CN101139426A - Method for grafting environment response macromolecule on nano silicon dioxde surface - Google Patents
Method for grafting environment response macromolecule on nano silicon dioxde surface Download PDFInfo
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- CN101139426A CN101139426A CNA2007101197163A CN200710119716A CN101139426A CN 101139426 A CN101139426 A CN 101139426A CN A2007101197163 A CNA2007101197163 A CN A2007101197163A CN 200710119716 A CN200710119716 A CN 200710119716A CN 101139426 A CN101139426 A CN 101139426A
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- 239000005543 nano-size silicon particle Substances 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 20
- 229920002521 macromolecule Polymers 0.000 title abstract 4
- 230000004044 response Effects 0.000 title description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 230000000977 initiatory effect Effects 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229960001866 silicon dioxide Drugs 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- ILLHORFDXDLILE-UHFFFAOYSA-N 2-bromopropanoyl bromide Chemical compound CC(Br)C(Br)=O ILLHORFDXDLILE-UHFFFAOYSA-N 0.000 claims description 4
- GFXHFYHUJAATBP-UHFFFAOYSA-N CO[Si](OC)(OC)CCCC(N)=O Chemical compound CO[Si](OC)(OC)CCCC(N)=O GFXHFYHUJAATBP-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 claims description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000031709 bromination Effects 0.000 abstract 1
- 238000005893 bromination reaction Methods 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 abstract 1
- RIBFXMJCUYXJDZ-UHFFFAOYSA-N propanoyl bromide Chemical compound CCC(Br)=O RIBFXMJCUYXJDZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000004043 responsiveness Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 10
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FRXLFVNGTPQFEJ-UHFFFAOYSA-N 3-bromopropanoyl bromide Chemical compound BrCCC(Br)=O FRXLFVNGTPQFEJ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000000233 Melia azedarach Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a preparation method for organic-inorganic hybrid materials through grafting polymerization-environment responsive macromolecules on the nanometer silicon dioxide surface, belonging to the organic-inorganic hybrid materials synthesis and preparation field. The present invention takes advantage of the action of silicon dioxide with hydroxyl on the surface with the silane coupling agent 3-amino-propyl silane to enable the end to be of an amino group; then the product reacts with the nanometer particle generated from the bromination propionyl bromine reaction; The end of the nanometer particle is the ATRP initiator; finally, the polymerization of the environmentally-responsive macromolecules on the nanometer silicon dioxide surface is initiated in the present of CuBr and PMDETA so as to obtain the target product. The graft rate of the silicon dioxide virgule environmentally-responsive macromolecule core-shell structure nanometer hybrid particles is 60 percent to 70 percent. No reunion of the nanometer hybrid particles appears. The nanometer hybrid particles are uniformly dispersed with environmental responsiveness.
Description
Technical field
The present invention relates to a kind of at nano-silica surface graft polymerization environment-responsive polymer to prepare the method for organic-inorganic hybrid material, belong to the synthetic and preparation field of organic-inorganic hybrid material.
Background technology
Along with science and technology development, the nanometer hybrid of functional materials is the trend of modern material development.By the hydridization of two or more organic/inorganic chemical compositions, make it performance complement and optimization, can prepare new-type functional material.And the nanometer organic/inorganic hybridization material combines the good characteristic of organic polymer, inorganic materials and nano material, has multifarious structure and unique physical and chemical performance, has opened up a brand-new approach for people explore type material.
Nano silicon and environment-responsive polymer can synthesize and obtain the inorganic-organic hybrid material.The nano silicon stable in properties, with low cost, favorable mechanical performance and resistance toheat can be provided; And the environmental response polymkeric substance has unique stimulating responsive because of it, at drug release (Kim E J, Cho S H, Yuk S H.Biomaterials, 2495～2499), enzyme fixes (Zhai MaoLin 2001,22 (18):, HaHongfei, Wu lian.Radiat.Phys.Chem.; 919), feed separation (MorrisG E, Vincent B 1993,42 (4-6):, Snowden MJ.J Colliod Inter Sci, 198～205), chemical machinery (Kuhn W 1997,190 (1):, Hargitay B, Katchalsky A, et al.Nature, 1950,165,514), photonic crystal (Weissman J M, Subkara H B, Tse A S, et al.Science, 1996,274 (5289): 959～963) field has shown good prospects for application.
Because the nano silicon particle diameter is little, specific surface area is big, surface energy is high, reunite very easily mutually, poor with most of polymer materials consistency, adopt the very difficult homodisperse that obtains on the nanoscale of existing general technology, do not reach the nano-filled purpose of particle, can influence the performance of material on the contrary.
Summary of the invention
The purpose of this invention is to provide and a kind ofly do not reunite by the target product that this method obtains in the high molecular method of nano-silica surface grafting environment-responsive, homodisperse has environment-responsive.
Technical scheme of the present invention is:
A. surperficial end group is the preparation of the nano silicon of amino
Add the 1-3g nano silicon successively, 20-60mL toluene and 4-12mL 3-aminocarbonyl propyl Trimethoxy silane (APTS), in reaction system, take out applying argon gas three times, under argon gas atmosphere in 115-120 ℃ of oil bath back flow reaction 12-36h, cooling is left standstill, successively with toluene and acetone supersound washing to remove the silane reagent of absorption, centrifugation, vacuum-drying;
The preparation of the nano silicon of the initiating radical that b. surperficial end is an atom transfer radical polymerization (ATRP)
Add 0.3-0.6g and connect amino nano silicon, 20-40mL toluene and 8-16mL triethylamine, in ice-water bath, splash into the mixing solutions of 4-8mL 2-bromo propionyl bromide and 8-16mL toluene, reaction 4-24h, staticly settle, be the solvent supersonic washing with toluene and acetone successively, centrifugation, vacuum-drying;
C. the preparation of silicon-dioxide/environment-responsive polymer nuclear shell structured nano-hybrid particle
Adding end successively is the nano silicon 0.05-0.3g of the initiating radical of atom transfer radical polymerization; tetrahydrofuran (THF) 1-10mL; environment-responsive high polymer monomer 0.01-0.05mol; cuprous bromide 0.01-0.05g and five methyl diethylentriamine (PMDETA) 17-72uL; under cooled with liquid nitrogen, reactor is taken out applying argon gas three times, under argon shield in 50-65.React 24-48h in ℃ oil bath, leave standstill cooling, successively with tetrahydrofuran (THF) and acetone supersound washing precipitation, centrifugation, vacuum-drying obtains final product.
Above-mentioned environment-responsive monomer is dimethylaminoethyl methacrylate (DMAEMA) or N-N-isopropylacrylamide (NIPA).
The inventive method is to utilize hydroxyl nano silicon in surface and the reaction of silane coupling agent 3-TSL 8330 to make end be with amino group, obtain the terminal nanoparticle of ATRP initiator that is with the reaction of bromo propionyl bromide again, the last environment-responsive monomer that causes in the presence of CuBr and PMDETA obtains target product in the ATRP of nanoparticle surface polymerization.ATRP is a kind of active free radical polymerization.The advantage of common radical polymerization is that the polymerisable monomer scope is wide, polymerizing condition is gentle, polymerization methods is diversified, living polymerization has the excellent controllability of molecular weight to polymerisate, molecular weight distribution, sequential structure, and active free radical polymerization has the advantage of common radical polymerization and living polymerization concurrently, can obtain polymer graft density height, finely dispersed hybrid material.
Experimental result shows, silicon-dioxide/environment-responsive polymer nuclear shell structured nano-hybrid particle the percentage of grafting that is prepared by the inventive method is 60%-70%, there is not agglomeration by transmission electron microscope observing, have good dispersiveness, its pH-temperature-responsive also is verified by the mensuration to nano particle fluid mechanics radius.
The inventive method has following beneficial effect:
1. adopt the ATRP method to obtain hybrid particle at the nanoparticle surface in-situ polymerization, this method is simple, not harsh to environmental requirement, organism is at inorganic nano-particle surface grafting rate height, and can regulate and control the organic composition amount that connects by reaction times and temperature.
2. the hybridized nanometer particle homodisperse that obtains of this method is not reunited, and can be used for further functionalization or industrial processes.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
A. add the 3g nano silicon successively, 60mL dry toluene and 12mL 3-aminocarbonyl propyl Trimethoxy silane, in reaction system, take out applying argon gas three times with the aqueous vapor in the eliminating system, under the Ar atmosphere in 120 ℃ of oil baths back flow reaction 36h, cooling is left standstill, successively with a large amount of toluene and acetone supersound washing to remove the silane reagent of absorption, centrifugation, vacuum-drying 24h under the room temperature obtains surperficial end group and is amino nano silicon;
B. in dry flask, add 0.3g and connect amino nano silicon, 20mL dry toluene and 8mL exsiccant triethylamine, in ice-water bath, slowly splash in the there-necked flask mixing solutions of 2-bromo propionyl bromide 4mL and dry toluene 8mL with dropping funnel, reaction 4h, staticly settling, is the solvent supersonic washing with a large amount of toluene and acetone successively, centrifugation, vacuum-drying 4h under the room temperature obtains the nano silicon of surface end for the initiating radical of ATRP;
C. adding end successively in flask is the nano silicon 0.05g of ATRP initiating radical; THF 2.5mL; monomer DMAEMA 0.03mol, CuBr 0.05g and PMDETA 72uL take out reactor under cooled with liquid nitrogen and fill Ar three times; under the Ar protection, in 50 ℃ of oil baths, react 48h; leave standstill cooling, successively with THF and acetone supersound washing precipitation, centrifugation; vacuum-drying 24h obtains silicon-dioxide/dimethylaminoethyl methacrylate nuclear shell structured nano-hybrid particle.
The particle grafted rate 66.8% of hybridized nanometer by present method preparation does not have agglomeration, has good dispersiveness and pH-temperature-responsive.
Embodiment 2
A. add the 1g nano silicon successively, 20mL dry toluene and 4mL 3-aminocarbonyl propyl Trimethoxy silane, in reaction system, take out applying argon gas three times with the aqueous vapor in the eliminating system, under the Ar atmosphere in 115 ℃ of oil baths back flow reaction 12h, cooling is left standstill, and uses a large amount of toluene successively, the acetone supersound washing is handled to remove the silane reagent of absorption, centrifugation, vacuum-drying 24h under the room temperature obtains surperficial end group and is amino nano silicon;
B. in dry flask, add 0.6g and connect amino nano silicon, 40mL dry toluene and 16mL exsiccant triethylamine, in ice-water bath, slowly splash in the there-necked flask mixing solutions of 2-bromo propionyl bromide 8mL and dry toluene 16mL with dropping funnel, reaction 24h, staticly settling, is the solvent supersonic washing with a large amount of toluene and acetone successively, centrifugation, vacuum-drying 24h under the room temperature obtains the nano silicon of surface end for the initiating radical of ATRP;
C. adding end successively in flask is the nano silicon 0.3g of ATRP initiating radical; THF 3mL, monomer NIPA 0.05mol, CuBr 0.03g and PMDETA 48uL; under cooled with liquid nitrogen, reactor taken out and fill Ar three times; under the Ar protection, in 65 ℃ of oil baths, react 24h, leave standstill cooling; successively with THF and acetone supersound washing precipitation; centrifugation, vacuum-drying 24h under the room temperature obtains silicon-dioxide/N-N-isopropylacrylamide nuclear shell structured nano-hybrid particle.
The particle grafted rate 60.2% of hybridized nanometer by present method preparation does not have agglomeration, has good dispersiveness and pH-temperature-responsive.
Embodiment 3
A and b step are with embodiment 1.
C. adding end successively in flask is the nano silicon 0.1g of ATRP initiating radical; THF 1mL; monomer DMAEMA 0.01mol, CuBr 0.019g and PMDETA 27uL take out reactor under cooled with liquid nitrogen and fill Ar three times; under the Ar protection, in 65 ℃ of oil baths, react 48h; leave standstill cooling, successively with THF and acetone supersound washing precipitation, centrifugation; vacuum-drying 2h under the room temperature obtains silicon-dioxide/dimethylaminoethyl methacrylate nuclear shell structured nano-hybrid particle.
The particle grafted rate 70.5% of hybridized nanometer by present method preparation does not have agglomeration, has good dispersiveness and pH-temperature-responsive.
Embodiment 4
A and b step are with embodiment 2.
C. adding end successively in flask is the nano silicon 0.3g of ATRP initiating radical; THF 10mL; monomer DMAEMA 0.02mol, CuBr 0.01g and PMDETA 17uL take out reactor under cooled with liquid nitrogen and fill Ar three times; under the Ar protection, in 65 ℃ of oil baths, react 48h; leave standstill cooling, successively with THF and acetone supersound washing precipitation, centrifugation; vacuum-drying 24h under the room temperature obtains silicon-dioxide/dimethylaminoethyl methacrylate nuclear shell structured nano-hybrid particle.
The particle grafted rate 64.5% of hybridized nanometer by present method preparation does not have agglomeration, has good dispersiveness and pH-temperature-responsive.
Embodiment 5
A and b step are with embodiment 1.
C. adding end successively in flask is the nano silicon 0.1g of ATRP initiating radical; THF 1mL; monomer NIPA 0.01mol, CuBr 0.019g and PMDETA 27uL take out reactor under cooled with liquid nitrogen and fill Ar three times; under the Ar protection, in 65 ℃ of oil baths, react 48h; leave standstill cooling, successively with THF and acetone supersound washing precipitation, centrifugation; vacuum-drying 24h under the room temperature obtains silicon-dioxide/N-N-isopropylacrylamide nuclear shell structured nano-hybrid particle.
The particle grafted rate 68.5% of hybridized nanometer by present method preparation does not have agglomeration, has good dispersiveness and pH-temperature-responsive.
Embodiment 6
A and b step are with embodiment 1.
C. adding end successively in flask is the nano silicon 0.1g of ATRP initiating radical; THF 1mL; monomer NIPA 0.0mol, CuBr 0.019g and PMDETA 27uL take out reactor under cooled with liquid nitrogen and fill Ar three times; under the Ar protection, in 65 ℃ of oil baths, react 48h; leave standstill cooling, successively with THF and acetone supersound washing precipitation, centrifugation; vacuum-drying 24h under the room temperature obtains silicon-dioxide/N-N-isopropylacrylamide nuclear shell structured nano-hybrid particle.
The particle grafted rate 67.6% of hybridized nanometer by present method preparation does not have agglomeration, has good dispersiveness and pH-temperature-responsive.
Claims (2)
1. one kind in the high molecular method of nano-silica surface grafting environment-responsive, it is characterized in that:
A. surperficial end group is the preparation of the nano silicon of amino
Add the 1-3g nano silicon successively, 20-60mL toluene and 4-12mL 3-aminocarbonyl propyl Trimethoxy silane, in reaction system, take out applying argon gas three times, under argon gas atmosphere in 115-120 ℃ of oil bath back flow reaction 12-36h, cooling is left standstill, successively with toluene and acetone supersound washing to remove the silane reagent of absorption, centrifugation, vacuum-drying;
The preparation of the nano silicon of the initiating radical that b. surperficial end is an atom transfer radical polymerization
Add 0.3-0.6g and connect amino nano silicon, 20-40mL toluene and 8-16mL triethylamine, in ice-water bath, splash into the mixing solutions of 4-8mL 2-bromo propionyl bromide and 8-16mL toluene, reaction 4-24h, staticly settle, be the solvent supersonic washing with toluene and acetone successively, centrifugation, vacuum-drying;
C. the preparation of silicon-dioxide/environment-responsive polymer nuclear shell structured nano-hybrid particle
Adding end successively is the nano silicon 0.05-0.3g of the initiating radical of atom transfer radical polymerization; tetrahydrofuran (THF) 1-10mL; environment-responsive high polymer monomer 0.01-0.05mol; cuprous bromide 0.01-0.05g and five methyl diethylentriamine 17-72uL; under cooled with liquid nitrogen, reactor is taken out applying argon gas three times; under argon shield, in 50-65 ℃ of oil bath, react 24-48h; leave standstill cooling; successively with tetrahydrofuran (THF) and acetone supersound washing precipitation; centrifugation; vacuum-drying obtains final product.
2. method according to claim 1 is characterized in that described environment-responsive high polymer monomer is dimethylaminoethyl methacrylate or N-N-isopropylacrylamide.
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