CN102161738A - Method for preparing multiple environment-responsive hairy polymer microspheres by loading photoinitiator and reversible addition-fragmentation chain transfer (RAFT) reagent onto different spheres respectively - Google Patents
Method for preparing multiple environment-responsive hairy polymer microspheres by loading photoinitiator and reversible addition-fragmentation chain transfer (RAFT) reagent onto different spheres respectively Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 326
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 60
- 239000004005 microsphere Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000002441 reversible effect Effects 0.000 title abstract description 3
- 238000013467 fragmentation Methods 0.000 title abstract 2
- 238000006062 fragmentation reaction Methods 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- -1 hydroxyethyl methacrylate ester Chemical class 0.000 claims description 35
- 239000000839 emulsion Substances 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 24
- 235000019394 potassium persulphate Nutrition 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000004044 response Effects 0.000 claims description 18
- 239000004160 Ammonium persulphate Substances 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 15
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000004159 Potassium persulphate Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical group C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical group [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 2
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims 1
- 239000012987 RAFT agent Substances 0.000 claims 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 238000010556 emulsion polymerization method Methods 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 238000005286 illumination Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 84
- 229920002125 Sokalan® Polymers 0.000 description 62
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 44
- 229910052757 nitrogen Inorganic materials 0.000 description 42
- 239000004584 polyacrylic acid Substances 0.000 description 40
- 238000002296 dynamic light scattering Methods 0.000 description 31
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 26
- 239000004926 polymethyl methacrylate Substances 0.000 description 26
- 239000004793 Polystyrene Substances 0.000 description 25
- 238000010792 warming Methods 0.000 description 24
- 229920002223 polystyrene Polymers 0.000 description 23
- 230000008859 change Effects 0.000 description 20
- 238000005406 washing Methods 0.000 description 18
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- 230000035945 sensitivity Effects 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000008014 freezing Effects 0.000 description 12
- 238000007710 freezing Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 3
- AZASWMGVGQEVCS-UHFFFAOYSA-N 4,4-dimethylpentan-2-one Chemical compound CC(=O)CC(C)(C)C AZASWMGVGQEVCS-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QMRRTXOVRPBDQV-UHFFFAOYSA-N C(C)C1=C(C(=C(C(=O)C2=CC=CC=C2)C=C1)C)CC Chemical compound C(C)C1=C(C(=C(C(=O)C2=CC=CC=C2)C=C1)C)CC QMRRTXOVRPBDQV-UHFFFAOYSA-N 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000003806 hair structure Effects 0.000 description 1
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000013033 iniferter Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Cosmetics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a method for preparing multiple environment-responsive hairy polymer microspheres by loading a photoinitiator and a reversible addition-fragmentation chain transfer (RAFT) reagent onto different spheres respectively. The method comprises the following steps of: 1) preparing first polymer microspheres by a soap-free emulsion polymerization method; 2) loading the RAFT reagent onto the first polymer microspheres to obtain second polymer microspheres; 3) preparing third polymer microspheres of which the surfaces are loaded with the photoinitiator by the soap-free emulsion polymerization method; and 4) mixing the second polymer microspheres and the third polymer microspheres, adding a first monomer, and initiating the polymerization under ultraviolet illumination to obtain fourth polymer microspheres and fifth polymer microspheres of which the surfaces are grafted with a homopolymerization polymer brush. In addition, a second monomer and a third monomer can also be added to prepare polymer microspheres with various structures according to requirements. The first monomer, the second monomer and the third monomer are N-isopropyl acrylamide, N-vinypyrrolidone or acrylic acid. In the method, the multiple environment-responsive hairy polymer microspheres are prepared by loading the photoinitiator and the RAFT onto the different spheres respectively; the method is simple and easy to implement; and experiment conditions are mild.
Description
Technical field
The present invention relates to a kind of different ball difference load light trigger and RAFT reagent of utilizing to prepare the method for the hair-like polymer microballoon of multiple environment response type, be specifically related to a kind ofly load on different microsphere surfaces respectively with light trigger, prepare the surface has stimulating responsive to temperature and pH the hair-like polymer microballoon novel method of many structures with RAFT reagent.
Technical background
The surface modifying method of material is a lot, and in fact hair-like microballoon is exactly the polymer chemistry modification to different microballoon stromal surface.Hair-like microballoon is meant that the end by polymer molecular chain is connected in microsphere surface or interface and a kind of special macromolecular structure that forms.Environmental response type hair mainly is by environmental stimulus, makes microsphere surface performance such as hydrophilic/hydrophobic, acidity/alkalescence, conduction/insulation, bonding/repulsion, absorption/desorption etc. that (reversible) take place and changes.These polymer brushes because in absorption, adhere to, lubricated and wetting aspect have distinguishing feature, be widely used in dispersion agent, chemical valve, biological reagent and absorption and every field such as separate, shown potential and huge researching value.
At present, the preparation method of this hair-like microballoon mainly contains two classes.One class is " being grafted to the surface ", and another kind of is " from surface grafting ".The latter mainly comprises traditional radical polymerization and active free radical polymerization.Prepare polymer brush at microsphere surface by traditional radical polymerization, because the polymerization mechanism that it causes slowly, increase soon, speed stops, easily shift has determined prepared polymer brush microtexture to be difficult to regulation and control, in order to overcome these defectives, active free radical polymerization has become one of focus of the research in the Polymer Synthesizing field in recent years.The living radical polymerization technique of successively succeeding in developing has the transfer of initiation to stop (Iniferter), nitrogen oxygen intermediate polymerization (NMP), atom transfer radical polymerization (ATRP), and RAFT polymerization (RAFT) etc.Wherein, RAFT polymeric major advantage is: i) the suitable monomers scope is wide; Ii) institute's synthetic macromolecule brush configuration is controlled, can prepare the block macromolecular brush, therefore is widely studied.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of different ball difference load light trigger and RAFT reagent to prepare the method for the hair-like polymer microballoon of multiple environment response type.
For realizing this purpose, the present invention is by the RAFT technology, earlier RAFT reagent is loaded to a kind of microsphere surface by radical reaction, light trigger is carried on another microsphere surface, the employing UV-light causes, functional monomer is prepared into the Adjustable structure polymer brush that is grafted to microsphere surface, and possesses multiple environment-responsive.
The present invention utilizes different ball, and load light trigger and RAFT reagent are as follows with the detailed process of the method for preparing the hair-like polymer microballoon of multiple environment response type respectively:
1) in reactor, adds first component, second component, the 3rd component and water, temperature of reaction system is risen to 60 ℃ ~ 90 ℃, add initiator for reaction 1-8h, the back drips hydroxyethyl methacrylate ester class 2-5h, and getting particle diameter is first polymer microballoon of 100nm ~ 900nm; By mass ratio, the 3rd group of branch ︰ initiator of the 2nd group of branch ︰ of the one group of branch ︰ of water ︰ is 4 ~ 100 ︰, 1 ︰, 0.0004 ~ 0.01 ︰, 0.0004 ~ 0.01 ︰ 0.0036 ~ 0.09, and hydroxyethyl methacrylate ester class ︰ first component is 0.01 ~ 0.3 ︰ 1; Described first component is vinylbenzene (St) or methyl methacrylate (MMA); Described second reactant is sodium bicarbonate (NaHCO
3), saleratus (KHCO
3) or bicarbonate of ammonia (NH
4HCO
3); Described the 3rd component is sodium hydroxide (NaOH), potassium hydroxide (KOH) or ammoniacal liquor (NH
3H
2O); Described initiator is Potassium Persulphate (KPS) and/or ammonium persulphate (APS);
2) the step 1) thus obtained microsphere is mixed with RAFT (RAFT) agent, the quality of described RAFT reagent is 1 ~ 5 times of the class of hydroxyethyl methacrylate ester described in the step 1), react 10 ~ 20h, get second polymer microballoon of area load RAFT reagent and light trigger;
3) in reactor, add first component, second component, the 3rd component and water, temperature of reaction system is risen to 60 ℃ ~ 90 ℃, add initiator for reaction 1-8h, the back drips light trigger 2-5h, and getting particle diameter is the terpolymer microballoon of the area load light trigger of 100nm ~ 900nm; By mass ratio, the 3rd group of branch ︰ initiator of the 2nd group of branch ︰ of the one group of branch ︰ of water ︰ is 4 ~ 100 ︰, 1 ︰, 0.0004 ~ 0.01 ︰, 0.0004 ~ 0.01 ︰ 0.0036 ~ 0.09, and it is 0.01 ~ 0.45 ︰ 100 that light draws agent ︰ first component; Described first component is vinylbenzene (St) or methyl methacrylate (MMA); Described second reactant is sodium bicarbonate (NaHCO
3), saleratus (KHCO
3) or bicarbonate of ammonia (NH
4HCO
3); Described the 3rd component is sodium hydroxide (NaOH), potassium hydroxide (KOH) or ammoniacal liquor (NH
3H
2O); Described initiator is Potassium Persulphate (KPS) and/or ammonium persulphate (APS);
4) with step 2) and 3) in second polymer microballoon and terpolymer microballoon to be mixed with solid holdup by mass ratio 1 ︰ 1 be 1% ~ 20% emulsion, in this emulsion, add first monomer, at 5 ℃ ~ 80 ℃ following ultraviolet lighting initiated polymerization 10min-5h, obtain all the 4th, the 5th polymer microballoons of grafting polymer brush of different ball surface; Described first monomer is N-N-isopropylacrylamide (NIPA), N-vinyl pyrrolidone (NVP) or vinylformic acid (AA); By mass ratio, newborn liquid ︰ the one single body ︰ is 100 ︰ 1 ~ 20.
Further, the present invention also comprises the steps 5):
It is 1% ~ 20% emulsion that the different ball of gained surface grafting polymer brush is made into solid holdup, in this emulsion, add second monomer, at 5 ℃ ~ 80 ℃ following ultraviolet lighting initiated polymerization 10min-5h, obtain two kinds of polymer microballoons, a kind of is the 6th polymer microballoon of surface grafting two block macromoleculars brush, and another kind is the 7th polymer microballoon of two kinds of homopolymerization types of surface grafting polymer brush; Described second monomer is NVP, NIPA or AA; By mass ratio, Ru Ye ︰ second monomer is 100 ︰ 1 ~ 20.
Further, the present invention also comprises the steps 6):
It is 1% ~ 20% emulsion that described the 6th polymer microballoon and the 7th polymer microballoon are hybridly prepared into solid holdup, in this emulsion, add the 3rd monomer, at 5 ℃ ~ 80 ℃ following ultraviolet lighting initiated polymerization 10min-5h, obtain the 8th polymer microballoon of surface grafting three block macromoleculars brush and the 9th polymer microballoon of three kinds of homopolymerization types of surface grafting polymer brush; Described the 3rd monomer is vinylformic acid, N-N-isopropylacrylamide or N-vinyl pyrrolidone; By mass ratio, Ru Ye ︰ the 3rd monomer is 100 ︰ 1 ~ 20.
Further, the present invention is in described step 1), and the structural formula of hydroxyethyl methacrylate ester class is as follows:
R wherein
1, R
2Be H or C
1-3Alkyl, R
3For containing the alkylidene group of 1-3 carbon.
Further, the structural formula of RAFT reagent of the present invention is as follows:
Wherein, R
4, R
5Be H or C
1-3Alkyl, R
6Be C
6H
5, (CH
3)
2CHCH
2Or (CH
3)
3CCH
2
Further, the structural formula of light trigger of the present invention is as follows:
Wherein, R
7Be C
6H
5, (CH
3)
2CHCH
2Or (CH
3)
3CCH
2, R
8, R
9For H or contain the alkyl of 1-3 carbon.
Further, the present invention is in described step 1), added linking agent before adding described initiator in reactor, described linking agent is Vinylstyrene (DVB) or Ethylene glycol dimethacrylate (EGDMA), and the mass ratio of described first component and linking agent is 1:0.05 ~ 0.5.
The hair structure on the hair-like polymer microballoon of the multiple environment response type surface that the present invention prepares is
Poly N-isopropyl acrylamide (PNIPA) homopolymerization type polymer brush, poly N-vinyl pyrrolidone (PVP) homopolymerization type polymer brush, polyacrylic acid (PAA) homopolymerization type polymer brush, poly N-isopropyl acrylamide-b-poly N-vinyl pyrrolidone (PNIPA-b-PVP) two block type polymers brush, poly N-isopropyl acrylamide-b-polyacrylic acid (PNIPA-b-PAA) two block type polymers brush, poly N-vinyl pyrrolidone-b-poly N-isopropyl acrylamide (PVP-b-PNIPA) two block type polymers brush, poly N-vinyl pyrrolidone-b-polyacrylic acid (PVP-b-PAA) two block type polymers brush, polyacrylic acid-b-poly N-isopropyl acrylamide (PAA-b-PNIPA) two block type polymers brush, polyacrylic acid-b-poly N-vinyl pyrrolidone (PAA-b-PVP) two block type polymers brush, poly N-isopropyl acrylamide-b-poly N-vinyl pyrrolidone-b-polyacrylic acid (PNIPA-b-PVP-b-PAA) three block type polymers brush, poly N-isopropyl acrylamide-b-polyacrylic acid-b-poly N-vinyl pyrrolidone (PNIPA-b-PAA-b-PVP) three block type polymers brush, poly N-vinyl pyrrolidone-b-poly N-isopropyl acrylamide-b-polyacrylic acid (PVP-b-PNIPA-b-PAA) three block type polymers brush, poly N-vinyl pyrrolidone-b-polyacrylic acid b-poly N-isopropyl acrylamide (PVP-b-PAA-b-PNIPA) three block type polymers brush, polyacrylic acid-b-poly N-isopropyl acrylamide-b-poly N-vinyl pyrrolidone (PAA-b-PNIPA-b-PVP) three block type polymers brush or polyacrylic acid-b-poly N-vinyl pyrrolidone-b-poly N-isopropyl acrylamide (PAA-b-PVP-b-PNIPA) three block type polymers brush.
Compared with prior art, the invention has the beneficial effects as follows: it is simple to operate that the present invention prepares the method for the hair-like polymer microballoon of environmental response type, the polymer brush controllable structure, and application prospect is extensive.The present invention provides developing direction for the practical application of polymer microballoon finishing.The present invention is widely used in carrying out the environmental response type polymer monomer of light initiation polymerization, the hair-like polymer microballoon of environmental response type of preparation comprises: temperature, the PNIPA of pH response type, PVP, PAA homopolymerization type polymer brush, PNIPA-b-PVP, PNIPA-b-PAA, PVP-b-PNIPA, PVP-b-PAA, PAA-b-PNIPA, PAA-b-PVP diblock type polymer brush, PNIPA-b-PVP-b-PAA, PNIPA-b-PAA-b-PVP, PVP-b-PNIPA-b-PAA, PVP-b-PAA-b-PNIPA, PAA-b-PNIPA-b-PVP, PAA-b-PVP-b-PNIPA three block type polymers brush.As seen, the present invention can prepare the polymer brush of various environmental response types effectively, has expanded the controllability of polymer brush structure.And the polymer brush of this controllable structure can be applied to multiple field, Liu Zheng (Biochemical Engineering Journal, 24 (2005) 55 – 64) etc. think that the polymer of temperature sensitive property because the surface has hydrophobic group, can be used for assisting protein renaturation; Ito people such as (J.Am.Chem.Soc., 119 (1997) 2739-2740) is covalently bonded to the polymer brush of pH susceptibility on the permeable membrane, comes controlled liq to flow through the speed of permeable membrane with this; The block type polymer brush that has temperature sensitive property and pH susceptibility simultaneously then can be applicable to the embedding of medicine, all many-sides such as load of catalyzer.
The different ball advantage of load light trigger and RAFT reagent respectively is: monomeric transformation efficiency is higher in this kind method, and the polymkeric substance major part all loads on two kinds of different balls of size; The partition ratio of gained polymer brush is than higher, and can obtain three block macromoleculars brush microballoon equally.
Embodiment
The present invention is further described technical scheme of the present invention with the following example.
Embodiment 1
Step 1)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 180g vinylbenzene (St), 1.8g NaHCO
3And 1.8gNaOH, nitrogen protection treats that system temperature reaches 60 ℃, in system, add 0.648g Potassium Persulphate (KPS) and be initiator (by mass ratio, H
2O ︰ St ︰ NaHCO
3︰ NaOH ︰ KPS is 4 ︰, 1 ︰, 0.01 ︰, 0.01 ︰ 0.0036), behind the reaction 8h, drip the 1.8g hydroxyethyl methylacrylate (by mass ratio, hydroxyethyl methacrylate Yi Zhi ︰ St is 0.01 ︰ 1), the dropping time is 2h, gets first polystyrene (PS) microballoon of particle diameter 900nm area load hydroxyethyl methylacrylate.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 6000rpm, and with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, a PS microballoon of the area load hydroxyethyl methylacrylate that must clean.
Step 2)
In the PS microballoon of the area load hydroxyethyl methylacrylate that step 1) is cleaned, add 3.6gRAFT reagent benzyl trithio ester group propionyl chloride (by mass ratio, benzyl trithio ester group propionyl Lv ︰ hydroxyethyl methylacrylate is 2 ︰ 1), under normal temperature condition, react 15h, the 2nd PS microballoon of area load RAFT reagent, repeat above method centrifuge washing three times repeatedly again.
Step 3)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 7.2gSt, 3.6g Vinylstyrene (DVB), 0.0144g KHCO
3And 0.0144gKOH, nitrogen protection treats that system temperature reaches 90 ℃, in system, add 0.648gAPS and be initiator (by mass ratio, H
2O ︰ St ︰ DVB ︰ NaHCO
3︰ NaOH ︰ APS is 100 ︰, 1 ︰, 0.5 ︰, 0.002 ︰, 0.002 ︰ 0.09), behind the reaction 1h, drip 0.0324g light trigger isopropyl benzene ketone methacrylic ester (by mass ratio, isopropyl benzene ketone Jia base Bing olefin(e) acid Zhi ︰ St is 0.45 ︰ 100), the dropping time is 3h, gets the 3rd crosslinked PS microballoon of particle diameter 100nm area load light trigger.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 12000rpm, and with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the 3rd crosslinked PS microballoon of the area load light trigger that must clean.
Step 4)
With step 2) and 3) in the 3rd crosslinked PS microballoon of the 2nd PS microballoon of area load RAFT reagent and area load light trigger to be mixed with solid holdup be 20% emulsion 450g; add 4.5g temperature sensitive monomer N-N-isopropylacrylamide (NIPA) (is 1 ︰ 0.01 by mass ratio Ru Ye ︰ NIPA); under the nitrogen protection; ultraviolet lighting reaction under 5 ℃ of temperature; polymerization 10min obtains the 4th and 45 polymer microballoons of surface grafting poly N-isopropyl acrylamide (PNIPA) polymer brush.At 25 ℃, to measure through dynamic light scattering (DLS) under the pH=7.0 condition, the thickness of the microsphere surface PNIPA polymer brush of load RAFT reagent is 5nm, is warming up to 40 ℃, then the thickness of PNIPA polymer brush becomes 1nm, has proved that it has temperature sensitivity; The thickness of the microsphere surface PNIPA polymer brush of load light trigger is 4nm, is warming up to 40 ℃, and then the thickness of PNIPA polymer brush becomes 1nm, has proved that it has temperature sensitivity.
Embodiment 2
Step 1)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 7.2gSt, 3.6g Vinylstyrene (DVB), 0.0144g KHCO
3And 0.0144gKOH, nitrogen protection treats that system temperature reaches 90 ℃, in system, add 0.648gKPS and be initiator (by mass ratio, H
2O ︰ St ︰ DVB ︰ NaHCO
3︰ NaOH ︰ KPS is 100 ︰, 1 ︰, 0.5 ︰, 0.002 ︰, 0.002 ︰ 0.09), behind the reaction 1h, drip the 0.72g Rocryl 410 (by mass ratio, methacrylic acid hydroxypropyl Zhi ︰ St is 0.1 ︰ 1), the dropping time is 3h, gets the crosslinked PS microballoon of particle diameter 100nm area load Rocryl 410.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 12000rpm, and with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the first crosslinked PS microballoon of the area load Rocryl 410 that must clean.
Step 2)
In the crosslinked PS microballoon of the area load Rocryl 410 that step 1) is cleaned, add 3.6gRAFT reagent isopentyl trithio ester group propionyl chloride (by mass ratio, isopentyl trithio ester group propionyl Lv ︰ Rocryl 410 is 1 ︰ 1), at normal-temperature reaction 15h, the second crosslinked PS microballoon of area load RAFT reagent, repeat above method centrifuge washing three times repeatedly again.
Step 3)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 36gSt, 1.8g Ethylene glycol dimethacrylate (EGDMA), 0.0144g NH
4HCO
3With 0.051g concentration be 28% NH
3H
2O, nitrogen protection treats that system temperature reaches 80 ℃, in system, add 0.72gKPS and 0.72g ammonium persulphate (APS) and be initiator (by mass ratio, H
2O ︰ St ︰ EGDMA ︰ NH
4HCO
3︰ NH
3H
2O ︰ KPS ︰ APS is 20 ︰, 1 ︰, 0.05 ︰, 0.0004 ︰, 0.0004 ︰, 0.02 ︰ 0.02), behind the reaction 5h, drip 0.0036 light trigger sec.-propyl isobutyl ketone methacrylic ester (by mass ratio, the sec.-propyl isobutyl ketone first base third olefin(e) acid ester ︰ St is 0.01 ︰ 100), the dropping time is 5h, gets the crosslinked PS microballoon of particle diameter 400nm area load light trigger.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 9500rpm, and with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the 3rd crosslinked PS microballoon of the area load light trigger that must clean.
Step 4)
With step 2) and 3) in the 3rd crosslinked PS microballoon of the second crosslinked PS microballoon of area load RAFT reagent and area load light trigger to be mixed with solid holdup be 1% emulsion 450g; add 90g pH sensitive monomer N-vinyl pyrrolidone (NVP) (is 1 ︰ 0.2 by mass ratio Ru Ye ︰ NVP); under the nitrogen protection; ultraviolet lighting reaction under 80 ℃ of temperature; polymerization 5h obtains the 4th, the 5th polymer microballoon of surface grafting poly N-vinyl pyrrolidone (PVP) polymer brush.At 25 ℃, to measure through DLS under the pH=7.0 condition, the thickness of the microsphere surface PVP polymer brush of load RAFT reagent is 100nm, changes pH=10.0, then the thickness of PVP polymer brush becomes 8nm, has proved that it has pH susceptibility; The thickness of the microsphere surface PVP polymer brush of load light trigger is 40nm, changes pH=10.0, and then the thickness of PVP polymer brush becomes 3nm, has proved that it has pH susceptibility.
Embodiment 3
Step 1)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 36gSt, 1.8g Ethylene glycol dimethacrylate (EGDMA), 0.0144g NH
4HCO
3With 0.051g concentration be 28% NH
3H
2O, nitrogen protection treats that system temperature reaches 80 ℃, in system, add 0.72gKPS and 0.72g ammonium persulphate (APS) and be initiator (by mass ratio, H
2O ︰ St ︰ EGDMA ︰ NH
4HCO
3︰ NH
3H
2O ︰ KPS ︰ APS is 20 ︰, 1 ︰, 0.05 ︰, 0.0004 ︰, 0.0004 ︰, 0.02 ︰ 0.02), behind the reaction 5h, drip 10.8g methacrylic acid hydroxyl isopropyl ester (by mass ratio, the different third ester ︰ St of methacrylic acid hydroxyl is 0.3 ︰ 1), the dropping time is 5h, gets the crosslinked PS microballoon of particle diameter 400nm area load methacrylic acid hydroxyl isopropyl ester.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 9500rpm, with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the first crosslinked PS microballoon of the area load methacrylic acid hydroxyl isopropyl ester that must clean.
Step 2)
In the crosslinked PS microballoon of the area load methacrylic acid hydroxyl isopropyl ester that step 1) is cleaned, add 10.8gRAFT reagent 2-benzyl trithio ester group butyryl chloride (by mass ratio, 2-benzyl trithio ester group butyryl chlorine ︰ methacrylic acid hydroxyl isopropyl ester is 1 ︰ 1), at normal-temperature reaction 20h, the second crosslinked PS microballoon of area load RAFT reagent, repeat above method centrifuge washing three times repeatedly again.
Step 3)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 72gMMA, 0.36g NaHCO
3And 0.36gKOH, nitrogen protection treats that system temperature reaches 75 ℃, in system, add 0.72gKPS and be initiator (by mass ratio, H
2O ︰ MMA ︰ NaHCO
3︰ KOH ︰ KPS is (10 ︰, 1 ︰, 0.005 ︰, 0.005 ︰ 0.01), behind the reaction 6h, drip 0.216g light trigger methyl neo-pentyl ketone methacrylic ester (by mass ratio, methyl neo-pentyl ketone Jia base Bing olefin(e) acid Zhi ︰ St is 0.3 ︰ 100), the dropping time is 4h, gets polymethylmethacrylate (PMMA) microballoon of particle diameter 700nm area load light trigger.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 7000rpm, and with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the 3rd PMMA microballoon of the area load light trigger that must clean.
Step 4)
With step 2) and 3) in the PMMA microballoon of the crosslinked PS microballoon of area load RAFT reagent and area load light trigger to be mixed with solid holdup be 5% emulsion 450g; add 22.5g pH sensitive monomer vinylformic acid (AA) (is 1 ︰ 0.05 by mass ratio Ru Ye ︰ AA); under the nitrogen protection; ultraviolet lighting reaction under 25 ℃ of temperature; polymerization 2h obtains the 4th and 45 polymer microballoons of surface grafting polyacrylic acid (PAA) polymer brush.At 25 ℃, to measure through DLS under the pH=7.0 condition, the thickness of the microsphere surface PAA polymer brush of load RAFT reagent is 40nm, changes pH=4.0, then the thickness of PAA polymer brush becomes 6nm, has proved that it has pH susceptibility; The thickness of the microsphere surface PAA polymer brush of load light trigger is 20nm, changes pH=4.0, and then the thickness of PAA polymer brush becomes 3nm, has proved that it has pH susceptibility
Embodiment 4
Step 1)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 72gMMA, 0.36g NaHCO
3And 0.36gNaOH, nitrogen protection treats that system temperature reaches 75 ℃, in system, add 0.72gKPS and be initiator (by mass ratio, H
2O ︰ MMA ︰ NaHCO
3︰ NaOH ︰ KPS is (10 ︰, 1 ︰, 0.005 ︰, 0.005 ︰ 0.01), behind the reaction 6h, drip 3.6g methacrylic acid hydroxyl isobutyl ester (by mass ratio, the different fourth ester of methacrylic acid hydroxyl ︰ St is 0.05 ︰ 1), the dropping time is 4h, gets polymethylmethacrylate (PMMA) microballoon of particle diameter 700nm area load methacrylic acid hydroxyl isobutyl ester.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 7000rpm, with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, a PMMA microballoon of the area load methacrylic acid hydroxyl isobutyl ester that must clean.
Step 2)
In the PMMA microballoon of the area load methacrylic acid hydroxyl isobutyl ester that step 1) is cleaned, add 3.6gRAFT reagent 2-isohexyl trithio ester group-3 methylbutyryl chlorine (by mass ratio, 2-isohexyl trithio ester group-3 methylbutyryl Lv ︰ hydroxyethyl methylacrylate is 1 ︰ 1), at normal-temperature reaction 15h, the 2nd PMMA microballoon of area load RAFT reagent, repeat above method centrifuge washing three times repeatedly again.
Step 3)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 14.4gMMA, 1.44gDVB, 0.0144g NH
4HCO
3And 0.0288gKOH, nitrogen protection treats that system temperature reaches 70 ℃, in system, add 0.432gKPS and be initiator (by mass ratio, H
2O ︰ MMA ︰ DVB ︰ NH
4HCO
3︰ NaOH ︰ KPS is 100 ︰, 1 ︰, 0.1 ︰, 0.002 ︰, 0.002 ︰ 0.09), behind the reaction 4h, drip 0.0576g light trigger diethylmethyl benzophenone propyl group acrylate (by mass ratio, diethylmethyl benzophenone propyl group Bing olefin(e) acid Zhi ︰ MMA is 0.4 ︰ 100), the dropping time is 5h, gets the crosslinked PMMA microballoon of particle diameter 200nm area load light trigger.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 11000rpm, and with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the 3rd crosslinked PMMA microballoon of the area load light trigger that must clean.
Step 4)
With step 2) and 3) in the 3rd crosslinked PMMA microballoon of the 2nd PS microballoon of area load RAFT reagent and area load light trigger to be mixed with solid holdup be 2% emulsion 450g; adding 22.5g temperature sensitive monomer NIPA(is 1 ︰ 0.05 by mass ratio Ru Ye ︰ NIPA); under the nitrogen protection; ultraviolet lighting reaction under 10 ℃ of temperature; polymerization 1h obtains the 4th and 45 polymer microballoons of surface grafting PNIPA polymer brush.At 25 ℃, to measure through DLS under the pH=7.0 condition, the thickness of the microsphere surface PNIPA polymer brush of load RAFT reagent is 60nm, is warming up to 40 ℃, then the thickness of PNIPA polymer brush becomes 3nm, has proved that it has temperature sensitivity; The thickness of the microsphere surface PNIPA polymer brush of load light trigger is 20nm, is warming up to 40 ℃, and then the thickness of PNIPA polymer brush becomes 2nm, has proved that it has temperature sensitivity
Embodiment 5
Step 1)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 14.4gMMA, 1.44gDVB, 0.0144g NH
4HCO
3And 0.0288gKOH, nitrogen protection treats that system temperature reaches 70 ℃, in system, add 0.432gKPS and be initiator (by mass ratio, H
2O ︰ MMA ︰ DVB ︰ NH
4HCO
3︰ NaOH ︰ KPS is 100 ︰, 1 ︰, 0.1 ︰, 0.002 ︰, 0.002 ︰ 0.09), behind the reaction 4h, drip 2.88g methacrylic acid hydroxy butyl ester (by mass ratio, hydroxyethyl methacrylate Ding Zhi ︰ MMA is 0.2 ︰ 1), the dropping time is 5h, gets the crosslinked PMMA microballoon of particle diameter 200nm area load methacrylic acid hydroxy butyl ester.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 11000rpm, with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the first crosslinked PMMA microballoon of the area load methacrylic acid hydroxy butyl ester that must clean.
Step 2)
In the crosslinked PMMA microballoon of the area load methacrylic acid hydroxy butyl ester that step 1) is cleaned, add 2.88gRAFT reagent 3-isohexyl trithio ester group-3-ethyl valeryl chloride (by mass ratio, 3-isohexyl trithio ester group-3-ethyl valeryl chlorine ︰ methacrylic acid hydroxy butyl ester is 1 ︰ 1), at normal-temperature reaction 10h, the second crosslinked PMMA microballoon of area load RAFT reagent, repeat above method centrifuge washing three times repeatedly again.
Step 3)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 9.0gMMA, 2.7gEGDMA, 0.018g KHCO
3With 0.064g concentration be 28% NH
3H
2O, nitrogen protection treats that system temperature reaches 65 ℃, in system, add 0.09gKPS and 0.09gAPS and be initiator (by mass ratio, H
2O ︰ St ︰ EGDMA ︰ NH
4HCO
3︰ NH
3H
2O ︰ KPS ︰ APS is 80 ︰, 1 ︰, 0.3 ︰, 0.002 ︰, 0.002 ︰, 0.01 ︰ 0.01), behind the reaction 5h, drip 0.04g light trigger dipropyl methyl iso-butyl ketone (MIBK) methacrylic ester (by mass ratio, dipropyl methyl iso-butyl ketone (MIBK) Jia base Bing olefin(e) acid Zhi ︰ MMA is 0.45 ︰ 100), the dropping time is 3h, gets the crosslinked PMMA microballoon of particle diameter 500nm area load light trigger.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 10000rpm, and with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the 3rd crosslinked PMMA microballoon of the area load light trigger that must clean.
Step 4)
With step 2) and 3) in the 3rd crosslinked PMMA microballoon of the second crosslinked PMMA microballoon of area load RAFT reagent and area load light trigger to be mixed with solid holdup be 3% emulsion 450g; adding 45g pH sensitive monomer NVP(is 1 ︰ 0.1 by mass ratio Ru Ye ︰ NVP); under the nitrogen protection; ultraviolet lighting reaction under 60 ℃ of temperature; polyase 13 h obtains the 4th and 45 polymer microballoons of surface grafting PVP polymer brush.At 25 ℃, to measure through DLS under the pH=7.0 condition, the thickness of the microsphere surface PVP polymer brush of load RAFT reagent is 50nm, changes pH=10.0, then the thickness of PVP polymer brush becomes 6nm, has proved that it has pH susceptibility; The thickness of the microsphere surface PVP polymer brush of load light trigger is 30nm, changes pH=10.0, and then the thickness of PVP polymer brush becomes 4nm, has proved that it has pH susceptibility.
Embodiment 6
Step 1)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 9.0gMMA, 2.7gEGDMA, 0.018g KHCO
3With 0.064g concentration be 28% NH
3H
2O, nitrogen protection treats that system temperature reaches 65 ℃, in system, add 0.09gKPS and 0.09gAPS and be initiator (by mass ratio, H
2O ︰ St ︰ EGDMA ︰ NH
4HCO
3︰ NH
3H
2O ︰ KPS ︰ APS is 80 ︰, 1 ︰, 0.3 ︰, 0.002 ︰, 0.002 ︰, 0.01 ︰ 0.01), behind the reaction 5h, drip 1.8g methacrylic acid hydroxyl isobutyl ester (by mass ratio, the different fourth ester of methacrylic acid hydroxyl ︰ MMA is 0.2 ︰ 1), the dropping time is 3h, gets the crosslinked PMMA microballoon of particle diameter 300nm area load methacrylic acid hydroxyl isobutyl ester.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 10000rpm, with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the first crosslinked PMMA microballoon of the area load methacrylic acid hydroxyl isobutyl ester that must clean.
Step 2)
In the crosslinked PMMA microballoon of the area load methacrylic acid hydroxyl isobutyl ester that step 1) is cleaned, add 3.6gRAFT reagent 4-isopentyl trithio ester group-3-propyl group caproyl chloride (by mass ratio, 3-isopentyl trithio ester group-3-propyl group valeryl chlorine ︰ methacrylic acid hydroxyl isobutyl ester is 2 ︰ 1), at normal-temperature reaction 15h, the second crosslinked PMMA microballoon of area load RAFT reagent, repeat above method centrifuge washing three times repeatedly again.
Step 3)
Logical in advance nitrogen is 10 minutes in having the 1000ml reactor of prolong, thermometer, mechanical stirrer, adds 720gH then
2O, 180g vinylbenzene (St), 1.8g NaHCO
3And 1.8gNaOH, nitrogen protection treats that system temperature reaches 60 ℃, in system, add 0.648g Potassium Persulphate (KPS) and be initiator (by mass ratio, H
2O ︰ St ︰ NaHCO
3︰ NaOH ︰ KPS is 4 ︰, 1 ︰, 0.01 ︰, 0.01 ︰ 0.0036), behind the reaction 8h, drip 0.18g light trigger sec.-propyl neo-pentyl ketone ethyl propylene acid esters (by mass ratio, sec.-propyl neo-pentyl ketone ethyl propylene acid esters ︰ St is 0.1 ︰ 100), the dropping time is 2h, gets polystyrene (PS) microballoon of particle diameter 900nm area load light trigger.With the microballoon centrifugal 15min in high speed freezing centrifuge for preparing, rotating speed is 6000rpm, and with the microballoon deionized water wash of gained, centrifuge washing is three times so repeatedly then, the 3rd PS microballoon of the area load light trigger that must clean.
Step 4)
With step 2) and 3) in the 3rd PS microballoon of the second crosslinked PMMA microballoon of area load RAFT reagent and area load light trigger to be mixed with solid holdup be 1% emulsion 450g; adding 9.0g pH sensitive monomer AA(is 1 ︰ 0.02 by mass ratio Ru Ye ︰ AA); under the nitrogen protection; ultraviolet lighting reaction under 30 ℃ of temperature; polymerization 40min obtains the 4th and 45 polymer microballoons of surface grafting polyacrylic acid (PAA) polymer brush.At 25 ℃, to measure through DLS under the pH=7.0 condition, the thickness of the microsphere surface PAA polymer brush of load RAFT reagent is 20nm, changes pH=4.0, then the thickness of PAA polymer brush becomes 3nm, has proved that it has pH susceptibility; The thickness of the microsphere surface PAA polymer brush of load light trigger is 15nm, changes pH=4.0, and then the thickness of PAA polymer brush becomes 2nm, has proved that it has pH susceptibility.
Embodiment 7
Step 1) is identical to step 4) and embodiment's 1.
Step 5)
It is 1% emulsion 450g that big minimicrosphere in embodiment 1 step 4) is mixed with solid holdup; adding 90g pH sensitive monomer NVP(is 1 ︰ 0.2 by mass ratio Ru Ye ︰ NVP); under the nitrogen protection; ultraviolet lighting reaction under 80 ℃ of temperature; polymerization 5h, the microsphere surface of load RAFT reagent obtain two block PNIPA-b-PVP polymer brushes (the 6th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 7th polymer microballoon) of PNIPA and two kinds of homopolymerization types of PVP.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting two block PNIPA-b-PVP polymer brushes is carried out DLS mensuration, the result shows that the thickness of two block PNIPA-b-PVP polymer brushes is 105nm, be warming up to 40 ℃, the thickness of this PNIPA-b-PVP polymer brush becomes 100nm, has proved that it has temperature sensitivity.Change pH=10.0, then the thickness of PNIPA-b-PVP polymer brush becomes 13nm, has proved that it has pH susceptibility.The microballoon that proves surface grafting two block PNIPA-b-PVP polymer brushes thus has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PNIPA and two kinds of homopolymerization types of PVP polymer brush is carried out DLS mensuration, the result shows that the thickness of polymer brush is 20nm, be warming up to 40 ℃, the thickness of this polymer brush becomes 20nm, changes pH=10.0, then the thickness of polymer brush becomes 4nm, prove that thus this is the polymer brush of two kinds of homopolymerization types, and the thickness of PNIPA polymer brush is 4nm, the thickness of PVP polymer brush is 20nm.
Embodiment 8
Step 1) is identical to step 4) and embodiment's 4.
Step 5)
It is 5% emulsion 450g that the sizes of balls of surface grafting PNIPA polymer brush in embodiment 4 step 4) is mixed with solid holdup; adding 22.5g pH sensitive monomer AA(is 1 ︰ 0.05 by mass ratio Ru Ye ︰ AA); under the nitrogen protection; ultraviolet lighting reaction under 25 ℃ of temperature; polymerization 2h; the microsphere surface of load RAFT reagent obtains two block PNIPA-b-PAA polymer brushes (the 6th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 7th polymer microballoon) of PNIPA and two kinds of homopolymerization types of PAA.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting two block PNIPA-b-PAA polymer brushes is carried out DLS mensuration, the result shows that the thickness of two block PNIPA-b-PAA polymer brushes is 100nm, be warming up to 40 ℃, the thickness of PNIPA-b-PAA polymer brush becomes 45nm, has proved that it has temperature sensitivity; Change pH=4.0, then the thickness of PNIPA-b-PAA polymer brush becomes 64nm, has proved that it has pH susceptibility.The microballoon that proves surface grafting two block PNIPA-b-PAA polymer brushes thus has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PNIPA and two kinds of homopolymerization types of PAA polymer brush is carried out DLS mensuration, the result shows that the thickness of polymer brush is 20nm, be warming up to 40 ℃, the thickness of this polymer brush becomes 15nm, changes pH=4.0, then the thickness of polymer brush is 20nm, prove that thus this is the polymer brush of two kinds of homopolymerization types, and the thickness of PNIPA polymer brush is 20nm, the thickness of PAA polymer brush is 15nm.
Embodiment 9
Step 1) is identical to step 4) and embodiment's 2.
Step 5)
It is 2% emulsion 450g that the sizes of balls of surface grafting PVP polymer brush in embodiment 2 step 4) is mixed with solid holdup; adding 22.5g temperature sensitive monomer NIPA(is 1 ︰ 0.05 by mass ratio Ru Ye ︰ NIPA); under the nitrogen protection; ultraviolet lighting reaction under 10 ℃ of temperature; polymerization 1h; the microsphere surface of load RAFT reagent obtains two block PVP-b-PNIPA polymer brushes (the 6th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 7th polymer microballoon) of PVP and two kinds of homopolymerization types of PNIPA.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting two block PVP-b-PNIPA polymer brushes is carried out DLS mensuration, the result shows that the thickness of two block PVP-b-PNIPA polymer brushes is 160nm, be warming up to 40 ℃, then the thickness of PVP-b-PNIPA polymer brush becomes 103nm, has proved that it has temperature sensitivity; Change pH=10.0, then the thickness of PVP-b-PNIPA polymer brush becomes 65nm, has proved that it has pH susceptibility.The microballoon that proves surface grafting two block PVP-b-PNIPA polymer brushes thus has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PVP and two kinds of homopolymerization types of PNIPA polymer brush is carried out DLS mensuration, the result shows that the thickness of polymer brush is 40nm, be warming up to 40 ℃, the thickness of this polymer brush becomes 40nm, changes pH=10.0, then the thickness of polymer brush is 20nm, prove that thus this is the polymer brush of two kinds of homopolymerization types, and the thickness of PVP polymer brush is 40nm, the thickness of PNIPA polymer brush is 20nm.
Embodiment 10
Step 1) is identical to step 4) and embodiment's 5.
Step 4)
It is 1% emulsion 450g that the sizes of balls of surface grafting PVP polymer brush in embodiment 5 step 4) is mixed with solid holdup; adding 9.0g pH sensitive monomer AA(is 1 ︰ 0.02 by mass ratio Ru Ye ︰ AA); under the nitrogen protection; ultraviolet lighting reaction under 30 ℃ of temperature; polymerization 40min; the microsphere surface of load RAFT reagent obtains two block PVP-b-PAA polymer brushes (the 6th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 7th polymer microballoon) of PVP and two kinds of homopolymerization types of PAA.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting two block PVP-b-PAA polymer brushes is carried out DLS mensuration, the result shows that the thickness of two block PVP-b-PAA polymer brushes is 70nm, change pH=4.0, then the thickness of PVP-b-PAA polymer brush becomes 56nm, changes pH=10.0, then the thickness of PVP-b-PAA polymer brush becomes 30nm, proved surface grafting two block PVP-b-PAA polymer brushes microballoon its have pH susceptibility.Under 25 ℃, pH=7.0 condition, the microballoon of two kinds of homopolymerization type polymer brushes of surface grafting PVP and PAA is carried out DLS to be measured, the result shows that the thickness of polymer brush is 30nm, change pH=4.0, then the thickness of polymer brush becomes 34nm, changes pH=10.0, then the thickness of polymer brush becomes 18nm, prove that thus this is the polymer brush of two kinds of homopolymerization types, and the thickness of PVP polymer brush is 30nm, the thickness of PAA polymer brush is 18nm.
Embodiment 11
Step 1) is identical to step 4) and embodiment's 3.
Step 5)
It is 20% emulsion 450g that the sizes of balls of surface grafting PAA polymer brush in embodiment 3 step 4) is mixed with solid holdup; adding 4.5g temperature sensitive monomer NIPA(is 1 ︰ 0.01 by mass ratio Ru Ye ︰ NIPA); under the nitrogen protection; ultraviolet lighting reaction under 5 ℃ of temperature; polymerization 10min; the microsphere surface of load RAFT reagent obtains two block PAA-b-PNIPA polymer brushes (the 6th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 7th polymer microballoon) of PAA and two kinds of homopolymerization types of PNIPA.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting two block PAA-b-PNIPA polymer brushes is carried out DLS mensuration, the result shows that the thickness of two block PAA-b-PNIPA polymer brushes is 45nm, be warming up to 40 ℃, then the thickness of PAA-b-PNIPA polymer brush becomes 41nm, has proved that it has temperature sensitivity; Change pH=4.0, then the thickness of PAA-b-PNIPA polymer brush becomes 10nm, has proved that it has pH susceptibility, proves that thus the microballoon of surface grafting two block PAA-b-PNIPA polymer brushes has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PAA and two kinds of homopolymerization types of PNIPA polymer brush is carried out DLS mensuration, the result shows that the thickness of polymer brush is 20nm, be warming up to 40 ℃, then the thickness of polymer brush becomes 20nm, changes pH=4.0, then the thickness of polymer brush becomes 4nm, prove that thus this is the polymer brush of two kinds of homopolymerization types, and the thickness of PAA polymer brush is 20nm, the thickness of PNIPA polymer brush is 4nm.
Embodiment 12
Step 1) is identical to step 4) and embodiment's 6.
Step 5)
It is 3% emulsion 450g that the sizes of balls of surface grafting PAA polymer brush in embodiment 6 step 4) is mixed with solid holdup; adding 45g pH sensitive monomer NVP(is 1 ︰ 0.1 by mass ratio Ru Ye ︰ NVP); under the nitrogen protection; ultraviolet lighting reaction under 60 ℃ of temperature; polyase 13 h; the microsphere surface of load RAFT reagent obtains two block PAA-b-PVP polymer brushes (the 6th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 7th polymer microballoon) of PAA and two kinds of homopolymerization types of PVP.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting two block PAA-b-PVP polymer brushes is carried out DLS mensuration, the result shows that the thickness of two block PAA-b-PVP polymer brushes is 70nm, change pH=4.0, then the thickness of PAA-b-PVP polymer brush becomes 56nm, changes pH=10.0, then the thickness of PAA-b-PVP polymer brush becomes 30nm, proved surface grafting two block PAA-b-PVP polymer brushes microballoon its have pH susceptibility.Under 25 ℃, pH=7.0 condition, the microballoon of two kinds of homopolymerization type polymer brushes of surface grafting PAA and PVP is carried out DLS to be measured, the result shows that the thickness of polymer brush is 30nm, change pH=4.0, then the thickness of polymer brush becomes 33nm, changes pH=10.0, then the thickness of polymer brush becomes 18nm, prove that thus this is the polymer brush of two kinds of homopolymerization types, and the thickness of PVP polymer brush is 30nm, the thickness of PAA polymer brush is 18nm.
Embodiment 13
Step 1) is identical to step 5) and embodiment's 8.
Step 6)
It is 5% emulsion 450g that big small difference ball in embodiment 7 step 5) is mixed with solid holdup; adding 22.5g pH sensitive monomer AA(is 1 ︰ 0.05 by mass ratio Ru Ye ︰ AA); under the nitrogen protection; ultraviolet lighting reaction under 25 ℃ of temperature; polymerization 2h; the microsphere surface of load RAFT reagent obtains three block PNIPA-b-PVP-b-PAA polymer brushes (the 8th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 9th polymer microballoon) of PNIPA, PVP and three kinds of homopolymerization types of PAA.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting three block PNIPA-b-PVP-b-PAA polymer brushes is carried out DLS mensuration, the result shows that the thickness of three block PNIPA-b-PVP-b-PAA polymer brushes is 145nm, be warming up to 40 ℃, then the thickness of PNIPA-b-PVP-b-PAA polymer brush becomes 140nm, has proved that it has temperature sensitivity; Change pH=4.0, then the thickness of PNIPA-b-PVP-b-PAA polymer brush becomes 110nm, changes pH=10.0, and then the thickness of PNIPA-b-PVP-b-PAA polymer brush becomes 52nm, has proved that it has pH susceptibility.Prove that thus surface grafting three block PNIPA-b-PVP-b-PAA polymer brush microballoons have temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PNIPA, PVP and three kinds of homopolymerization types of PAA polymer brush is carried out DLS measure, the result shows that the thickness of polymer brush is 20nm, is warming up to 40 ℃, then the thickness of polymer brush is 20nm; Change pH=4.0, then the thickness of polymer brush is 23nm, changes pH=10.0, and then the thickness of polymer brush is 25nm, proves that this is the polymer brush of three kinds of homopolymerization types.
Embodiment 14
Step 1) is identical to step 5) and embodiment's 8.
Step 6)
It is 3% emulsion 450g that big minimicrosphere in embodiment 8 step 5) is mixed with solid holdup; adding 45g pH sensitive monomer NVP(is 1 ︰ 0.1 by mass ratio Ru Ye ︰ NVP); under the nitrogen protection; ultraviolet lighting reaction under 60 ℃ of temperature; polyase 13 h; the microsphere surface of load RAFT reagent obtains three block PNIPA-b-PAA-b-PVP polymer brushes (the 8th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 9th polymer microballoon) of PNIPA, PAA and three kinds of homopolymerization types of PVP.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting three block PNIPA-b-PAA-b-PVP polymer brushes is carried out DLS mensuration, the result shows that the thickness of three block PNIPA-b-PVP-b-PAA polymer brushes is 150nm, be warming up to 40 ℃, then the thickness of PNIPA-b-PAA-b-PVP polymer brush becomes 92nm, has proved that it has temperature sensitivity; Change pH=4.0, then the thickness of PNIPA-b-PAA-b-PVP polymer brush becomes 118nm, changes pH=10.0, and then the thickness of PNIPA-b-PAA-b-PVP polymer brush becomes 109nm, has proved that it has pH susceptibility.Prove that thus the microballoon of surface grafting three block PNIPA-b-PAA-b-PVP polymer brushes has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PNIPA, PAA and three kinds of homopolymerization types of PVP polymer brush is carried out DLS measure, the result shows that the thickness of polymer brush is 20nm, is warming up to 40 ℃, then the thickness of polymer brush is 15nm; Change pH=4.0, then the thickness of polymer brush is 20nm, changes pH=10.0, and then the thickness of polymer brush is 20nm, proves that this is the polymer brush of three kinds of homopolymerization types.
Embodiment 15
Step 1) is identical to step 5) and embodiment's 9.
Step 6)
It is 1% emulsion 450g that sizes of balls in embodiment 9 step 5) is mixed with solid holdup; adding 9.0g pH sensitive monomer AA(is 1 ︰ 0.02 by mass ratio Ru Ye ︰ AA); under the nitrogen protection; ultraviolet lighting reaction under 30 ℃ of temperature; polymerization 40min; the microsphere surface of load RAFT reagent obtains three block PVP-b-PNIPA-b-PAA polymer brushes (the 8th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 9th polymer microballoon) of PVP, PNIPA and three kinds of homopolymerization types of PAA.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting three block PVP-b-PNIPA-b-PAA polymer brushes is carried out DLS mensuration, the result shows that the thickness of three block PVP-b-PNIPA-b-PAA polymer brushes is 180nm, be warming up to 40 ℃, then the thickness of PVP-b-PNIPA-b-PAA polymer brush becomes 123nm, has proved that it has temperature sensitivity; Change pH=4.0, then the thickness of PVP-b-PNIPA-b-PAA polymer brush becomes 168nm, changes pH=10.0, and then the thickness of PVP-b-PNIPA-b-PAA polymer brush becomes 89nm, has proved that it has pH susceptibility.Prove that thus the microballoon of surface grafting three block PVP-b-PNIPA-b-PAA polymer brushes has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PVP, PNIPA and three kinds of homopolymerization types of PAA polymer brush is carried out DLS measure, the result shows that the thickness of polymer brush is 40nm, is warming up to 40 ℃, then the thickness of polymer brush is 20nm; Change pH=4.0, then the thickness of polymer brush is 43nm, changes pH=10.0, and then the thickness of polymer brush is 20nm, proves that this is the polymer brush of three kinds of homopolymerization types.
Embodiment 16
Step 1) is identical to step 5) and embodiment's 10.
Step 6)
It is 20% emulsion 450g that sizes of balls in embodiment 10 step 5) is mixed with solid holdup; adding 4.5g temperature sensitive monomer NIPA(is 1 ︰ 0.01 by mass ratio Ru Ye ︰ NIPA); under the nitrogen protection; ultraviolet lighting reaction under 5 ℃ of temperature; polymerization 10min; the microsphere surface of load RAFT reagent obtains three block PVP-b-PAA-b-PNIPA polymer brushes (the 8th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 9th polymer microballoon) of PVP, PAA and three kinds of homopolymerization types of PNIPA.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting three block PVP-b-PAA-b-PNIPA polymer brushes is carried out DLS mensuration, the result shows that the thickness of three block macromoleculars brush is 75nm, be warming up to 40 ℃, then the thickness of PVP-b-PAA-b-PNIPA polymer brush becomes 71nm, has proved that it has temperature sensitivity; Change pH=4.0, then the thickness of PVP-b-PAA-b-PNIPA polymer brush becomes 58nm, changes pH=10.0, and then the thickness of PVP-b-PAA-b-PNIPA polymer brush becomes 32nm, has proved that it has pH susceptibility.Prove that thus the microballoon of surface grafting three block PVP-b-PAA-b-PNIPA polymer brushes has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PVP, PAA and three kinds of homopolymerization types of PNIPA polymer brush is carried out DLS measure, the result shows that the thickness of polymer brush is 30nm, is warming up to 40 ℃, then the thickness of polymer brush is 30nm; Change pH=4.0, then the thickness of polymer brush is 35nm, changes pH=10.0, and then the thickness of polymer brush is 20nm, proves that this is the polymer brush of three kinds of homopolymerization types.
Embodiment 17
Step 1) is identical to step 5) and embodiment's 11.
Step 6)
It is 1% emulsion 450g that sizes of balls in embodiment 11 step 5) is mixed with solid holdup; adding 90g pH sensitive monomer NVP(is 1 ︰ 0.2 by mass ratio Ru Ye ︰ NVP); under the nitrogen protection; ultraviolet lighting reaction under 80 ℃ of temperature; polymerization 5h; the microsphere surface of load RAFT reagent obtains three block PAA-b-PNIPA-b-PVP polymer brushes (the 8th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 9th polymer microballoon) of PAA, PNIPA and three kinds of homopolymerization types of PVP.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting three block PAA-b-PNIPA-b-PVP polymer brushes is carried out DLS mensuration, the result shows that the thickness of three block PAA-b-PNIPA-b-PVP polymer brushes is 145nm, be warming up to 40 ℃, then the thickness of PAA-b-PNIPA-b-PVP polymer brush becomes 140nm, has proved that it has temperature sensitivity; Change pH=4.0, then the thickness of PAA-b-PNIPA-b-PVP polymer brush becomes 110nm, changes pH=10.0, and then the thickness of PAA-b-PNIPA-b-PVP polymer brush becomes 52nm, has proved that it has pH susceptibility.Prove that thus the microballoon of surface grafting three block PAA-b-PNIPA-b-PVP polymer brushes has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PAA, PNIPA and three kinds of homopolymerization types of PVP polymer brush is carried out DLS measure, the result shows that the thickness of polymer brush is 50nm, is warming up to 40 ℃, then the thickness of polymer brush is 50nm; Change pH=4.0, then the thickness of polymer brush is 54nm, changes pH=10.0, and then the thickness of polymer brush is 23nm, proves that this is the polymer brush of three kinds of homopolymerization types.
Embodiment 18
Step 1) is identical to step 5) and embodiment's 12.
Step 6)
It is 2% emulsion 450g that sizes of balls in embodiment 12 step 5) is mixed with solid holdup; adding 22.5g temperature sensitive monomer NIPA(is 1 ︰ 0.05 by mass ratio Ru Ye ︰ NIPA); under the nitrogen protection; ultraviolet lighting reaction under 10 ℃ of temperature; polymerization 1h; the microsphere surface of load RAFT reagent obtains three block PAA-b-PVP-b-PNIPA polymer brushes (the 8th polymer microballoon), and the microsphere surface of load light trigger obtains the polymer brush (the 9th polymer microballoon) of PAA, PVP and three kinds of homopolymerization types of PNIPA.At 25 ℃, under the pH=7.0 condition, the microballoon of surface grafting three block PAA-b-PNIPA-b-PVP polymer brushes is carried out DLS mensuration, the result shows that the thickness of three block PAA-b-PVP-b-PNIPA polymer brushes is 130nm, be warming up to 40 ℃, then the thickness of PAA-b-PVP-b-PNIPA polymer brush becomes 73nm, has proved that it has temperature sensitivity; Change pH=4.0, then the thickness of PAA-b-PVP-b-PNIPA polymer brush becomes 116nm, changes pH=10.0, and then the thickness of PAA-b-PVP-b-PNIPA polymer brush becomes 86nm, has proved that it has pH susceptibility.Prove that thus the crosslinked PMMA microballoon of surface grafting three block PAA-b-PVP-b-PNIPA polymer brushes has temperature sensitive property and pH susceptibility simultaneously.Under 25 ℃, pH=7.0 condition, the microballoon of surface grafting PAA, PVP and three kinds of homopolymerization types of PNIPA polymer brush is carried out DLS measure, the result shows that the thickness of polymer brush is 30nm, is warming up to 40 ℃, then the thickness of polymer brush is 30nm; Change pH=4.0, then the thickness of polymer brush is 34nm, changes pH=10.0, and then the thickness of polymer brush is 25nm, proves that this is the polymer brush of three kinds of homopolymerization types.
Claims (7)
1. load light trigger and RAFT reagent is characterized in that comprising the steps: to prepare the method for the hair-like polymer microballoon of multiple environment response type respectively for a different ball
1) add first component, second component, the 3rd component and water in reactor, temperature of reaction system is risen to 60 ℃ ~ 90 ℃, add initiator for reaction 1-8h, the back drips hydroxyethyl methacrylate ester class 2-5h, the polymer microballoon of winning; By mass ratio, the 3rd group of branch ︰ initiator of the 2nd group of branch ︰ of the one group of branch ︰ of water ︰ is 4 ~ 100 ︰, 1 ︰, 0.0004 ~ 0.01 ︰, 0.0004 ~ 0.01 ︰ 0.0036 ~ 0.09, and hydroxyethyl methacrylate ester class ︰ first component is 0.01 ~ 0.3 ︰ 1; Described first component is vinylbenzene or methyl methacrylate; Described second component is sodium bicarbonate, saleratus or bicarbonate of ammonia; Described the 3rd component is sodium hydroxide, potassium hydroxide or ammoniacal liquor; Described initiator is Potassium Persulphate and/or ammonium persulphate;
2) the step 1) thus obtained microsphere is mixed with the RAFT agent react 10 ~ 20h, the quality of described RAFT reagent is 1 ~ 5 times of the class of hydroxyethyl methacrylate ester described in the step 1), second polymer microballoon of area load RAFT reagent;
3) add first component, second component, the 3rd component and water in reactor, temperature of reaction system is risen to 60 ℃ ~ 90 ℃, add initiator for reaction 1-8h, the back drips light trigger 2-5h, gets the terpolymer microballoon of area load light trigger; By mass ratio, the 3rd group of branch ︰ initiator of the 2nd group of branch ︰ of the one group of branch ︰ of water ︰ is 4 ~ 100 ︰, 1 ︰, 0.0004 ~ 0.01 ︰, 0.0004 ~ 0.01 ︰ 0.0036 ~ 0.09, and it is 0.01 ~ 0.45 ︰ 100 that light draws agent ︰ first component; Described first component is vinylbenzene or methyl methacrylate; Described second component is sodium bicarbonate, saleratus or bicarbonate of ammonia; Described the 3rd component is sodium hydroxide, potassium hydroxide or ammoniacal liquor; Described initiator is Potassium Persulphate and/or ammonium persulphate;
4) with step 2) and 3) to be mixed with solid holdup by mass ratio 1 ︰ 1 be 1% ~ 20% emulsion for gained second polymer microballoon and terpolymer microballoon, in this emulsion, add first monomer, at 5 ℃ ~ 80 ℃ following ultraviolet lighting initiated polymerization 10min-5h, obtain different ball surface all the 4th polymer microballoon and the 5th polymer microballoon of grafting polymer brush; Described first monomer is N-N-isopropylacrylamide, N-vinyl pyrrolidone or vinylformic acid; By mass ratio, newborn liquid ︰ the one single body ︰ is 100 ︰ 1 ~ 20.
2. different ball difference load light trigger according to claim 1 and RAFT reagent is characterized in that also comprising the steps 5 to prepare the method for the hair-like polymer microballoon of multiple environment response type):
It is 1% ~ 20% emulsion that described the 4th polymer microballoon and the 5th polymer microballoon are made into solid holdup, in this emulsion, add second monomer, at 5 ℃ ~ 80 ℃ following ultraviolet lighting initiated polymerization 10min-5h, obtain the 6th polymer microballoon of surface grafting two block macromoleculars brush and the 7th polymer microballoon of two kinds of polyamino polymer brushes of surface grafting; Described second monomer is N-vinyl pyrrolidone, N-N-isopropylacrylamide or vinylformic acid; By mass ratio, Ru Ye ︰ second monomer is 100 ︰ 1 ~ 20.
3. different ball difference load light trigger according to claim 2 and RAFT reagent is characterized in that also comprising the steps 6 to prepare the method for the hair-like polymer microballoon of multiple environment response type):
It is 1% ~ 20% emulsion that described the 6th polymer microballoon and the 7th polymer microballoon are hybridly prepared into solid holdup, in this emulsion, add the 3rd monomer, at 5 ℃ ~ 80 ℃ following ultraviolet lighting initiated polymerization 10min-5h, obtain the 8th polymer microballoon of surface grafting three block macromoleculars brush and the 9th polymer microballoon of three kinds of homopolymerization types of surface grafting polymer brush; Described the 3rd monomer is vinylformic acid, N-N-isopropylacrylamide or N-vinyl pyrrolidone; By mass ratio, Ru Ye ︰ the 3rd monomer is 100 ︰ 1 ~ 20.
4. different ball difference load light trigger according to claim 1 and RAFT reagent is characterized in that to prepare the method for the hair-like polymer microballoon of multiple environment response type:
In described step 1), the structural formula of hydroxyethyl methacrylate ester class is as follows:
R wherein
1, R
2Be H or C
1-3Alkyl, R
3Alkylidene group for 1-3 carbon.
5. different ball difference load light trigger according to claim 1 and RAFT reagent is characterized in that to prepare the method for the hair-like polymer microballoon of multiple environment response type the structure of described synthetic RAFT reagent is as follows
Wherein, R
4, R
5Be H or C
1-3Alkyl, R
6Be C
6H
5, (CH
3)
2CHCH
2Or (CH
3)
3CCH
2
6. different ball difference load light trigger according to claim 1 and RAFT reagent is characterized in that to prepare the method for the hair-like polymer microballoon of multiple environment response type the structure of described light trigger is as follows:
Wherein, R
7Be C
6H
5, (CH
3)
2CHCH
2Or (CH
3)
3CCH
2, R
8, R
9For H or contain the alkyl of 1-3 carbon.
7. it is characterized in that to prepare the method for the hair-like polymer microballoon of multiple environment response type according to each described different ball difference load light trigger and RAFT reagent in the claim 1 to 6:
In described step 1), before adding described initiator, in reactor, add linking agent, described linking agent is Vinylstyrene or Ethylene glycol dimethacrylate, the mass ratio of described first component and linking agent is 1:0.05 ~ 0.5.
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Application publication date: 20110824 |