CN102634044B - Method for synthesizing superfine nano hybridization microspheres by use of nanoreactor - Google Patents
Method for synthesizing superfine nano hybridization microspheres by use of nanoreactor Download PDFInfo
- Publication number
- CN102634044B CN102634044B CN 201210098103 CN201210098103A CN102634044B CN 102634044 B CN102634044 B CN 102634044B CN 201210098103 CN201210098103 CN 201210098103 CN 201210098103 A CN201210098103 A CN 201210098103A CN 102634044 B CN102634044 B CN 102634044B
- Authority
- CN
- China
- Prior art keywords
- nano
- superfine
- solvent
- organic
- gel particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000009396 hybridization Methods 0.000 title claims abstract description 11
- 239000004005 microsphere Substances 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000007863 gel particle Substances 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 230000005291 magnetic effect Effects 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000009423 ventilation Methods 0.000 claims description 8
- -1 dodecyl benzenesulfonyl Chemical group 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 239000004567 concrete Substances 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 244000144992 flock Species 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 230000002459 sustained effect Effects 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- UJMZZAZBRIPOHZ-UHFFFAOYSA-N 2-ethylhexan-1-ol;titanium Chemical compound [Ti].CCCCC(CC)CO UJMZZAZBRIPOHZ-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical class [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 229920004890 Triton X-100 Polymers 0.000 claims description 2
- 239000013504 Triton X-100 Substances 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- JPQBRSQJGWOTGC-UHFFFAOYSA-N methyl(silyloxysilyloxy)silane Chemical class C[SiH2]O[SiH2]O[SiH3] JPQBRSQJGWOTGC-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 2
- DJVKJGIZQFBFGS-UHFFFAOYSA-N n-[2-[2-(prop-2-enoylamino)ethyldisulfanyl]ethyl]prop-2-enamide Chemical compound C=CC(=O)NCCSSCCNC(=O)C=C DJVKJGIZQFBFGS-UHFFFAOYSA-N 0.000 claims 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 11
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- OOTFVKOQINZBBF-UHFFFAOYSA-N cystamine Chemical compound CCSSCCN OOTFVKOQINZBBF-UHFFFAOYSA-N 0.000 description 1
- 229940099500 cystamine Drugs 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 231100000647 material safety data sheet Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a method for synthesizing superfine nano hybridization microspheres by use of a nanoreactor, belonging to the technical field of inorganic/organic hybridization materials. The method comprises the following steps of: preparing superfine nano-polymer gel particles below 10nm by use of a reverse micro-emulsion system and a thermal initiation polymerization mode; and complexing organic compounds of Ti, Si and the like by taking the superfine nano-polymer gel particles as a nanoreactor to form organic/inorganic hybridization microspheres consistent with the original nano-polymer particles in form and size. The method disclosed by the invention has a simple operation technology and low cost, and is safe and convenient to operate, and the product has the advantages of superfine size, controllability within 10nm range, uniform size distribution and the like, thereby laying a good foundation for the industrial application of synthesizing superfine controllable nano-polymer particles, providing new thoughts of designing/synthesizing multifunctional size-controllable organic/inorganic hybridization nano-particles, and widening the synthesis and application prospects of new materials.
Description
Technical field
The invention belongs to inorganic-organic hybrid material technology field, particularly a kind of method of utilizing nano-reactor synthesizing superfine nano hybridization microballoon.
Background technology
Nano material is owing to have the peculiar property that obviously is different from bulk material and individual molecule: surface effects, volume effect, quantum size effect and macroscopical tunnel effect etc., and in the important value of all many-sides such as electronics, optics, chemical industry, pottery, biology and medicine, it has caused countries in the world scientific workers' great interest, this makes closely during the last ten years, the research of each side such as the preparation of nano material, performance and application has all obtained great successes.Along with the continuous development of nanotechnology, the concept of nano-reactor also is suggested, and relevant research is becoming focus.
Usually said chemical reactor refers to take place a particular place that chemical reaction is required, generally is concrete reactor and other chemical industry equipments.Different with the chemical reactor on the conventional meaning, nano-reactor is not general concrete mechanical means, but reflects and residingly be subjected to Jie of nano-scale modulation to see environment, is embodied as the medium, carrier, interface of reaction etc.Nano-reactor should be nano material or material with nanostructure usually, they provide a kind of space of nanoscale, be that reaction-limited is in this nanometer spatial dimension, by the product that size, material and other factors of controlling nano-reactor can obtain to have special construction and character, this product has four big effects of above-mentioned nano material.
Inorganic/organic polymer hybrid nano composite material is an importance in the nano material development and application, inorganic component and organic constituent are compound at nano level, merged high flexibility, workability of the high strength of inorganic materials, high rigidity, high rigidity, high stability and organic materials etc., made that the material after compound has character such as the special optics of inorganic nano material, electricity, magnetics.Organic polymer can solve the unstable of nano material physics and chemistry as the supporting carrier of nano material, is the factor of crucial importance that nano material is succeedd and used.This class hybridized nano composite material had not only had the toughness of macromolecular material and workability but also had had rigidity and the property of inorganic nano material.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing nano-reactor synthesizing superfine nano hybridization microballoon, this method prepares the following superfine nano polymer gel particle of 10nm earlier by reverse microemulsion liquid system, thermal-initiated polymerization mode; As nano-reactor, organic compound such as complexing Ti, Si form with former nanometer polymer particle form consistent size, polymer/metal hybrid microspheres (organic inorganic hybridization microballoon) with it.The place that hybrid microspheres forms by the adjusting to the nano-reactor size, can be regulated the size of organic inorganic hybridization microballoon in " kernel water surrounding " that the nanometer polymer micro-gel particles provides indirectly.
The concrete operations step of the method for the invention is:
1) with the 3-6g emulsifiers dissolve in the solvent of 10-30ml, add the deionized water of the liquid hydrophilic monomer of 0.3-1g and 0.03-0.1g linking agent and 0-10ml then, after the ultrasonic 10-60min, obtain the reverse microemulsion liquid system of stable transparent clarification;
2) the ultrasonic system afterwards of step 1) is poured in the single port reaction flask that having a ventilation mouth, sealing, under the condition of ice bath, by a ventilation mouthful connection evacuation system, behind the intact air of pump drainage, degassing circulation under protection of inert gas, to guarantee that in the reaction flask be inert gas environment, 0-30 ℃ of constant temperature water bath stirs 10-60min then; Then in system, add initiator system, and bath temperature is risen to 30-40 ℃, constant temperature sustained reaction 1-24h under the magnetic agitation;
3) after reaction finishes, stop heated and stirred, system is left standstill or add the 50-500ml solvent and leave standstill 12-72h, make product separate out with white flocks form; Use the solvent supersonic centrifuge washing to removing residual emulsifying agent, centrifugal speed 5000-8000r/min, centrifugation time 5-30min then; Normal temperature vacuum-drying then obtains the nanometer polymer micro-gel particles;
4) the nanometer polymer micro-gel particles that obtains with step 3) is scattered in its 1-30mg in the THF solvent of 5-20ml as nano-reactor, and ultrasonic 10-30min is evenly distributed it; 10-38wt% hydrochloric acid with 10-100mg organic titanic compound or silicoorganic compound and 10-100mg joins in the above-mentioned system simultaneously then, and feeds protection of inert gas to be used for getting rid of oxygen, and the room temperature lower magnetic force stirs 1-24h;
5) after reaction finishes, remove solvent in the system by the rotary evaporation method, vacuum-drying under the normal temperature obtains the superfine nano hybrid microspheres.
Described liquid hydrophilic monomer is selected from N, N-DMAA (DMAA), Methacrylamide (MAM), vinylformic acid (AA), methacrylic acid (MAA), dimethyl diallyl ammonium chloride (DADMAC), methacrylic acid N, N-dimethylaminoethyl (DMAEMA), hydroxyethyl methylacrylate (HEMA) or Propylene glycol monoacrylate (HPA).
Described linking agent is N, N '-methylene-bisacrylamide (MBA) or cystamine bisacrylamide (CBA).
Described emulsifying agent is selected from two-(2-ethylhexyl) sodium sulfosuccinate (AOT), Triton X-100 (TritonX-100, the ethoxylated dodecyl alcohol of polymerization degree n=9-10), sodium lauryl sulphate (SDS), cetyl trimethylammonium bromide (CTAB) or polymerization degree n=30-35.
Described solvent is selected from normal hexane, hexanaphthene, octane-iso, n-decane, normal heptane or toluene.
Described rare gas element is selected from nitrogen, argon gas or helium, preferred nitrogen.
Described initiator system is that concentration is persulphate aqueous solution 10-30 μ l and the N of 10-100mg/ml, N, and N ', N '-Tetramethyl Ethylene Diamine 10-30 μ l, described persulphate is ammonium persulphate or Potassium Persulphate.
Described nanometer polymer micro-gel particles is the size homogeneous, the spheroidal particle that is evenly distributed, and particle size range is at 2-10nm.
The described organic titanic compound of step 4) is selected from titanium tetraisopropylate (TTIP), tetra-n-butyl titanate (TBT), titanium tetrachloride, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester, four (octadecyl) orthotitanate, four trimethyl carbinol titaniums, four titanium isobutoxides, four tertiary amyl alcohol titaniums, 2-ethyl-1-hexanol titanium (MSDS) or isooctyl alcohol titanium.
The described silicoorganic compound of step 4) are selected from tetraethoxy (TEOS), isopropyl silicate (TIOS), methacrylic acid-3-trimethoxy silicon propyl ester (MPS), tetramethyl disiloxane (HMM), pentamethyl disiloxane, hexamethyldisiloxane, seven methyl trisiloxanes, dimethyl cyclosiloxane (DMC), octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane or tetramethyl-tetrem thiazolinyl cyclotetrasiloxane.
The method of utilizing nano-reactor synthesizing superfine nanometer polymer hybrid microspheres provided by the invention has that technology is simple, cost is low, easy-to-operate, speed of response is very fast, product size is ultra-fine, the 10nm scope is with advantages such as interior controlled, even size distribution.The present invention combines characteristics organic and inorganic, nanoparticle three aspects, for the industrial applications that ultra-fine controllable nanon size polymer particle is synthetic has been created new possibility, for the hybrid nanoparticle that designs/synthesize other multifunction, controllable size provides new approaches, to developing high-performance, having the matrix material of specific function significant, also widened the synthetic and application prospect of novel material simultaneously.
Description of drawings
Among Fig. 1 embodiment 1, as the nanometer polymer micro-gel particles of nano-reactor and the contrast HRTEM photo before and after the organic titanium complexing; (a) before the complexing, the electromicroscopic photograph of nanometer polymer micro-gel particles, (b) after the complexing, the electromicroscopic photograph of superfine nano hydridization organic titanium microballoon.
Among Fig. 2 embodiment 1, the ultimate analysis figure of gained superfine nano hydridization organic titanium microballoon.
Among Fig. 3 embodiment 2, increase the size of nanometer polymer microgel, as the nanometer polymer micro-gel particles of nano-reactor and the contrast HRTEM photo before and after the organic titanium complexing; (a) before the complexing, the electromicroscopic photograph of nanometer polymer micro-gel particles, (b) after the complexing, the electromicroscopic photograph of superfine nano hydridization organic titanium microballoon.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.The invention is not restricted to these specific embodiments.
The sign of product pattern uses HR-TEM (Japan produces JEOL JEM-3010 type High Resolution TEM) to observe, and instrument HRTEM/EDS is on the same stage also used in ultimate analysis, and acceleration voltage is 200kV.
Fluorescence micrograph uses Japan to produce OLYMPUS CX21 fluorescence microscope.
Embodiment 1
1) 5.625g AOT is dissolved in the normal hexane of 20ml, adds 0.5574g DMAA and 0.045g MBA then, after the ultrasonic 30min, obtain the reverse microemulsion liquid system of stable transparent clarification;
2) the ultrasonic system afterwards of step 1) is poured in the single port reaction flask that having a ventilation mouth, sealing, under the condition of ice bath, by a ventilation mouthful connection evacuation system, behind the intact air of pump drainage, degassing circulation under nitrogen protection, to guarantee that in the reaction flask be nitrogen environment, 25 ℃ of constant temperature water baths stir 30min then; Then in system, add initiator system ammonium persulfate solution (100mg/ml, 10 μ l) and TEMDA 10 μ l, and bath temperature is risen to 35 ℃, constant temperature sustained reaction 12h under the magnetic agitation;
3) after reaction finishes, stop heated and stirred, system is added the 100ml normal hexane leave standstill 24h, make product separate out with white flocks form; Use the ultrasonic centrifuge washing of normal hexane to removing residual AOT, centrifugal speed 5000r/min, centrifugation time 20min then; Normal temperature vacuum-drying then obtains PDMAA nanometer polymer micro-gel particles;
4) the PDMAA nanometer polymer micro-gel particles that obtains with step 3) is made nano-reactor, its 5mg is scattered in the THF solvent of 5ml, and ultrasonic 30min is evenly distributed it; Then the 37wt% hydrochloric acid of 35mg titanium tetraisopropylate (TTIP) with 40mg is joined in the above-mentioned system simultaneously, and feed nitrogen protection to be used for getting rid of oxygen, the room temperature lower magnetic force stirs 1h;
5) after reaction finishes, remove solvent in the system by the rotary evaporation method, vacuum-drying under the normal temperature obtains superfine nano hydridization organic titanium microballoon.
The THF solvent adds Mg (OH) before use
2Solid and reflux are with the moisture in the desolventizing.
In the water nuclear environment that the polymer nanocomposite micro-gel particles provides, hydrochloric acid is as catalyzer, induce hydrolysis in the nanometer environment of TTIP composition in water nuclear, form the reticulated structure of Ti-O, and and the nanometer polymer gel particles between interact, generate the superfine nano hydridization particle of polymkeric substance and organic titanium hydridization.
As the contrast HRTEM photo before and after the nanometer polymer micro-gel particles of nano-reactor and the organic titanium complexing as shown in Figure 1.The ultimate analysis of gained superfine nano hydridization organic titanium microballoon as shown in Figure 2.
Embodiment 2
The nanogel particle that uses different size is as the reactor made hybrid microspheres:
1) 5.625g AOT is dissolved in the normal hexane of 20ml, add 0.5574g DMAA and 0.045g MBA and 1.14ml deionized water (make water and AOT mol ratio w=5) then, after the ultrasonic 30min, obtain the reverse microemulsion liquid system of stable transparent clarification;
2) the ultrasonic system afterwards of step 1) is poured in the single port reaction flask that having a ventilation mouth, sealing, under the condition of ice bath, by a ventilation mouthful connection evacuation system, behind the intact air of pump drainage, degassing circulation under nitrogen protection, to guarantee that in the reaction flask be nitrogen environment, 25 ℃ of constant temperature water baths stir 30min then; Then in system, add initiator system ammonium persulfate solution (100mg/ml 10 μ l) and TEMDA 10 μ l, and bath temperature is risen to 35 ℃, constant temperature sustained reaction 12h under the magnetic agitation;
3) after reaction finishes, stop heated and stirred, system is added the 100ml normal hexane leave standstill 24h, make product separate out with white flocks form; Use the ultrasonic centrifuge washing of normal hexane to removing residual AOT, centrifugal speed 5000r/min, centrifugation time 20min then; Normal temperature vacuum-drying then obtains PDMAA nanometer polymer micro-gel particles;
4) the PDMAA nanometer polymer micro-gel particles that obtains with step 3) is made nano-reactor, its 5mg is scattered in the THF solvent of 5ml, and ultrasonic 30min is evenly distributed it; Then the 37wt% hydrochloric acid of 35mg titanium tetraisopropylate (TTIP) with 40mg is joined in the above-mentioned system simultaneously, and feed nitrogen protection to be used for getting rid of oxygen, the room temperature lower magnetic force stirs 1h;
5) after reaction finishes, remove solvent in the system by the rotary evaporation method, vacuum-drying under the normal temperature obtains superfine nano hydridization organic titanium microballoon.
The THF solvent adds Mg (OH) before use
2Solid and reflux are with the moisture in the desolventizing.
Varying sized, as the nanometer polymer micro-gel particles of nano-reactor and the contrast HRTEM photo before and after the organic titanium complexing as shown in Figure 3.
Claims (8)
1. a method of utilizing nano-reactor synthesizing superfine nano hybridization microballoon is characterized in that, its concrete operations step is:
1) with the 3-6g emulsifiers dissolve in the solvent of 10-30ml, add the deionized water of the liquid hydrophilic monomer of 0.3-1g and 0.03-0.1g linking agent and 0-10ml then, after the ultrasonic 10-60min, obtain the reverse microemulsion liquid system of stable transparent clarification;
2) the ultrasonic system afterwards of step 1) is poured in the single port reaction flask that having a ventilation mouth, sealing, under the condition of ice bath, by a ventilation mouthful connection evacuation system, behind the intact air of pump drainage, degassing circulation under protection of inert gas, to guarantee that in the reaction flask be inert gas environment, 0-30 ℃ of constant temperature water bath stirs 10-60min then; Then in system, add initiator system, and bath temperature is risen to 30-40 ℃, constant temperature sustained reaction 1-24h under the magnetic agitation;
3) after reaction finishes, stop heated and stirred, system is left standstill or add the 50-500ml solvent and leave standstill 12-72h, make product separate out with white flocks form; Use the solvent supersonic centrifuge washing to removing residual emulsifying agent, centrifugal speed 5000-8000r/min, centrifugation time 5-30min then; Normal temperature vacuum-drying then obtains the nanometer polymer micro-gel particles;
4) the nanometer polymer micro-gel particles that obtains with step 3) is scattered in its 1-30mg in the THF solvent of 5-20ml as nano-reactor, and ultrasonic 10-30min is evenly distributed it; 10-38wt% hydrochloric acid with 10-100mg organic titanic compound or silicoorganic compound and 10-100mg joins in the above-mentioned system simultaneously then, and feeds protection of inert gas to be used for getting rid of oxygen, and the room temperature lower magnetic force stirs 1-24h;
5) after reaction finishes, remove solvent in the system by the rotary evaporation method, vacuum-drying under the normal temperature obtains the superfine nano hybrid microspheres;
Described solvent is selected from normal hexane, hexanaphthene, octane-iso, n-decane, normal heptane or toluene;
Described initiator system is that concentration is persulphate aqueous solution 10-30 μ l and the N of 10-100mg/ml, N, and N ', N '-Tetramethyl Ethylene Diamine 10-30 μ l, described persulphate is ammonium persulphate or Potassium Persulphate.
2. the method for claim 1, it is characterized in that, described liquid hydrophilic monomer is selected from N, N-DMAA, Methacrylamide, vinylformic acid, methacrylic acid, dimethyl diallyl ammonium chloride, methacrylic acid N, N-dimethylaminoethyl, hydroxyethyl methylacrylate or Propylene glycol monoacrylate.
3. the method for claim 1 is characterized in that, described linking agent is N, N '-methylene-bisacrylamide or cystamine bisacrylamide.
4. the method for claim 1, it is characterized in that described emulsifying agent is selected from the ethoxylated dodecyl alcohol of Triton X-100, sodium lauryl sulphate, cetyl trimethylammonium bromide or the polymerization degree n=30-35 of two-(2-ethylhexyl) sodium sulfosuccinates, polymerization degree n=9-10.
5. the method for claim 1 is characterized in that, described rare gas element is selected from nitrogen, argon gas or helium.
6. the method for claim 1 is characterized in that, described nanometer polymer micro-gel particles is the size homogeneous, the spheroidal particle that is evenly distributed, and particle size range is at 2-10nm.
7. the method for claim 1; it is characterized in that the described organic titanic compound of step 4) is selected from titanium tetraisopropylate, tetra-n-butyl titanate, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester, four (octadecyl) orthotitanate, four trimethyl carbinol titaniums, four titanium isobutoxides, four tertiary amyl alcohol titaniums, 2-ethyl-1-hexanol titanium or isooctyl alcohol titanium.
8. the method for claim 1, it is characterized in that the described silicoorganic compound of step 4) are selected from tetraethoxy, isopropyl silicate, methacrylic acid-3-trimethoxy silicon third, tetramethyl disiloxane, pentamethyl disiloxane, hexamethyldisiloxane, seven methyl trisiloxanes, dimethyl cyclosiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane or tetramethyl-tetrem thiazolinyl cyclotetrasiloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210098103 CN102634044B (en) | 2012-04-05 | 2012-04-05 | Method for synthesizing superfine nano hybridization microspheres by use of nanoreactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210098103 CN102634044B (en) | 2012-04-05 | 2012-04-05 | Method for synthesizing superfine nano hybridization microspheres by use of nanoreactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102634044A CN102634044A (en) | 2012-08-15 |
| CN102634044B true CN102634044B (en) | 2013-08-07 |
Family
ID=46618627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210098103 Expired - Fee Related CN102634044B (en) | 2012-04-05 | 2012-04-05 | Method for synthesizing superfine nano hybridization microspheres by use of nanoreactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102634044B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641032B (en) * | 2018-04-10 | 2020-06-26 | 常州大学 | Method for preparing nano hollow reactor by inverse miniemulsion polymerization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517411A (en) * | 2003-01-14 | 2004-08-04 | 华东理工大学 | Preparing of dispersed-in-water nono-SIO2 with durable stability at ordinary temp and its hybridized materaial |
| CN101250313A (en) * | 2008-03-19 | 2008-08-27 | 中国科学院化学研究所 | Nano-particle compound and preparation method thereof |
| CN101921447A (en) * | 2010-04-16 | 2010-12-22 | 江苏大学 | Method for preparing a waterborne poly(urethane acrylate)/nano-titanium dioxide hybrid material |
-
2012
- 2012-04-05 CN CN 201210098103 patent/CN102634044B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517411A (en) * | 2003-01-14 | 2004-08-04 | 华东理工大学 | Preparing of dispersed-in-water nono-SIO2 with durable stability at ordinary temp and its hybridized materaial |
| CN101250313A (en) * | 2008-03-19 | 2008-08-27 | 中国科学院化学研究所 | Nano-particle compound and preparation method thereof |
| CN101921447A (en) * | 2010-04-16 | 2010-12-22 | 江苏大学 | Method for preparing a waterborne poly(urethane acrylate)/nano-titanium dioxide hybrid material |
Non-Patent Citations (2)
| Title |
|---|
| "Ultrafine Hydrogel Nanoparticles: Synthetic Approach and Therapeutic Application in Living Cells";De Gao et al.;《Angew. Chem. Int. Ed.》;20070220;第46卷;第2224–2227页 * |
| De Gao et al.."Ultrafine Hydrogel Nanoparticles: Synthetic Approach and Therapeutic Application in Living Cells".《Angew. Chem. Int. Ed.》.2007,第46卷 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102634044A (en) | 2012-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wei et al. | 2D particles at fluid–fluid interfaces: assembly and templating of hybrid structures for advanced applications | |
| Lee et al. | Advanced silica/polymer composites: Materials and applications | |
| Schmid et al. | Polystyrene− silica colloidal nanocomposite particles prepared by alcoholic dispersion polymerization | |
| Hartlen et al. | Facile preparation of highly monodisperse small silica spheres (15 to> 200 nm) suitable for colloidal templating and formation of ordered arrays | |
| Castelvetro et al. | Nanostructured hybrid materials from aqueous polymer dispersions | |
| Hyde et al. | Colloidal silica particle synthesis and future industrial manufacturing pathways: a review | |
| Qi et al. | Recent advances in the preparation of hybrid nanoparticles in miniemulsions | |
| Zhai et al. | Water-in-oil Pickering emulsion polymerization of N-isopropyl acrylamide using starch-based nanoparticles as emulsifier | |
| Schmid et al. | Polystyrene− silica nanocomposite particles via alcoholic dispersion polymerization using a cationic azo initiator | |
| Percy et al. | Synthesis of vinyl polymer− silica colloidal nanocomposites prepared using commercial alcoholic silica sols | |
| CN102343239B (en) | Oxidized graphene or graphene/inorganic particle core/shell material and preparation method thereof | |
| Duan et al. | Synthesis and characterization of poly (N-isopropylacrylamide)/silica composite microspheres via inverse Pickering suspension polymerization | |
| Percy et al. | Surfactant-free synthesis of colloidal poly (methyl methacrylate)/silica nanocomposites in the absence of auxiliary comonomers | |
| CN104292493B (en) | Multistage pore polymer microsphere of a kind of magnetic, fluorescent hollow and preparation method thereof | |
| CN102604006B (en) | Preparation method for acidic silica sol in-situ modified acrylate emulsion | |
| Park et al. | Heterophase polymer dispersion: A green approach to the synthesis of functional hollow polymer microparticles | |
| Qi et al. | In situ emulsion copolymerization of methyl methacrylate and butyl acrylate in the presence of SiO 2 with various surface coupling densities | |
| CN101611084A (en) | Novel nanoparticle | |
| CN101891867A (en) | Method for preparing SiO2-poly(dimethylaminoethyl methacrylate) (PDMAEMA) nanoparticles having core-shell structure | |
| Liu et al. | Preparation of polymer@ titania raspberry-like core–corona composite via heterocoagulated self-assembly based on hydrogen-bonding interaction | |
| Yook et al. | A novel method for preparing silver nanoparticle–hydrogel nanocomposites via pH-induced self-assembly | |
| CN104386699B (en) | Double-template legal system is for the method for many shells mesoporous silicon oxide nanomaterial | |
| Du et al. | Growth of aragonite CaCO3 whiskers in a microreactor with calcium dodecyl benzenesulfonate as a control agent | |
| CN108276593A (en) | A kind of preparation method of the selfreparing Nanometer composite hydrogel of collection ultraviolet-visible-near infrared light induction | |
| Sharifzadeh et al. | Direct and reverse desymmetrization process in O/W Pickering emulsions to produce hollow graphene oxide Janus micro/nano-particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130807 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |