CN102675654A - Preparation method of segmented polymer brush - Google Patents
Preparation method of segmented polymer brush Download PDFInfo
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- CN102675654A CN102675654A CN2012101053702A CN201210105370A CN102675654A CN 102675654 A CN102675654 A CN 102675654A CN 2012101053702 A CN2012101053702 A CN 2012101053702A CN 201210105370 A CN201210105370 A CN 201210105370A CN 102675654 A CN102675654 A CN 102675654A
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- AWTMQOWVDOCBFI-UHFFFAOYSA-N CC(C)(C(NCCC[Si](OC)(OC)OC)=O)Br Chemical compound CC(C)(C(NCCC[Si](OC)(OC)OC)=O)Br AWTMQOWVDOCBFI-UHFFFAOYSA-N 0.000 description 1
- OZYLROBYEPHSJK-UHFFFAOYSA-N CC1O[Si+]2(CCCN)OC1C(C)O2 Chemical compound CC1O[Si+]2(CCCN)OC1C(C)O2 OZYLROBYEPHSJK-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a preparation method of a segmented polymer brush. The preparation method comprises the following steps: a) soaking a substrate of which the surface is modified with hydroxyl in an amino-group modifying solution, and introducing amino group onto the substrate; b) reacting polybasic halogen-containing initiator with the amino group on the substrate to obtain a substrate containing an initiator group; c) mixing the substrate containing the initiator group with a catalyst, a ligand and a styrene monomer to perform atom transfer radical polymerization so as to obtain a styrene polymer brush; and d) performing click chemical reaction between the styrene polymer brush subjected to azidation treatment and methoxypolyethylene glycol acetylene to obtain the styrene-b-vinol polymer brush. The preparation method of the stimuli responsive segmented polymer brush has the advantages that conditions are mild, the selection range of the monomer is wide, and the production application range is wide.
Description
Technical field
The present invention relates to the synthetic field of polymkeric substance, be specifically related to a kind of preparation method of block polymer brush.
Background technology
Polymer brush is meant that an end of polymer molecular chain is connected in substrate surface or interface and a kind of special macromolecular structure that forms; It is the typical model of the many actual Polymer Systems of research; As: polymer micelle; Adsorb or be grafted on the segmented copolymer of liquid liquid, liquid gas, solid-liquid interface, be grafted to the polymkeric substance of substrate surface etc.Be meant that polymer brush can make response change under certain ambient conditions (like light, temperature, solvent, electric field, magnetic field, stress etc.) stimulates and have stimulating responsive polymer brush, thereby the conformation of polymer chain changes surface properties such as surface wettability, frictional property, cementability, adsorptivity etc. is changed.Stimulating responsive polymer brush has purposes very widely, in fields such as stable, the delivery of drug of colloidal particle, proteic identification and reversible adsorption, micro flow chip, chemical sensors important use is arranged.
At present, preparation block polymer brush mainly contains " being grafted to the surface " and " from surface grafting " two kinds of methods.Method is meant under suitable condition " to be grafted to the surface ", has the polymer chain of function end group and the functional group of substrate surface and reacts, thereby polymer chain is grafted to substrate surface.This method is comparatively easy, but finally the density of polymers grafted chain is lower (to be generally less than 0.1chains/nm because the influence of the reactive behavior of sterically hindered and end group makes
2).
" from surface grafting " method is meant that polymer monomer passes through covalent linkage and at the initiator initiated polymerization on surface, forms the polymer chain that is grafted to the surface.This method mainly contains several kinds of polymerization means: active ring-opening polymerization, active anionic polymerization, living cationic polymerization, ring opening metathesis polymerization, nitrogen oxygen regulation and control polymerization, reversible addition-fragmentation chain transfer free radical polymerization, ATRP.Because of this method through monomer polymerization reactions, effectively overcome sterically hindered, so, can reach higher grafting density usually.But this method has restriction to monomer, must be that the monomer that contains vinyl could cause ATRP, has limited the kind of polymer brush.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of mild condition, the preparation method of the block polymer brush that the monomer range of choice is wide.
In order to solve above technical problem, the invention provides a kind of preparation method of block polymer brush, comprising:
The substrate of a) surface hydroxyl being modified is soaked in amido modified agent solution, in said substrate, introduces amino;
B) with polynary Halogen initiator and said suprabasil amino reaction, obtain containing the substrate of initiator group;
C) the said substrate that contains the initiator group is mixed with catalyzer, part, styrene monomer, ATRP takes place, obtain the styrene polymer brush;
D) said styrene polymer brush is taken place to click chemical reaction with methoxypolyethylene glycol acetylene after azide is handled, obtain vinylbenzene-b-polyvinyl alcohol polymer brush.
Preferably, said polynary Halogen initiator is 2-bromine isobutyl acylbromide or 2-chlorine isobutyryl chloride.
Preferably, the substrate in the step a) is silicon chip, slide or polyester chips.
Preferably, said amido modified agent solution is the toluene solution of (3-aminopropyl) Trimethoxy silane.
Preferably, said catalyzer is one or more in cupric chloride, cuprous chloride, cupric bromide and the cuprous bromide.
Preferably, said part is N, N, N ', N ", N " PMDETA.
Preferably, styrene monomer and methoxypolyethylene glycol acetylene are 1: 400～800 in molar ratio.
Preferably, step d) is specially:
D1) the styrene polymer brush that step c) is obtained immerses and contains in the organic solution of azide reagent, reacts, and obtains the end capped styrene polymer brush of azido group;
D2) immersion of the end capped styrene polymer brush of said azido group is contained in the organic solution of methoxypolyethylene glycol acetylene and part, take place to click chemical reaction, obtain vinylbenzene-b-polyvinyl alcohol polymer brush.
Preferably, said azide reagent is sodiumazide or potassium azide.
Preferably, the solvent of said organic solution is toluene or N, dinethylformamide.
The invention provides a kind of preparation method of block polymer brush, comprising: the substrate of a) surface hydroxyl being modified is soaked in amido modified solution, in said substrate, introduces amino; B) with polynary Halogen initiator and said suprabasil amino reaction, obtain containing the substrate of initiator group; C) the said substrate that contains the initiator group is mixed with catalyzer, part, styrene monomer, ATRP takes place, obtain the styrene polymer brush; D) said styrene polymer brush is taken place to click chemical reaction with methoxypolyethylene glycol acetylene after azide is handled, obtain vinylbenzene-b-polyvinyl alcohol polymer brush.Preparing method provided by the invention is to prepare polymer brush with " surface grafting " method, is forming the block polymer brush through reacting with glycol methyl ether acetylene through click chemistry behind the styrene monomer ATRP in the substrate that hydroxyl modified is arranged again.Because after forming vinylbenzene, ATRP has just stopped, need modifying the end group of styrene polymer brush, just can carry out click chemistry reaction with the polyoxyethylene glycol block.And the modifier of said end group is an azido group, can combine rapidly with ethynyl, does not need conditions such as HTHP, and with regard to polymerizable, condition is gentle under the normal temperature; In addition, what preparation method provided by the invention selected for use is that monomer also has methoxypolyethylene glycol acetylene except that vinylbenzene, makes polymkeric substance be brushed with new function, so expanded the use field of styrene polymer brush.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
Explanation of nouns:
ATRP (Atom Transfer Radical Polymerization; ATRP): this method is an initiator with simple Organohalogen compounds mainly; Transition metal complex is the halogen atom carrier; Through redox reaction, between spike and dormancy kind, set up running balance, realize control to polyreaction.
The ATRP reaction mechanism
The transition metal complex M of low-oxidation-state
t nLY is from Organohalogen compounds P
m" extraction " halogen atom X among the X produces high oxidation state species M
t N+1(being the dormancy kind) and radical P
m, follow radical P
mProduce monomer radical (being spike) with monomer M reaction, spike can continue trigger monomer carry out living polymerization also can be from high oxidation state transition metal complex XM
t N+1Capture halogen atom self among the LY and become the dormancy kind.K wherein
a, k
dBe respectively activation and inactivation reaction rate constant; k
p, k
tFor increasing and rate constant of termination.(macromole, 2000,33,4039.Macromolecules?2000，33，4039。)
Click chemistry reaction (click chemistry):
The Click chemical reaction is through Cu (I) catalysis alkynyl and azido-reaction, generates 1 of regioselectivity, the 4-triazole, and its reaction mechanism is as follows.
The click chemistry reaction mechanism
The invention provides a kind of preparation method of block polymer brush, comprising:
The substrate of a) surface hydroxyl being modified is soaked in amido modified solution, in said substrate, introduces amino;
B) with polynary Halogen initiator and said suprabasil amino reaction, obtain containing the substrate of initiator group;
C) the said substrate that contains the initiator group is mixed with catalyzer, part, styrene monomer, ATRP takes place, obtain the styrene polymer brush;
D) said styrene polymer brush is taken place to click chemical reaction with methoxypolyethylene glycol acetylene after azide is handled, obtain vinylbenzene-b-polyvinyl alcohol polymer brush.
The present invention so used " from surface grafting " this method, uses ATRP to combine with the click chemistry reacting phase in order to obtain the higher block polymer brush of grafting density earlier,, through monomer polymerization reactions, effectively overcome sterically hindered.Use the principle of click chemistry reaction on this basis, polyoxyethylene glycol and PS are reacted in substrate, form the block polymer brush.
Click chemistry reaction is meant selects the raw material that is easy to get for use, through reliable, efficient and tool optionally chemical reaction realize that the carbon heteroatoms connects (C-X-C), low-cost, fast synthetic a large amount of new compounds compound method.Its core is to utilize a series of reliable, modular reactions to generate to contain heteroatomic compound.These reactions have following characteristic usually: (1) is raw materials used to be easy to get; (2) operation is simple, and mild condition is insensitive to oxygen, water; (3) product yield is high, selectivity is good; (4) product is prone to purifying, aftertreatment is simple.On this basis, the inventor is through discovering, azido group and ethynyl have good reactive behavior, and the catalysis of the higher copper catalyst in cheapness of transformation efficiency causes down polymerization fast, mild condition.
According to the present invention, the preparation polymer brush must carry out the preparation of substrate earlier.At first hydroxyl modified is carried out in substrate.The substrate that the present invention uses is preferably silicon chip, slide or polyester chips; Silicon chip more preferably.Silicon chip is soaked in the mixing solutions of sulfuric acid and ydrogen peroxide 50, the hydroxyl that obtains after the decomposing hydrogen dioxide solution is grafted on the silicon chip, obtain the substrate of hydroxyl modified.According to the present invention, said sulfuric acid and said ydrogen peroxide 50 are 5～7 by volume: 3～5 are mixed with mixing solutions.
In the substrate of the said hydroxyl modified for preparing, introduce amino, method is specially, and the substrate of the said hydroxyl modified for preparing is soaked 20～30min in amido modified dose dissolves, and more elects 22-28min as, most preferably is 24～26min.The purpose that immerses amido modified dose of broad liquid is amino in order in the substrate of hydroxyl modified, to introduce; According to the present invention, said amido modified dose is preferably (3-aminopropyl) Trimethoxy silane.Methoxyl group wherein and hydroxyl reaction; Hydroxyl loses Wasserstoffatoms; Methoxyl group weakens disconnection with the Siliciumatom bond energy and combines to generate methyl alcohol with Wasserstoffatoms, and Siliciumatom combines with the Sauerstoffatom that loses Wasserstoffatoms, and firm is connected the 3-aminopropyl in the substrate of said hydroxyl modified through Siliciumatom.According to the present invention; Said (3-aminopropyl) Trimethoxy silane solution is preferably the toluene solution of (3-aminopropyl) Trimethoxy silane; The concentration of the toluene solution of said (3-aminopropyl) Trimethoxy silane is preferably 5mM-20mM, more elects 5mM-10mM as, most preferably is 5mM～6mM.According to the present invention, also comprise having the substrate of (3-aminopropyl) Trimethoxy silane under 25 ℃, to dry up said surface grafting with nitrogen.The amido modified reaction equation of substrate is following:
In order to obtain having multiple responsiveness, multi-functional block polymer brush, the present invention uses to have the responsive PS of environmental change and polyethylene glycols compound as grafted monomer.Said polysiloxane compound is preferably YSR 3286; And in order with vinylbenzene chemical reaction to take place to click; With azido group with ethenyl blocking; Polyethylene glycol compound uses methoxypolyethylene glycol acetylene, becomes the click chemistry of ring to react with azido group with ethynyl, obtains product fast.
According to the present invention, polystyrene block obtains through ATRP, can react with amino in order to make styrene monomer; The inventor has used polynary Halogen initiator; With a halogen atom and amino reaction, another halogen atom causes styrene polymerization then, after the finishing polymerization earlier; Obtain the styrene polymer brush, the end group of said polymer brush has the halogen atom end-blocking.According to the present invention, said polynary Halogen initiator is preferably: 2-bromine isobutyl acylbromide or 2-chlorine isobutyryl chloride.According to the present invention, said initiator exists with the solution form, preferred use be toluene or THF as solvent, the mass concentration degree of wherein said polynary Halogen initiator in toluene is 1%～3%.
The substrate preparation process that contains initiator is following:
The preparation process of poly styrene polymer brush is following:
According to the present invention, in order to improve the speed of ATRP, the present invention also has been to use part and catalyzer.Said part is N, N, N ', N ", N " PMDETA (PDMETA).Said catalyzer is preferably one or more in cupric chloride, cuprous chloride, cupric bromide and the cuprous bromide, more preferably, in cupric bromide and the cuprous bromide one or more.
Had the thickness of 12～15nm through the polymer brush of above-mentioned steps preparation, percentage of grafting reaches 0.60～0.69chains/nm
2And has uncle's bromine end-blocking on the said polymer brush.
After obtaining the styrene polymer brush, need end capped halogen atom be removed, change the group that chemical reaction can take place to click with polyoxyethylene glycol into.The inventor discovers that azido group can take place to click chemical reaction with phenylethynyl group, and the methoxypolyethylene glycol acetylene that the present invention uses can use azide reagent to replace end capped halogen atom.So azide provided by the invention reaches the process of reacting with click chemistry and is specially:
D1) the styrene polymer brush that step c) is obtained immerses and contains in the organic solution of azide reagent, reacts, and obtains the end capped styrene polymer brush of azido group;
D2) immersion of the end capped styrene polymer brush of said azido group is contained in the organic solution of methoxypolyethylene glycol acetylene and part, take place to click chemical reaction, obtain vinylbenzene-b-polyvinyl alcohol polymer brush.
According to the present invention, the end-capping reagent of said replacement halogen atom is preferably sodiumazide or potassium azide.The reaction process of azido reaction is following:
The process of click chemistry prepared in reaction vinylbenzene-b-polyvinyl alcohol polymer brush is following:
Block polymer through the above-mentioned steps preparation is brushed the thickness that has had 17～21nm, and percentage of grafting reaches 0.70～0.77chains/nm
2
Preparing method provided by the invention is to prepare polymer brush with " surface grafting " method, is forming the block polymer brush through reacting with glycol methyl ether acetylene through click chemistry behind the styrene monomer ATRP in the substrate that hydroxyl modified is arranged again.Because after forming vinylbenzene, ATRP has just stopped, need modifying the end group of styrene polymer brush, just can carry out click chemistry reaction with the polyoxyethylene glycol block.And the modifier of said end group is an azido group, can combine rapidly with ethynyl, does not need conditions such as HTHP, and with regard to polymerizable, condition is gentle under the normal temperature; In addition, what preparation method provided by the invention selected for use is that monomer also has methoxypolyethylene glycol acetylene except that vinylbenzene, makes polymkeric substance be brushed with new function, so expanded the use field of styrene polymer brush.
Below be specific embodiment provided by the invention, set forth the present invention program in detail: need to prove N provided by the invention, N, N ', N ", N " Pentamethyldiethylenetriamine (PMDETA), methoxypolyethylene glycol (M
w=5000g/mol), α-bromine isobutyl acylbromide (BIBB), 2 bromo 2 methyl propionic acid ethyl ester (EBIB), (3-aminopropyl) Trimethoxy silane (APTMS), sodium hydride (NaH) and propine bromine (Propargyl bromide) be available from Aldrich company; Styrene monomer (St), N, dinethylformamide (DMF), toluene, cupric bromide (CuBr
2), cuprous bromide (CuBr) and sodiumazide (NaN
3) all purchase in Chemical Reagent Co., Ltd., Sinopharm Group.
After styrene monomer was handled three times with 5% aqueous sodium hydroxide solution, washing was to neutral.Spend the night with anhydrous magnesium sulfate drying in the back, underpressure distillation behind the suction filtration, and distillate is collected with the ampoule that dewaters.Cuprous bromide with acetate purify, after the washing with alcohol, vacuum-drying.DMF uses the hydrolith dried overnight, and underpressure distillation is collected with the ampoule that dewaters.Toluene and triethylamine reflux until solution turned blue with sodium and UVNUL MS-40 respectively, collect with the ampoule that dewaters.Single-sided polishing silicon chip Si (111) purchases in Shanghai Alloy Silicon Material Co., Ltd..
Embodiment 1:
To carrying out the modification of 2-bromine isobutyl acylbromide at the bottom of the silicon wafer-based
Cleaning silicon wafer is placed the toluene solution (10mM) of 30ml (3-aminopropyl) Trimethoxy silane, nitrogen protection reaction 24 hours down.After reaction finishes, silicon chip is taken out, wash repeatedly with toluene and ethanol, and sonic oscillation three times (each 20 minutes), the back dries up subsequent use with nitrogen.The silicon chip of said silicon chip for handling with sulfuric acid and hydrogen peroxide mixed solution (volume ratio is 7: 3).
Above-mentioned APTMS is handled 2-bromine isobutyl acylbromide (BIBB)/toluene solution that the back silicon chip places 30ml 3% (mass ratio), normal temperature hold over night.After reaction finishes, silicon chip is taken out, wash repeatedly with toluene and ethanol, and sonic oscillation three times (each 20 minutes), the back dries up with nitrogen, obtains the silicon base that the ATRP initiator is contained on the surface.
Embodiment 2:
ATRP synthetic polystyrene homopolymerization brush
Cupric bromide (18mg), cuprous bromide (250mg), N, N, N ', N ", " pentamethyl-diethylenetriamine (339 μ l) adds in the polymerizing pipe of 30ml N successively, adds the 30ml styrene monomer subsequently.This heterogeneous solution through four times freezing-vacuumize-the thaw cycles deoxygenation.Silicon chip after the initiator modification is placed the Schlenk bottle of 30ml, through vacuumize-three bouts of inflated with nitrogen remove oxygen.After being stirred to homogeneous phase solution under 90 ℃, be transferred in the Schlenk bottle that silicon chip is housed with syringe, 90 ℃ were reacted 7.5 hours.Silicon chip is taken out in the reaction back that finishes, and washes repeatedly with THF, removes not grafting material of surface in ultrasonic 20 minutes with being placed in the tetrahydrofuran solution, dries up with nitrogen again.
Embodiment 3:
The synthetic Si/SiO of Click reaction
2/ PS-b-PEG
Silicon chip after the surface-treated is placed the N of 30ml, in the dinethylformamide solution, add the 0.7g sodiumazide again, after stirring 12 hours under the lucifuge condition, take out silicon chip; Use N, N-N, acetone; Deionized water washes repeatedly, and nitrogen dries up, and obtains the end capped Si/SiO of nitrine
2/ PS-N
3
With 0.6g methoxypolyethylene glycol acetylene, N, N, N ', N ", " dinethylformamide (30ml) joins in the Schlenk bottle that fills nitrine end-blocking silicon chip N for pentamethyl-diethylenetriamine (21 μ l), N.Through twice freezing-vacuumize-thaw cycles after, under nitrogen protection, add cuprous bromide (14.3g).Again through 2 times freezing-vacuumize-feed nitrogen again after the thaw cycles, 60 ℃ of reactions 12 hours.After reaction finishes, take out silicon chip, wash repeatedly to remove surperficial unreacted matters with absolute ethyl alcohol and deionized water, nitrogen dries up, and obtains polystyrene-poly terepthaloyl moietie segmented copolymer brush.
Embodiment 4:
The synthetic Si/SiO of Click reaction
2/ PS-b-PEG
Prepare the poly styrene polymer brush according to embodiment 1-3.
The silicon chip that will contain the PS brush places the N of 30ml, in the dinethylformamide solution, adds the 0.7g sodiumazide again, after stirring 12 hours under the lucifuge condition, takes out silicon chip; Use N, dinethylformamide, acetone; Deionized water washes repeatedly, and nitrogen dries up, and obtains the end capped Si/SiO of nitrine
2/ PS-N
3
With 0.7g methoxypolyethylene glycol acetylene, N, N, N ', N ", " dinethylformamide (30ml) joins in the Schlenk bottle that fills nitrine end-blocking silicon chip N for pentamethyl-diethylenetriamine (21 μ l), N.Through twice freezing-vacuumize-thaw cycles after, under nitrogen protection, add cuprous bromide (14.3g).Again through 2 times freezing-vacuumize-feed nitrogen again after the thaw cycles, 60 ℃ of reactions 8 hours.After reaction finishes, take out silicon chip, wash repeatedly to remove surperficial unreacted matters with absolute ethyl alcohol and deionized water, nitrogen dries up, and obtains polystyrene-poly terepthaloyl moietie segmented copolymer brush.
Embodiment 5:
The synthetic Si/SiO of Click reaction
2/ PS-b-PEG
Prepare the poly styrene polymer brush according to embodiment 1-3.
The silicon chip that will contain the PS brush places the N of 30ml, in the dinethylformamide solution, adds the 0.7g sodiumazide again, after stirring 12 hours under the lucifuge condition, takes out silicon chip; Use N, dinethylformamide, acetone; Deionized water washes repeatedly, and nitrogen dries up, and obtains the end capped Si/SiO of nitrine
2/ PS-N
3
With 1.0g methoxypolyethylene glycol acetylene, N, N, N ', N ", " dinethylformamide (30ml) joins in the Schlenk bottle that fills nitrine end-blocking silicon chip N for pentamethyl-diethylenetriamine (21 μ l), N.Through twice freezing-vacuumize-thaw cycles after, under nitrogen protection, add cuprous bromide (14.3g).Again through 2 times freezing-vacuumize-feed nitrogen again after the thaw cycles, 60 ℃ of reactions 12 hours.After reaction finishes, take out silicon chip, wash repeatedly to remove surperficial unreacted matters with absolute ethyl alcohol and deionized water, nitrogen dries up, and obtains polystyrene-poly terepthaloyl moietie segmented copolymer brush.
More than the preparation method of a kind of block polymer brush provided by the invention has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and embodiment; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of a block polymer brush is characterized in that, comprising:
The substrate of a) surface hydroxyl being modified is soaked in amido modified agent solution, and hydroxyl and said amido modified dose of reaction are introduced amino in said substrate;
B) with polynary Halogen initiator and said suprabasil amino reaction, obtain containing the substrate of initiator group;
C) the said substrate that contains the initiator group is mixed with catalyzer, part, styrene monomer, ATRP takes place, obtain the styrene polymer brush;
D) said styrene polymer brush is taken place to click chemical reaction with methoxypolyethylene glycol acetylene after azide is handled, obtain vinylbenzene-b-polyvinyl alcohol polymer brush.
2. preparation method according to claim 1 is characterized in that, said polynary Halogen initiator is 2-bromine isobutyl acylbromide or 2-chlorine isobutyryl chloride.
3. preparation method according to claim 1 is characterized in that, the substrate in the step a) is silicon chip, slide or polyester chips.
4. preparation method according to claim 4 is characterized in that, said amido modified agent solution is the toluene solution of (3-aminopropyl) Trimethoxy silane.
5. preparation method according to claim 1 is characterized in that, said catalyzer is one or more in cupric chloride, cuprous chloride, cupric bromide and the cuprous bromide.
6. preparation method according to claim 1 is characterized in that,
Said part is N, N, N ', N ", N " PMDETA.
7. preparation method according to claim 1 is characterized in that, styrene monomer and methoxypolyethylene glycol acetylene are 1: 400～800 in molar ratio.
8. preparation method according to claim 1 is characterized in that step d) is specially:
D1) the styrene polymer brush that step c) is obtained immerses and contains in the organic solution of azide reagent, reacts, and obtains the end capped styrene polymer brush of azido group;
D2) immersion of the end capped styrene polymer brush of said azido group is contained in the organic solution of methoxypolyethylene glycol acetylene and part, take place to click chemical reaction, obtain vinylbenzene-b-polyvinyl alcohol polymer brush.
9. preparation method according to claim 8 is characterized in that, said azide reagent is sodiumazide or potassium azide.
10. preparation method according to claim 9 is characterized in that, the solvent of said organic solution is toluene or N, dinethylformamide.
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| CN103819684A (en) * | 2014-02-17 | 2014-05-28 | 上海交通大学 | Thermo-crosslinked polystyrene polymer, preparation method and applications thereof |
| CN110975329A (en) * | 2019-12-11 | 2020-04-10 | 安徽大学 | Polymer modified straw based on agricultural waste straw and preparation method and application thereof |
| CN111333759A (en) * | 2020-02-26 | 2020-06-26 | 青岛科技大学 | Preparation method of zwitterionic polymer pattern on surface of solid substrate |
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| CN101386672A (en) * | 2008-11-24 | 2009-03-18 | 中国科学院长春应用化学研究所 | Poly(3-butylthiophen)block copolymers and preparation method thereof |
| CN102295731A (en) * | 2011-06-27 | 2011-12-28 | 中国科学院长春应用化学研究所 | Graft modified styrene thermoplastic elastomer and preparation method thereof |
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| CN1486995A (en) * | 2003-07-31 | 2004-04-07 | 上海交通大学 | Multiple-arm star-shaped super-branched polymer brush with several hydroxy groups and its prepn process |
| CN101386672A (en) * | 2008-11-24 | 2009-03-18 | 中国科学院长春应用化学研究所 | Poly(3-butylthiophen)block copolymers and preparation method thereof |
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| CN103819684A (en) * | 2014-02-17 | 2014-05-28 | 上海交通大学 | Thermo-crosslinked polystyrene polymer, preparation method and applications thereof |
| CN103819684B (en) * | 2014-02-17 | 2016-05-04 | 上海交通大学 | Poly styrene polymer of heat cross-linking and preparation method thereof, purposes |
| CN110975329A (en) * | 2019-12-11 | 2020-04-10 | 安徽大学 | Polymer modified straw based on agricultural waste straw and preparation method and application thereof |
| CN111333759A (en) * | 2020-02-26 | 2020-06-26 | 青岛科技大学 | Preparation method of zwitterionic polymer pattern on surface of solid substrate |
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