtains is spent the night; the DMF solution that adds 35mlPVA22K; guarantee that PVA concentration is 10mg/ml in the reaction system; under the stirring rake whipped state, add cetyl trimethylammonium bromide 0.44g successively; potassium hydroxide 1.10g, 70 ℃ of oil bath reaction 24h.Reacting liquor while hot is filtered, then solid matter is used a large amount of hot washes, remove the adherent PVA of modified polystyrene microsphere surface, filter then and vacuum-drying, the microballoon hydroxy radical content 3.867mmol/g dry bulb that obtains, PVA coupling amount is 0.86mg/m
2Dry bulb.
Embodiment four
The chloromethylation of A polystyrene
Add the 10g polystyrene microsphere in the 250ml flask, the 70ml chloromethyl ether, stirring rake stirs, and 25 ℃ of constant temperature 1h drop into Zinc Chloride Anhydrous 8g, and solution becomes brown, begins to heat up 50 ℃ of oil bath reaction 10h then.With reaction solution suction filtration under anhydrous state, separate the solid matter obtain and pour into rapidly in the cryosel acid and stir, filter once more and be washed till neutrality with deionized water, filter with absolute ethanol washing more at last, dry in vacuum drying oven.The microballoon cl content is 19.28% after the modification.
B chloromethylated polystyrene coupling PVA
With 50mlDMF the above-mentioned chloromethylated polystyrene microballoon 5g swelling that obtains is spent the night, the DMF solution that adds 250mlPVA22K, guarantee that PVA concentration is 15mg/ml in the reaction system, under the stirring rake whipped state, add 4-butyl ammonium hydrogen sulfate 4.61g successively, sodium hydroxide 8.70g, 70 ℃ of oil bath reaction 24h.Reacting liquor while hot is filtered, then solid matter is used a large amount of hot washes, remove the adherent PVA of modified polystyrene microsphere surface, filter then and vacuum-drying, the microballoon hydroxy radical content 3.837mmol/g dry bulb that obtains, PVA coupling amount is 0.98mg/m
2Dry bulb.
Embodiment five
The chloromethylation of A polystyrene
Add the 2g polystyrene microsphere in the 100ml flask, the 40ml methylene dichloride, 1,4-dichloro methyl butyl ether 10ml, stirring rake stirs and makes the abundant swelling of Archon, adds anhydrous stannic chloride 3ml again, 40 ℃ of oil bath reaction 6h.With reaction solution suction filtration under anhydrous state, separate the solid matter obtain and pour into rapidly in the cryosel acid and stir, filter once more and be washed till neutrality with deionized water, filter with absolute ethanol washing more at last, dry in vacuum drying oven.The microballoon cl content is 16.8% after the modification.
B chloromethylated polystyrene coupling PVA
With 5mlDMF the above-mentioned chloromethylated polystyrene microballoon 0.6g swelling that obtains is spent the night, the DMSO solution that adds 35mlPVA13K～23K, guarantee that PVA concentration is 10mg/ml in the reaction system, under the stirring arm whipped state, add tetrabutylammonium iodide 0.53g successively, sodium hydroxide 0.91g, 70 ℃ of oil bath reaction 24h.Reacting liquor while hot is filtered, then solid matter is used a large amount of hot washes, remove the adherent PVA of modified polystyrene microsphere surface, filter then and vacuum-drying, the microballoon hydroxy radical content 4.012mmol/g dry bulb that obtains, PVA coupling amount is 1.01mg/m
2Dry bulb.
Embodiment six
The acetobrom reaction of A polystyrene
Add the 10g polystyrene microsphere in the 250ml flask, the 150ml methylene dichloride, aluminum trichloride (anhydrous) 19.5g, stirring arm stirs, the solution becomes yellowly,, dripping bromine acetyl bromide 8.5ml then, 50 ℃ of oil baths reaction 3h.With reaction solution suction filtration under anhydrous state, separate the solid matter obtain and pour into rapidly in the cryosel acid and stir, filter once more and be washed till neutrality with deionized water, filter with absolute ethanol washing more at last, dry in vacuum drying oven.The microballoon bromine content is 27.78% after the modification.
B acetobrom polystyrene coupling PVA
With 50mlDMSO the above-mentioned acetobrom polystyrene microsphere 6g swelling that obtains is spent the night; the DMSO solution that adds 350mlPVA13K～23K; guarantee that PVA concentration is 15mg/ml in the reaction system; under the stirring arm whipped state, add Tetrabutyl amonium bromide 3.362g successively; sodium hydroxide 6.68g, 70 ℃ of oil bath reaction 36h.Reacting liquor while hot is filtered, then solid matter is used a large amount of hot washes, remove the adherent PVA of modified polystyrene microsphere surface, filter then and vacuum-drying, the microballoon hydroxy radical content 3.733mmol/g dry bulb that obtains, PVA coupling amount is 0.95mg/m
2Dry bulb.
Claims (18)
1. the method for hydrophilic modifying is carried out on a p-poly-phenyl vinyl material surface, comprises the steps:
A. benzene ring of polystyrene is reacted the substance A that obtains possessing following general formula through Friedel-Crafts,
Wherein, R is C=O or H, and X is Cl or Br.
B. under the alkaline matter existence condition, the A and the phase-transfer catalyst of gained joined in the organic solvent that is dissolved with PVA, make PVA and polystyrene by the ehter bond coupling, the coupling amount of PVA is at 0.8-1.0mg/m
2In the scope.
2. method according to claim 1 is characterized in that, described polystyrene is a crosslinked polystyrene.
3. method according to claim 1 is characterized in that, described polystyrene is crosslinked polystyrene microsphere or polystyrene board.
4. method according to claim 1 is characterized in that, the functional group RCHX of described substance A is halogen ethanoyl or monochloromethyl.
5. method according to claim 1 is characterized in that, the functional group RCHX of described substance A is chloracetyl or chloromethyl.
6. method according to claim 1 is characterized in that, described PVA molecular weight ranges is 2k～95K.
7. method according to claim 1 is characterized in that, described PVA molecular weight ranges is 5-25K.
8. method according to claim 1 is characterized in that described alkaline matter is selected from one or several in tertiary butyl potassium alcoholate, butyllithium, sodium amide, potassium hydroxide, sodium hydroxide, potassium hydride KH and the sodium hydride.
9. method according to claim 1 is characterized in that, among the described step b in the substance A consumption mol ratio of X and alkali be 1～20.
10. method according to claim 1 is characterized in that, among the described step b in the substance A consumption mol ratio of X and alkali be 5～10.
11. method according to claim 1 is characterized in that, described organic solvent is selected from N, one or several of dinethylformamide and dimethyl sulfoxide (DMSO).
12. method according to claim 1 is characterized in that, the reaction times among the described step b is 1～100h, 0～100 ℃ of temperature of reaction.
13. method according to claim 1 is characterized in that, the reaction times among the described step b is 24～36h, 50～70 ℃ of temperature of reaction.
14. method according to claim 1, it is characterized in that described phase-transfer catalyst is selected from one or several in Tetrabutyl amonium bromide, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, 4-butyl ammonium hydrogen sulfate and the tetrabutylammonium iodide.
15. method according to claim 1 is characterized in that, among the described step b in the substance A consumption mol ratio of X and phase-transfer catalyst be 0.01～1.
16. method according to claim 1 is characterized in that, among the described step b in the substance A consumption mol ratio of X and phase-transfer catalyst be 0.1～0.5.
17. the product of the method for surface hydrophilic modification polystyrene material according to claim 1 preparation, it is characterized in that the polystyrene material surface comprise the internal surface grafting coupling of microballoon duct one deck be rich in the hydrophilic PVA molecular chain of hydroxyl, can be used for further modification or derive.
18. the product of the polystyrene macroporous microsphere hydrophilic modifying of method preparation according to claim 1, it is characterized in that the outside surface of microballoon and the wetting ability macromole PVA that duct internal surface coupling one deck is rich in hydroxyl, can be used as the chromatographic media of sharp separation biomacromolecule after further deriving.
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| EP2428499A1 (en) | 2010-09-13 | 2012-03-14 | Construction Research & Technology GmbH | Use of compounds containing aluminium and silicon for producing a hydrophilic material product |
| WO2013030011A1 (en) | 2011-08-26 | 2013-03-07 | Construction Research & Technology Gmbh | Hydrophilic building products |
| CN102872732A (en) * | 2012-10-22 | 2013-01-16 | 浙江理工大学 | Hydrophilic modification method for polytetrafluoroethylene microporous material |
| CN102974238B (en) * | 2012-11-02 | 2014-08-13 | 东华大学 | Film surface hydrophilicity modifying method through PVA grafting by utilizing biological preparation |
| CN103601854B (en) * | 2013-07-25 | 2015-10-14 | 中国石油大学(华东) | A kind of method of surface hydrophilic modification of polystyrene material |
| 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 |
| CN103897205B (en) * | 2014-04-02 | 2016-04-13 | 四川大学 | A kind of modified styrene polymer surface hydrophilic modification masterbatch and preparation method thereof |
| CN104497214B (en) * | 2015-01-19 | 2017-04-26 | 北京石油化工学院 | Preparation method of solid phase synthesis medium based on integrated polymer material |
| CN104815631B (en) * | 2015-04-20 | 2017-08-11 | 青岛盛瀚色谱技术有限公司 | Synthetic method of the hydrophilic ionic to chromatograph packing material |
| 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 |
| CN110540671A (en) * | 2019-09-25 | 2019-12-06 | 合肥科拜耳材料科技有限公司 | Preparation method of modified HIPS (high impact polystyrene) composite material |
| CN111040226A (en) * | 2019-12-02 | 2020-04-21 | 中南大学 | Preparation method of hypercrosslinked polymer rich in hydrogen bond acceptor oxygen atoms and application of hypercrosslinked polymer |
| CN112538183B (en) * | 2020-10-27 | 2022-05-24 | 福建农林大学 | Preparation method of surface hydroxylated polystyrene resin |
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