CN107099005B - A kind of CO based on inierpeneirating network structure2Response type polymer microballoon and preparation method thereof - Google Patents
A kind of CO based on inierpeneirating network structure2Response type polymer microballoon and preparation method thereof Download PDFInfo
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- CN107099005B CN107099005B CN201710314926.1A CN201710314926A CN107099005B CN 107099005 B CN107099005 B CN 107099005B CN 201710314926 A CN201710314926 A CN 201710314926A CN 107099005 B CN107099005 B CN 107099005B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000008367 deionised water Substances 0.000 claims abstract description 48
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 48
- 230000004044 response Effects 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 230000008961 swelling Effects 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229940126062 Compound A Drugs 0.000 claims abstract description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004005 microsphere Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 18
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 7
- -1 acrylic acid glycol esters Chemical class 0.000 claims description 7
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001409 amidines Chemical class 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- KGMXPXPXPAAUMD-UHFFFAOYSA-N propane;dihydrochloride Chemical compound Cl.Cl.CCC KGMXPXPXPAAUMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 2
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 235000011078 sorbitan tristearate Nutrition 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 4
- 229940005605 valeric acid Drugs 0.000 claims 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 229940099500 cystamine Drugs 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000010926 purge Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 87
- 239000006185 dispersion Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 12
- 229920002401 polyacrylamide Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 206010049244 Ankyloglossia congenital Diseases 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FCDZZFLRLVQGEH-UHFFFAOYSA-N ethane-1,2-diol;prop-2-enoic acid Chemical compound OCCO.OC(=O)C=C FCDZZFLRLVQGEH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
CO of the present invention based on inierpeneirating network structure2The preparation method of responsive polymer microballoon: (1) compound A and crosslinking agent are dissolved in deionized water and obtain solution I, initiator is dissolved in deionized water and obtains solution II, at room temperature the maintaining nitrogen purge deoxygenation into two kinds of solution respectively；Emulsifier is dissolved in organic solvent and obtains emulsifier solution；In N2Under protection by solution I and the solution II after deoxygenation synchronize be added drop-wise in emulsifier solution, be stirred to react at 40~80 DEG C；(2) after skeleton polymer microballoon being mixed with compound B, crosslinking agent, initiator, deionized water, swelling obtains swollen mixt under room temperature, emulsifier is dissolved in organic solvent and obtains emulsifier solution, swollen mixt is uniformly mixed with emulsifier solution, in N2It protects, be stirred to react under the conditions of 40~80 DEG C.The method of the present invention can improve CO2The dispersibility and CO of response type polymer microballoon2Responsiveness, and make CO2Responsiveness is controllable.
Description
Technical field
The invention belongs to intelligent macromolecule microballoon fields, are related to a kind of CO2Response type polymer microballoon and preparation method thereof.
Background technique
Intelligent macromolecule microballoon be one kind can sensing external environment variation, and by self response adjustment realize performance
And the new material of change in size.CO2It is not only cheap and easy to get as a kind of greenhouse gases, but also be also a kind of biological cell metabolism
Product has good biocompatibility and membrane permeability, not only easy to operate as the stimuli responsive factor, at low cost
It is honest and clean, and will not donor frenulum carry out new pollution, have in fields such as medicine controlled releasing, bio-sensing, energy environment protection, oil exploitations
With potential using value.CO at present2The preparation of micro-tapping responsive polymer microballoon mainly includes two kinds of approach: the first is
Microballoon is first prepared, then by CO2It responds monomer and carries out graft copolymerization in microsphere surface；Second is by radically homo or to be total to
Poly- mode directly prepares CO2Response type microballoon.Second of approach preparation process is easy, more meets the reality of Macroscopic single crystal technique
It is required that being conducive to large-scale production, but have the defects that inhibit its response performance because of microsphere adhesive.Therefore, it studies a kind of new
Synthetic route is prepared with good dispersion and CO2Response performance, and CO2The controllable intelligent microsphere of response performance has important
Meaning.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of CO based on inierpeneirating network structure2Response
Type polymer microballoon and preparation method thereof, to improve CO2The dispersibility and CO of response type polymer microballoon2Responsiveness, and make CO2
Responsiveness is controllable.
The preparation method of CO2 response type polymer microballoon of the present invention based on inierpeneirating network structure, steps are as follows:
(1) 10~15 mass part compound A and 0.02~0.8 mass parts crosslinking agent are dissolved in deionized water and obtain solution
I, 0.05~0.5 mass parts initiator is dissolved in deionized water and obtains solution II, is held respectively into two kinds of solution at room temperature
It is continuous to be passed through nitrogen to remove oxygen；0.2~1.0 mass parts emulsifier is dissolved in organic solvent and obtains emulsifier solution；In N2
Under protection by solution I and the solution II after deoxygenation synchronize be added drop-wise in emulsifier solution, after solution I and solution II drip,
N2Protection is stirred to react 1~7h under the conditions of 40~80 DEG C, isolates reaction thus obtained microsphere after reaction, with ethyl alcohol and go from
Sub- water is alternately dried in vacuo after washing microballoon removes impurity, obtains skeleton polymer microballoon；
The structural formula of the compound A are as follows:
In structure above, R1For H ,-CH2CH3Or-CH (CH3)2；
(2) by 0.5~2.0 mass parts of skeleton polymer microballoon obtained by step (1) and 1.0~5.0 mass part compound B,
After 0.01~0.05 mass parts crosslinking agent, 0.02~0.05 mass parts initiator and deionized water mixing, it is swollen under room temperature
0.5~5h obtains swollen mixt, and 0.8~2.0 mass parts emulsifier is dissolved in organic solvent and obtains emulsifier solution, will be molten
Swollen mixture is mixed with emulsifier solution, in N2It protects, be stirred to react 1~15h under the conditions of 40~80 DEG C, separate after reaction
Thus obtained microsphere is reacted out, is alternately dried in vacuo with ethyl alcohol and deionized water after washing microballoon removes impurity to get with interpenetrating net
The CO of network structure2Response type polymer microballoon；
The structural formula of the compound B is
In structural formula, R2For-CH3Or-CH2CH3。
In the above method, the emulsifier be span-60, span-65, span-80, span-85, Tween-40,
One of Tween-60, Tween-80, Tween-85.
In the above method, the crosslinking agent is methylene bisacrylamide, in double acrylic acid glycol esters, double acryloyl cystamines
One kind.
In the above method, the initiator is water soluble starter ammonium persulfate (APS), potassium peroxydisulfate (K2S2O4), azo
Dicyano valeric acid (ACVA), azo diisobutyl amidine hydrochloride (AIBA), azo diimidazole quinoline base propane dihydrochloride (AIBI)
One of.
In the above method, the organic solvent of the emulsifier solution is hexamethylene, in n-hexane, kerosene, saxol
One kind.
In the above method, deionized water described in step (1) and step (2) and the dosage of organic solvent are corresponding can make
Be added thereto solute dissolution be limited.
In the above method, when selection crosslinking agent is methylene bisacrylamide, chemical equation are as follows:
The present invention also provides the CO based on inierpeneirating network structure of above method preparation2Response type polymer microballoon.
Compared with prior art, the invention has the following advantages:
1, CO of the present invention2Response type polymer microballoon has inierpeneirating network structure, soap-free emulsion polymeization between microballoon, dispersibility
It is good.
2, CO of the present invention2Response type polymer microballoon is alternately being passed through CO2And N2Under the conditions of, it is able to achieve microballoon system
PH value transformation and microsphere volume reversible change, show it with excellent CO2Response performance.
3, the method for the invention is swollen list by changing in the micro-sphere crosslinked degree of skeleton polymer, and change swelling process
The concentration of body (compound B) can prepare different CO2The intelligent microsphere of expansion rate is responded, realizes and responds expansile controllable stimuli.
4, the method for the invention synthesizes CO2The reaction condition of response type polymer microballoon is mild, and yield is high, operation letter
It is single, be conducive to large-scale production.
Detailed description of the invention
Fig. 1 is to CO made from Examples 1 to 52The scanning electron microscope (SEM) photograph of response type polymer microballoon.
Fig. 2 is CO made from embodiment 32The infrared spectrum of response type polymer microballoon.
Fig. 3 is CO made from embodiment 32Microsphere volume and transparency change before and after the response of response type polymer microballoon
Microphoto.
Fig. 4 is CO made from Examples 1 to 52Response type polymer microballoon is in CO2Respond the size and aqueous dispersion of front and back
It is pH value variation.
Fig. 5 is the degree of cross linking of polyacrylamide microsphere (skeleton polymer microballoon) in Examples 1 to 3 to interpenetrating net obtained
Network microballoon CO2The influence of response type expansion rate.
CO of the concentration to polymer microballoon obtained that Fig. 6 is compound DMAPMA in embodiment 3~5 (swelling monomer)2
Respond the influence of expansion rate.
Specific embodiment
Below by embodiment to the CO of the present invention based on inierpeneirating network structure2Response type polymer microballoon and its system
Preparation Method is described further.
In following embodiment, dosage when deionized water and hexamethylene are as solvent is to meet corresponding solute dissolution i.e.
It can.
Embodiment 1
(1) acrylamide 12.30g and crosslinking agent methylene bisacrylamide 0.61g (degree of cross linking 4.9wt%) are dissolved in
Solution I is obtained in ionized water, and initiator A IBI 0.1g is dissolved in deionized water and obtains solution II, it is molten to two kinds at room temperature
It is passed through nitrogen deoxygenation 0.5h in liquid, emulsifier Span-60 0.5g is dissolved in hexamethylene and obtains emulsifier solution, in N2Protection
The lower solution I by after deoxygenation and solution II synchronize be added drop-wise in emulsifier solution, after solution I and solution II drip, in N2It protects
It protects, be stirred to react 6h at 60 DEG C, isolate reaction thus obtained microsphere after reaction, alternately wash microballoon with ethyl alcohol and deionized water
Vacuum drying is after removing impurity to get skeleton polymer microballoon (polyacrylamide microsphere)；
(2) by skeleton polymer microballoon obtained by 1.05g step (1) and 2.8g DMAPMA (dimethylamino-propyl metering system
Amide), crosslinking agent methylene bisacrylamide 0.03g, initiator A CVA 0.03g and 27mL deionized water mixing after (DMAPMA
Concentration is 0.10gmL-1), it is swollen 3h at room temperature and obtains swollen mixt, emulsifier Span-80 0.8g is dissolved in hexamethylene
In obtain emulsifier solution, swollen mixt is uniformly mixed with emulsifier solution, in N2It protects, be stirred to react under the conditions of 70 DEG C
12h isolates reaction thus obtained microsphere after reaction, and vacuum is dry after alternately washing microballoon removal impurity with ethyl alcohol and deionized water
It is dry that get the CO2 response type polymer microballoon with inierpeneirating network structure, scanning electron microscopic observation result is as shown in Figure 1a, from
It can be seen that the interpenetrating networks microballoon obtained sphere smooth for surface, and good dispersion in figure.
Embodiment 2
(1) it by acrylamide 12.30g and crosslinking agent methylene bisacrylamide 0.025g (degree of cross linking 0.2wt%), is dissolved in
Solution I is obtained in deionized water, initiator A IBI 0.1g is dissolved in deionized water and obtains solution II, at room temperature to two kinds
It is passed through nitrogen deoxygenation 0.5h in solution, emulsifier Span-60 0.5g is dissolved in hexamethylene and obtains emulsifier solution, in N2It protects
Under shield by solution I and the solution II after deoxygenation synchronize be added drop-wise in emulsifier solution, after solution I and solution II drip, in N2
It protects, be stirred to react 6h at 60 DEG C, isolate reaction thus obtained microsphere after reaction, alternately washed with ethyl alcohol and deionized water micro-
Vacuum drying is after ball removes impurity to get skeleton polymer microballoon (polyacrylamide microsphere)；
(2) by skeleton polymer microballoon obtained by 1.05g step (1) and 2.8g DMAPMA, crosslinking agent methylene bisacrylamide
(DMAPMA concentration is 0.10gmL after 0.03g, the mixing of initiator A CVA0.03g and 27mL deionized water-1), it is molten at room temperature
Swollen 3h obtains swollen mixt, and emulsifier Span-80 0.8g is dissolved in hexamethylene and obtains emulsifier solution, and swelling is mixed
Object is uniformly mixed with emulsifier solution, in N2It protects, be stirred to react 12h under the conditions of 70 DEG C, isolate reaction institute after reaction
Microballoon is obtained, is alternately dried in vacuo with ethyl alcohol and deionized water after washing microballoon removes impurity to get with inierpeneirating network structure
CO2 response type polymer microballoon, scanning electron microscopic observation result is as shown in Figure 1 b, and prepared interpenetrating networks are micro- as we know from the figure
Ball surface can adhere to a little membranaceous material, but still have excellent dispersibility, not bond.Analyze reason are as follows: swelling process
In the too low degree of cross linking cause to be absorbed into excessive monomer so that hydrogen bond provided by polyacrylamide seed microballoon is not enough to
Stabilized so many monomer, monomer are easily migrated to seed microsphere surface.When being warming up to reaction temperature, Yi Fasheng monomer is poly- third
The polymerization of acrylamide microsphere surface forms the pattern of final microsphere surface attachment film.
Embodiment 3
(1) it by acrylamide 12.30g and crosslinking agent methylene bisacrylamide 0.12g (degree of cross linking 0.97wt%), is dissolved in
Solution I is obtained in deionized water, initiator A IBI 0.1g is dissolved in deionized water and obtains solution II, at room temperature to two kinds
It is passed through nitrogen deoxygenation 0.5h in solution, emulsifier Span-60 0.5g is dissolved in hexamethylene and obtains emulsifier solution, in N2It protects
Under shield by solution I and the solution II after deoxygenation synchronize be added drop-wise in emulsifier solution, after solution I and solution II drip, in N2
It protects, be stirred to react 6h at 60 DEG C, isolate reaction thus obtained microsphere after reaction, alternately washed with ethyl alcohol and deionized water micro-
To get skeleton polymer microballoon (polyacrylamide microsphere), infrared spectrum is shown in Fig. 2 for vacuum drying after ball removes impurity；
(2) by skeleton polymer microballoon 1.05g obtained by step (1) and 2.8g DMAPMA (infrared spectrum is shown in Fig. 2), crosslinking
(DMAPMA concentration is 0.10g after agent methylene bisacrylamide 0.03g, the mixing of initiator A CVA0.03g and 27mL deionized water
mL-1), it is swollen 3h at room temperature and obtains swollen mixt, emulsifier Span-80 1.0g is dissolved in hexamethylene and obtains emulsifier
Swollen mixt is uniformly mixed, in N by solution with emulsifier solution2It protects, be stirred to react 12h under the conditions of 70 DEG C, reaction terminates
After isolate reaction thus obtained microsphere, have with vacuum drying after ethyl alcohol and deionized water alternately washing microballoon removal impurity
The CO of inierpeneirating network structure2Response type polymer microballoon (infrared spectrum is shown in Fig. 2), scanning electron microscopic observation result such as Fig. 1 c institute
Show it can be seen that obtained inierpeneirating network structure microballoon has smooth spherical structure, and there is excellent dispersibility.
Embodiment 4
(1) acrylamide 12.30g and crosslinking agent methylene bisacrylamide 0.12g (degree of cross linking 0.97wt%) are dissolved in
Solution I is obtained in deionized water, initiator A IBI 0.1g is dissolved in deionized water and obtains solution II, at room temperature to two kinds
It is passed through nitrogen deoxygenation 0.5h in solution, emulsifier Span-60 0.5g is dissolved in hexamethylene and obtains emulsifier solution, in N2It protects
Under shield by solution I and the solution II after deoxygenation synchronize be added drop-wise in emulsifier solution, after solution I and solution II drip, in N2
It protects, be stirred to react 6h at 60 DEG C, isolate reaction thus obtained microsphere after reaction, alternately washed with ethyl alcohol and deionized water
Vacuum drying is after microballoon removes impurity to get skeleton polymer microballoon (polyacrylamide microsphere)；
(2) skeleton polymer microballoon 1.05g and 2.8g DMAPMA, crosslinking agent methylene bisacrylamide obtained by institute's step (1)
(DMAPMA concentration is 0.078gmL after 0.03g, the mixing of initiator A CVA 0.03g and 36mL deionized water-1), at room temperature
Swelling 3h obtain swollen mixt, emulsifier Span-80 is dissolved in hexamethylene and obtains emulsifier solution, by swollen mixt with
Emulsifier solution is uniformly mixed, in N2It protects, be stirred to react 12h under the conditions of 70 DEG C, it is micro- to isolate reaction gained after reaction
Ball is alternately dried in vacuo with ethyl alcohol and deionized water after washing microballoon removes impurity to get the CO with inierpeneirating network structure2It rings
Type polymer microballoon is answered, scanning electron microscopic observation result is as shown in Figure 1 d, it can be seen that finally obtained inierpeneirating network structure
Microballoon has smooth spherical structure, and has dispersibility well.
Embodiment 5
(1) it by acrylamide 12.30g and crosslinking agent methylene bisacrylamide 0.12g (degree of cross linking 0.97wt%), is dissolved in
Solution I is obtained in deionized water, initiator A IBI 0.1g is dissolved in deionized water and obtains solution II, at room temperature to two kinds
It is passed through nitrogen deoxygenation 0.5h in solution, 60 0.5g of emulsifier Span is dissolved in hexamethylene and obtains emulsifier solution, in N2It protects
Under shield by solution I and the solution II after deoxygenation synchronize be added drop-wise in emulsifier solution, after solution I and solution II drip, in N2
It protects, be stirred to react 6h at 60 DEG C, isolate reaction thus obtained microsphere after reaction, alternately washed with ethyl alcohol and deionized water micro-
Vacuum drying is after ball removes impurity to get skeleton polymer microballoon (polyacrylamide microsphere)；
(2) by skeleton polymer microballoon 1.05g obtained by step (1) and 2.8g DMAPMA, crosslinking agent methylene bisacrylamide
(DMAPMA concentration of aqueous solution is 0.16gmL after 0.03g, the mixing of initiator A CVA and 18mL deionized water-1), it is molten at room temperature
Swollen 3h obtains swollen mixt, and emulsifier Span-80 0.8g is dissolved in hexamethylene and obtains emulsifier solution, and swelling is mixed
Object is uniformly mixed with emulsifier solution, in N2It protects, be stirred to react 12h under the conditions of 70 DEG C, isolate reaction institute after reaction
Microballoon is obtained, is alternately dried in vacuo with ethyl alcohol and deionized water after washing microballoon removes impurity to get with inierpeneirating network structure
CO2Response type polymer microballoon, scanning electron microscopic observation result as shown in fig. le, it can be seen that microsphere surface will appear film
Shape substance, but good dispersibility is still maintained between microballoon, do not bond.This is because when swelling monomer concentration is excessively high,
Hydrogen bond provided by polyacrylamide seed microballoon is not enough to stabilized so many monomer, and monomer is caused to move to seed microsphere surface
It moves.When being warming up to reaction temperature, it is attached to form final microsphere surface in polyacrylamide microsphere surface aggregate for Yi Fasheng monomer
The pattern of film.
Embodiment 6
(1) it by acrylamide 10g and the double acrylic acid glycol ester 0.02g of crosslinking agent, is dissolved in deionized water and obtains solution
I, initiator A IBI 0.05g is dissolved in deionized water and obtains solution II, is passed through nitrogen deoxygenation into two kinds of solution at room temperature
Emulsifier Span-60 0.2g is dissolved in hexamethylene and obtains emulsifier solution, in N by 0.5h2By the solution I after deoxygenation under protection
With solution II synchronize be added drop-wise in emulsifier solution, after solution I and solution II drip, in N2It protects, be stirred to react at 70 DEG C
5h isolates reaction thus obtained microsphere after reaction, and vacuum is dry after alternately washing microballoon removal impurity with ethyl alcohol and deionized water
It is dry to get skeleton polymer microballoon (polyacrylamide microsphere)；
(2) by skeleton polymer microballoon 0.5g obtained by step (1) and 1.0g DMAPMA, the double acrylic acid ethylene glycol of crosslinking agent
After ester 0.01g, initiator A CVA and deionized water mix, it is swollen 3h at room temperature and obtains swollen mixt, by emulsifier Span
80 0.8g, which are dissolved in hexamethylene, obtains emulsifier solution, swollen mixt is uniformly mixed with emulsifier solution, in N2Protection,
It is stirred to react 12h under the conditions of 80 DEG C, isolates reaction thus obtained microsphere after reaction, is alternately washed with ethyl alcohol and deionized water micro-
Vacuum drying is after ball removes impurity to get the CO with inierpeneirating network structure2Response type polymer microballoon.
Embodiment 7
(1) it by acrylamide 15g and crosslinking agent methylene bisacrylamide 0.8g, is dissolved in deionized water and obtains solution I, it will
Initiator A IBI 0.5g, which is dissolved in deionized water, obtains solution II, is passed through nitrogen deoxygenation 0.5h into two kinds of solution at room temperature,
60 1.0g of emulsifier Span is dissolved in hexamethylene and obtains emulsifier solution, in N2By solution I after deoxygenation and molten under protection
Liquid II, which synchronizes, to be added drop-wise in emulsifier solution, after solution I and solution II drip, in N2It protects, be stirred to react 6h at 60 DEG C, instead
Reaction thus obtained microsphere is isolated after answering, and is alternately dried in vacuo after washing microballoon removes impurity with ethyl alcohol and deionized water, i.e.,
It obtains skeleton polymer microballoon (polyacrylamide microsphere)；
(2) by skeleton polymer microballoon 2.0g obtained by step (1) and 5.0g DMAPMA, crosslinking agent methylene bisacrylamide
After 0.05g, initiator A CVA and deionized water mix, it is swollen 3h at room temperature and obtains swollen mixt, by emulsifier Span 80
2.0g, which is dissolved in hexamethylene, obtains emulsifier solution, swollen mixt is uniformly mixed with emulsifier solution, in N2Protection, 70
It is stirred to react 12h under the conditions of DEG C, isolates reaction thus obtained microsphere after reaction, alternately washs microballoon with ethyl alcohol and deionized water
Vacuum drying is after removing impurity to get the CO2 response type polymer microballoon with inierpeneirating network structure.
The CO of the polymer microballoon of 8 Examples 1 to 5 of embodiment preparation2Response performance test
1, optical microphotograph sem observation
Optical microphotograph sem observation instrument model stereomicroscope XTL-340 (Shanghai optical instrument Co., Ltd).
Test process are as follows: be successively passed through enough CO in the aqueous dispersion of the CO2 response type polymer microballoon prepared to embodiment 32
And N2, then it is sucked out with suction pipe one after another drop of on glass slide, with micro- sem observation, and shoots microballoon picture.
Test result such as Fig. 3 is passed through CO as can be seen from Figure 32Microballoon afterwards shows apparent size increase and transparency
Enhancing, be passed through N2After return back to original state.Interpretation of result are as follows: since the tertiary amine component in microballoon is by CO2Protonation generates season
Ammonium salt, causes microballoon hydrophily to enhance, and more water penetrations are into microballoon.Final Microsphere Size is caused to increase and respond transparent
Degree enhancing.It is passed through N2Afterwards, the quaternary ammonium salt of protonation is returned to tertiary amine state again, causes microballoon hydrophobicity to enhance, replys microballoon
To initial smaller size and weaker transparency.
2, aqueous microsphere dispersion system pH value is tested
The test instrument of the pH value of aqueous microsphere dispersion system is pH meter (Sartorius basic pH meter PB-
10).Test process are as follows: take the CO of a certain amount of each embodiment preparation respectively2Response type polymer microballoon falls with 400mL deionized water
Enter 500mL beaker, is successively passed through enough CO2And N2Afterwards, it by the pH meter insertion aqueous microsphere dispersion system after correction, is read after stablizing
Take pH value.
Test results are shown in figure 4, and the pH value of initial aqueous dispersion is 8.8 or so, is passed through CO2Aqueous dispersion afterwards
PH value drops to 4.9 or so, then is passed through N2CO is discharged2The pH value of aqueous dispersion is returned to 8.7 or so again afterwards.Analysis on Mechanism: microballoon
CO is passed through in aqueous dispersion2Afterwards, CO2It reacts to form weak acid carbonic acid with water, and generates ammonium carbonate in conjunction with tertiary amine, lead to body
It is pH value decline；It is passed through N2Afterwards, weak acid carbonic acid is gradually decomposed with ammonium carbonate, and with CO2The form of gas is escaped from dispersion
Out, thus system pH reply.
Test result shows CO of the present invention2The aqueous dispersion of response type polymer microballoon is with CO2Be passed through with
Discharge, can lead to the reversible change of aqueous microsphere dispersion system pH value.
3, microspherulite diameter test analysis
The test instrument of Microsphere Size is 2000 laser particle analyzer of Malvern (Malvern, UK), is equipped with 633nm
Helium-neon laser and 466nm solid-state blue laser.To the CO of each embodiment preparation2Response type polymer microballoon carries out
Following operation: a certain amount of CO is taken2Response type polymer microballoon and 400mL deionized water are mixed in beaker, are first led into beaker
Enter enough CO2And adjust the speed Malvern ParticleSizer agitating paddle to 1000rpm, it clicks and tests and carry out reading data, test is completed
It is passed through N again afterwards2, Microsphere Size is tested according to same method.
According to formula volume expansion rate=(CO2The diameter of microballoon/initial microballoon diameter after response)3Calculate each implementation
The cubical expansivity of the CO2 response type polymer microballoon of example preparation.
Test data and result:
Embodiment 1: microballoon CO2Response performance is as shown in Fig. 4-embodiment 1.Microsphere diameter variation is 277 μm to 335 μm,
That is the CO of resulting polymers microballoon2Responding cubical expansivity is 1.8.
Embodiment 2: microballoon CO2Response performance is as shown in Fig. 4-embodiment 2.Microsphere diameter variation is 286 μm to 648 μm,
That is the CO of resulting polymers microballoon2Responding cubical expansivity is 11.6.
Embodiment 3: microballoon CO2Response performance is as shown in Fig. 4-embodiment 3.Microsphere diameter variation is 312 μm to 433 μm,
The CO of resulting polymers microballoon2Responding cubical expansivity is 2.7.
Embodiment 4: microballoon CO2Response performance is as shown in Fig. 4-embodiment 4.Microsphere diameter variation is 307 μm to 385 μm,
The CO of resulting polymers microballoon2Responding cubical expansivity is 2.0.
Embodiment 5: microballoon CO2Response performance is as shown in Fig. 4-embodiment 5.Microsphere diameter variation is 296 μm to 485 μm,
The CO of resulting polymers microballoon2Responding cubical expansivity is 4.4.
Test results are shown in figure 4, and Microsphere Size is distributed as unimodal dispersion, illustrates not bond between microballoon；Relatively
CO is being passed through in the microballoon of initial microballoon, different formulations2It (generates quaternary ammonium salt) afterwards and shows different degrees of expansion multiplying power, be passed through
N2(quaternary ammonium salt reverts back to tertiary amine) Microsphere Size is returned to original state afterwards.
Interpretation of result: embodiment 2,3,1 with polyacrylamide backbone polymer microballoon the degree of cross linking increase (from
0.2wt%, 0.97wt% to 4.9wt%), the CO being prepared2Tertiary amine content reduces in response type polymer microballoon, causes
Microballoon response expansion rate gradually decreases (from 11.6,2.7 to 1.8), as shown in Figure 5.Embodiment 4,3,5 is with swelling monomer concentration
Increase (from 0.078,0.10 to 0.16gmL -1), the CO that is prepared2Tertiary amine content increases in response type polymer microballoon,
Microballoon response expansion rate is caused to gradually rise (from 2.0,2.7 to 4.4), as shown in Figure 6.Illustrate that this patent the method can pass through
Change the micro-sphere crosslinked degree of skeleton polymer, changes the concentration for being swollen monomer (compound B) in swelling process, prepare different CO2It rings
The intelligent microsphere of expansion rate is answered, realizes and responds expansile controllable stimuli.
Claims (10)
1. a kind of CO based on inierpeneirating network structure2The preparation method of response type polymer microballoon, it is characterised in that steps are as follows:
(1) 10~15 mass part compound A and 0.02~0.8 mass parts crosslinking agent are dissolved in deionized water and obtain solution I, it will
0.05~0.5 mass parts initiator, which is dissolved in deionized water, obtains solution II, persistently leads into two kinds of solution respectively at room temperature
Enter nitrogen to remove oxygen；0.2~1.0 mass parts emulsifier is dissolved in organic solvent and obtains emulsifier solution；In N2Protection
The lower solution I by after deoxygenation and solution II synchronize be added drop-wise in emulsifier solution, after solution I and solution II drip, in N2It protects
It protects, be stirred to react 1~7h under the conditions of 40~80 DEG C, reaction thus obtained microsphere is isolated after reaction, with ethyl alcohol and deionized water
It is alternately dried in vacuo after washing microballoon removal impurity, obtains skeleton polymer microballoon；
The structural formula of the compound A are as follows:
In structure above, R1For H ,-CH2CH3Or-CH (CH3)2；
(2) by 0.5~2.0 mass parts of skeleton polymer microballoon and 1.0~5.0 mass part compound B, 0.01 obtained by step (1)
After~0.05 mass parts crosslinking agent, 0.02~0.05 mass parts initiator and deionized water mixing, 0.5~5h is swollen under room temperature
Swollen mixt is obtained, 0.8~2.0 mass parts emulsifier is dissolved in organic solvent and obtains emulsifier solution, swelling is mixed
Object is mixed with emulsifier solution, in N2It protects, be stirred to react 1~15h under the conditions of 40~80 DEG C, isolate reaction after reaction
Thus obtained microsphere is alternately dried in vacuo with ethyl alcohol and deionized water after washing microballoon removes impurity to get with inierpeneirating network structure
CO2Response type polymer microballoon；
The structural formula of the compound B is
In structural formula, R2For-CH3Or-CH2CH3。
2. according to claim 1 based on the CO of inierpeneirating network structure2The preparation method of response type polymer microballoon, feature
Be emulsifier described in step (1) and step (2) be span-60, span-65, span-80, span-85, Tween-40,
One of Tween-60, Tween-80, Tween-85.
3. the CO according to claim 1 or claim 2 based on inierpeneirating network structure2The preparation method of response type polymer microballoon, it is special
Sign is that crosslinking agent described in step (1) and step (2) is methylene bisacrylamide, double acrylic acid glycol esters, double propylene
One of acyl cystamine.
4. the CO according to claim 1 or claim 2 based on inierpeneirating network structure2The preparation method of response type polymer microballoon, it is special
Sign is that initiator described in step (1) and step (2) is water soluble starter ammonium persulfate, potassium peroxydisulfate, azo dicyan
One of base valeric acid, azo diisobutyl amidine hydrochloride, azo diimidazole quinoline base propane dihydrochloride.
5. according to claim 3 based on the CO of inierpeneirating network structure2The preparation method of response type polymer microballoon, feature
It is that initiator described in step (1) and step (2) is water soluble starter ammonium persulfate, potassium peroxydisulfate, azo dicyano
One of valeric acid, azo diisobutyl amidine hydrochloride, azo diimidazole quinoline base propane dihydrochloride.
6. the CO according to claim 1 or claim 2 based on inierpeneirating network structure2The preparation method of response type polymer microballoon, it is special
Sign is that the organic solvent of emulsifier solution described in step (1) and step (2) is hexamethylene, n-hexane, kerosene, liquid stone
One of wax oil.
7. according to claim 3 based on the CO of inierpeneirating network structure2The preparation method of response type polymer microballoon, feature
The organic solvent for being emulsifier solution described in step (1) and step (2) is hexamethylene, n-hexane, kerosene, atoleine
One of oil.
8. according to claim 4 based on the CO of inierpeneirating network structure2The preparation method of response type polymer microballoon, feature
The organic solvent for being emulsifier solution described in step (1) and step (2) is hexamethylene, n-hexane, kerosene, atoleine
One of oil.
9. the CO according to claim 1 or claim 2 based on inierpeneirating network structure2The preparation method of response type polymer microballoon, it is special
Sign is deionized water described in step (1) and step (2) and the dosage of organic solvent can make to be added thereto accordingly
Solute dissolution is limited.
10. the CO based on inierpeneirating network structure that in claim 1 to 9 prepared by any claim the method2Response type polymerization
Object microballoon.
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| US5849594A (en) * | 1994-12-19 | 1998-12-15 | Sealed Air (Nz) Limited | Carbon dioxide sensitive material |
| CN101260173A (en) * | 2008-04-22 | 2008-09-10 | 东华大学 | High elastic semi-interpenetrating network composite gel and preparation method thereof |
| CN101985484A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院成都有机化学有限公司 | Novel temperature stimuli responsive macromonomer |
| CN105037593A (en) * | 2014-04-18 | 2015-11-11 | 中国科学院成都有机化学有限公司 | CO2-responding monomer and polymer thereof |
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| US7913541B2 (en) * | 2007-04-30 | 2011-03-29 | Honeywell International Inc. | Matrix nanocomposite containing aminocarbon nanotubes for carbon dioxide sensor detection |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849594A (en) * | 1994-12-19 | 1998-12-15 | Sealed Air (Nz) Limited | Carbon dioxide sensitive material |
| CN101260173A (en) * | 2008-04-22 | 2008-09-10 | 东华大学 | High elastic semi-interpenetrating network composite gel and preparation method thereof |
| CN101985484A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院成都有机化学有限公司 | Novel temperature stimuli responsive macromonomer |
| CN105037593A (en) * | 2014-04-18 | 2015-11-11 | 中国科学院成都有机化学有限公司 | CO2-responding monomer and polymer thereof |
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