CN103044594B - Method for preparing solation-gelation hybridized nano self-assembly aggregation - Google Patents
Method for preparing solation-gelation hybridized nano self-assembly aggregation Download PDFInfo
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- CN103044594B CN103044594B CN201210563910.1A CN201210563910A CN103044594B CN 103044594 B CN103044594 B CN 103044594B CN 201210563910 A CN201210563910 A CN 201210563910A CN 103044594 B CN103044594 B CN 103044594B
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- 238000001338 self-assembly Methods 0.000 title claims abstract description 20
- 238000001879 gelation Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 title abstract description 4
- 238000004220 aggregation Methods 0.000 title abstract 4
- 230000002776 aggregation Effects 0.000 title abstract 4
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000009466 transformation Effects 0.000 claims description 11
- 238000010257 thawing Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000021050 feed intake Nutrition 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a method for preparing solation-gelation hybridized nano self-assembly aggregation. A polymethylacrylic acid gamma-trimethoxy silane ester macromolecular chain transfer agent regulates and controls reversible addition-fragmentation chain transfer polymerization of styrene in a selective solvent, so that the solation-gelation self-assembly aggregation with different shapes is prepared in an in-situ self-assembly manner. The self-assembly aggregation can stabilize a micellar structure or introduce functional hybridized components through further solation-gelation.
Description
Technical field
The present invention relates to a kind of can the hybridized nanometer self-assembly aggregate and preparation method thereof of sol gel.
Background technology
Macromolecular self-assembly belongs to the crossing research field of supramolecular chemistry and polymer chemistry.Wherein, the solution self-assembly of segmented copolymer is the main flow in Macromolecular self-assembly field.Block copolymer solution self-assembly is a complex process relating to factors, form a series of form in the solution as ball, rod, vesica and large composite micelle etc., enjoy the concern of academia and industry member, be regarded as constructing one of main path with regular texture functional nanomaterials, using value potential in fields such as medicine controlled releasing, separation, microelectronics, optics, catalysis etc.At present, the solution self-assembly research about pure organic block polymer is more.But as a kind of " pure soft material ", there is the shortcomings such as lower, the recyclable rate variance of use temperature, Application Areas be limited in it.For improving this weak point, in segmented copolymer, introduce high thermal stability inorganic components is one of effective way.Organosilicon/inorganic nano-hybrid material combines due to its synergistic the excellent properties that organic polymer and inorganic materials character shows, and causes very large research interest in recent years.A kind of construct nano hybridization aggregate material usually effective way be the self-assembly of the segmented copolymer by silicone-containing, siloxanes carries out the crosslinked [Du of sol gel reaction more subsequently, J.Z.and Y.M.Chen, Organic-inorganic hybrid nanoparticles with a complex hollow structure. [J] .AngewandteChemie-International Edition, 2004.43 (38): p.5084-5087.Du, J.Z.and Y.M.Chen, Preparationof organic/inorganic hybrid hollow particles based on gelation of polymer vesicles. [J] .Macromolecules, 2004.37 (15): p.5710-5716.Du, J.Z., et al., Organic/inorganic hybrid vesiclesbased on a reactive block copolymer. [J] .Journal of the American Chemical Society, 2003.125 (48): p.14710-14711.].Be limited to its lower concentration, consuming time length to the method realizing self-assembly to prepare nanoassemble aggregate because traditional employing drips selective solvent in the solution of segmented copolymer, be difficult to batch production.
Summary of the invention
The invention provides a kind of can the preparation method of hybridized nanometer self-assembly aggregate of sol gel.In selective solvent, regulate and control the polymerization of cinnamic reversible addion-fragmentation chain transfer with polymethyl acrylic acid γ-Trimethoxy silane ester large molecule chain-transfer agent, primary reconstruction prepares having of different-shape can the self-assembly aggregate of sol gel.This self-assembly aggregate can carry out stable micellar structure by further sol gel or introduce functional hydridization component.
The present invention comprises following steps:
1. Macromolecular chain transfer agent synthesis: methacrylic acid γ-Trimethoxy silane ester (MPS), dithiobenzoic acid cumyl ester CDB and Diisopropyl azodicarboxylate (AIBN) are dissolved in toluene, after degassed 3 times of freeze thawing under argon shield 65 ° of C polymerizations.After dissolution with solvents, obtain red thick liquid PMPS in sherwood oil 60 ~ 90 ° of C cuts of 10 ~ 20 times of volumes after precipitation purification removing monomer, be Macromolecular chain transfer agent.
2. the synthesis of nanoassemble aggregate: Macromolecular chain transfer agent PMPS is dissolved in the mixed solution of vinylbenzene and propyl carbinol, after degassed 3 times of freeze thawing argon shield and under stirring in 110 ° of C polymerizations.
In step 1, by mole when transformation efficiency of regulation and control MPS and CDB, make the polymerization degree of MPS be 30 ~ 60, be too lowly not suitable for precipitate and separate, too high, be unfavorable for follow-up micella preparation process.
In step 2, in step 2, in St and PMPS that feed intake, the ratio of the mole number of MPS unit is 25 ~ 75, and conversion rate control is below 60%.
Accompanying drawing explanation
Accompanying drawing 1: figure a, b, c, d, e, f respectively corresponding embodiment 1,5,6 obtain vesica, nano wire, Nano microsphere TEM, the SEM of the MULTIPLE COMPOSITE vesica that embodiment 4 obtains, and embodiment 1 obtain vesica sol gel reaction before and after SEM
Embodiment
Embodiment 1
1. Macromolecular chain transfer agent synthesis: by MPS(2.5mL, 2mmol), CDB(54.5mg; 0.2mmol) and AIBN(6.6mg; 0.04mmol)) be dissolved in toluene (1ml), after degassed 3 times of freeze thawing, under argon shield, be polymerized 5 hours at 65 ° of C, transformation efficiency 74%.Pink thick liquid PMPS, M is obtained twice through 60 ~ 90 ° of C cut petroleum ether precipitations
n(SEC, vs PS)=9400, PDI=1.12,
2. the synthesis of nanoassemble aggregate: PMPS Macromolecular chain transfer agent (75mg) is dissolved in St(1ml; 8.4mmol) with the mixed solvent of propyl carbinol (1.5ml); 24h are polymerized in argon shield and under stirring in 110 ° of C through freeze thawing is degassed after degassed 3 times of freeze thawing; nuclear-magnetism records transformation efficiency 37%, obtains vesica.
Embodiment 2
In step 2, PMPS consumption is 150mg, reaction times 24h, and all the other, with embodiment 1. transformation efficiency 36%, obtain nano thread structure.
Embodiment 3
In step 2, PMPS consumption is 200mg, reaction times 24h, and all the other, with embodiment 1. transformation efficiency 34%, obtain nanometer globular micelle.
Embodiment 4
In step 2, PMPS consumption is 50mg, reaction times 40h, and all the other, with embodiment 1. transformation efficiency 52%, obtain MULTIPLE COMPOSITE imitated vesicle structure.
Embodiment 5
In step 2, propyl carbinol consumption is 2mL, PMPS consumption is 41mg, and reaction times 16h, all the other, with embodiment 1. transformation efficiency 27%, obtain vesica.
Embodiment 6
In step 2, propyl carbinol consumption is 2mL, PMPS consumption is 62mg, and reaction times 16h, all the other, with embodiment 1. transformation efficiency 26%, obtain the mixed structure of vesica and nano wire.
Embodiment 7
1. Macromolecular chain transfer agent synthesis: by MPS(2mL, 8.5mmol), CDB(27.3mg; 0.1mmol) and AIBN(0.82mg; 0.005mmol)) be dissolved in toluene (1ml), after degassed 3 times of freeze thawing under argon shield 65 ° of C polyase 13s 6 hours, transformation efficiency 77%.Pink thick liquid PMPS, M is obtained twice through 60 ~ 90 ° of C cut petroleum ether precipitations
n(SEC, vs PS)=18000, PDI=1.38,
2. the synthesis of nanoassemble aggregate: PMPS Macromolecular chain transfer agent (41mg) is dissolved in St(1ml; 8.4mmol) with the mixed solvent of propyl carbinol (1.5ml); 18h are polymerized in argon shield and under stirring in 110 ° of C through freeze thawing is degassed after degassed 3 times of freeze thawing; nuclear-magnetism records transformation efficiency 36%, obtains the large microballoon of 200 ~ 500nm.
Claims (3)
1. can the preparation method of hybridized nanometer self-assembly aggregate of sol gel, it is characterized in that comprising following steps:
(1). Macromolecular chain transfer agent is synthesized: be dissolved in toluene by methacrylic acid γ-Trimethoxy silane ester (MPS), dithiobenzoic acid cumyl ester CDB and Diisopropyl azodicarboxylate (AIBN), after degassed 3 times of freeze thawing under argon shield 65 DEG C of polymerizations; After dissolution with solvents, obtain red thick liquid PMPS in sherwood oil 60 ~ 90 DEG C of cuts of 10 ~ 20 times of volumes after precipitation purification removing monomer, be Macromolecular chain transfer agent;
(2). the synthesis of nanoassemble aggregate: Macromolecular chain transfer agent PMPS is dissolved in the mixed solution of vinylbenzene and propyl carbinol, after degassed 3 times of freeze thawing argon shield and under stirring in 110 DEG C of polymerizations.
2. according to claim 1 a kind of can the preparation method of hybridized nanometer self-assembly aggregate of sol gel, it is characterized in that, in step (1), mole when transformation efficiency of regulation and control MPS and CDB, makes the polymerization degree of MPS be 30 ~ 60.
3. according to claim 1 a kind of can the preparation method of hybridized nanometer self-assembly aggregate of sol gel, it is characterized in that, in its step (2), in St and PMPS that feed intake, the ratio of the mole number of MPS unit is 25 ~ 75, and conversion rate control is below 60%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199262A (en) * | 2011-04-12 | 2011-09-28 | 厦门大学 | Polyhedral oligomeric silsesquioxane amphiphilic block copolymer and preparation method thereof |
| CN102675568A (en) * | 2012-06-01 | 2012-09-19 | 同济大学 | Preparation method for organic-inorganic hybrid skin-friendly efficient sunscreen product |
| CN102731738A (en) * | 2012-07-06 | 2012-10-17 | 厦门大学 | Polyhedral oligomeric silsesquioxane (POSS) based patterned nano microsphere and preparation method thereof |
| EP2607101A1 (en) * | 2011-12-21 | 2013-06-26 | The Goodyear Tire & Rubber Company | Method of making a graft copolymer and rubber composition comprising such a graft copolymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199262A (en) * | 2011-04-12 | 2011-09-28 | 厦门大学 | Polyhedral oligomeric silsesquioxane amphiphilic block copolymer and preparation method thereof |
| EP2607101A1 (en) * | 2011-12-21 | 2013-06-26 | The Goodyear Tire & Rubber Company | Method of making a graft copolymer and rubber composition comprising such a graft copolymer |
| CN102675568A (en) * | 2012-06-01 | 2012-09-19 | 同济大学 | Preparation method for organic-inorganic hybrid skin-friendly efficient sunscreen product |
| CN102731738A (en) * | 2012-07-06 | 2012-10-17 | 厦门大学 | Polyhedral oligomeric silsesquioxane (POSS) based patterned nano microsphere and preparation method thereof |
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