CN103044642A - Preparation method of surface amino-modified nano self-assembled aggregate - Google Patents
Preparation method of surface amino-modified nano self-assembled aggregate Download PDFInfo
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- CN103044642A CN103044642A CN2012105643802A CN201210564380A CN103044642A CN 103044642 A CN103044642 A CN 103044642A CN 2012105643802 A CN2012105643802 A CN 2012105643802A CN 201210564380 A CN201210564380 A CN 201210564380A CN 103044642 A CN103044642 A CN 103044642A
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Abstract
The invention provides a preparation method of a surface amino-modified nano self-assembled aggregate. A polymethacrylic acid glycidyl methacrylate (PGMA) macromolecule chain transfer agent adjusts and controls reversible addition-fragmentation chain transfer polymerization of common monomers in a selective solvent, and further the surface functionalization is carried out to prepare surface amination self-assembled aggregates in different appearances. As the mixed solution of the solvent and the monomers is a two-block critical solvent, the system can maintain homogeneous phase at the polymerization temperature, and the block polymer can be separated after cooling. Through directly adding amine into the system, then heating to obtain homogeneous phase, and cooling to the room temperature while stirring, the self-assembled aggregate can be acquired. Through controlling the second-block chain length, the functionalization degree or solvent components, the appearance of the aggregate can be controlled. A methacrylic acid glycidyl methacrylate (GMA) unit not participating in the reaction or amino introduced by the reaction provides a structural foundation for further self-assembly functionalization.
Description
Technical field
The present invention relates to a kind of surface amino groups decorated nanometer self-assembly aggregate and preparation method thereof.
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.The self-assembly of amphiphilic diblock copolymer in selective solvent is a complex process that relates to factors, provide a clear and definite approach for preparing supramolecular aggregation such as globular micelle, wire micella, vesica, MULTIPLE COMPOSITE micella, circle and spiral etc., enjoy the concern of academia and industry member, be regarded as constructing one of main path with regular texture functional nanomaterials, in potential using values such as field such as medicine controlled releasing, separation, microelectronics, optics, catalysis.
Because traditional employing drips selective solvent in the solution of segmented copolymer and realizes that the method for self-assembly prepares the nanoassemble aggregate and is subject to its lower concentration, length consuming time, is difficult to produce in batches.Address this problem more easily strategy and be by in the selective solvent of macromolecular chain transfer agent, carrying out the active controllable free-radical polymerisation of vinyl monomer, but usually all have to the globular micelle structure.The latest developments such as Pan a kind of method, can be successfully with the synthetic various nanoassemble aggregates of RAFT polymerization " one kettle way ", called after " polymerisation induced self-assembly and again tissue (PISR) " [Wan, W.M., C.Y.Hong, and C.Y.Pan, One-pot synthesis of nanomaterials via RAFT poly merization induced self-assembly and morphology transition.[J] .Chemical Communications, 2009 (39): p.5883-5885.Wan, W.M., X.L.Sun, and C.Y.Pan, Formation of Vesicular Morphologies via Poly merization InducedSelf-Assembly and Re-Organization.[J] .Macromolecular Rapid Communications, 2010.31 (4): p.399-404.].The RAFT polymerization is celebrated well with functional group's tolerance, but the existence of primary amine and secondary amine can make two thioesters inactivations, thereby preparation contains amino segmented copolymer and self-assembly aggregate thereof and has certain challenge.
Summary of the invention
Among the present invention, provide a kind of preparation method of surface amino groups decorated nanometer self-assembly aggregate.Regulate and control the reversible addition of common monomer-fracture chain transfer polymerization with poly (glycidyl methacrylate) (PGMA) macromolecular chain transfer agent in selective solvent, the step of going forward side by side carries out functionalisation of surfaces and prepares different-shape surface amination self-assembly aggregate.Because the mixed solution of solvent and monomer is the critical solvent of two blocks, system can be kept homogeneous phase under polymerization temperature, and block polymer then can be separated out after the cooling.And directly drip amine toward system and be heated to homogeneous phase after under agitation be cooled to room temperature, then can obtain the self-assembly aggregate.By controlling the second block chain length, degree of functionalization or solvent composition, can control the aggregate pattern.Have neither part nor lot in the glycidyl methacrylate GMA unit of reaction or react the amino of introducing the further functionalized architecture basics that provides of self-assembly is provided.
The present invention comprises following steps:
1. the macromolecular chain transfer agent is synthetic: GMA, dithiobenzoic acid cumyl ester CDB and Diisopropyl azodicarboxylate (AIBN) are dissolved in the toluene, after degassed 3 times of freeze thawing under argon shield 65 ° of C polymerizations.After monomer is removed in the precipitation purification in 60 ~ 90 ° of C cuts of sherwood oil at 10 ~ 20 times of volumes after the dissolution with solvents, get red powder, be the macromolecular chain transfer agent.
2. the nanoassemble aggregate is synthetic: the macromolecular chain transfer agent is dissolved in the mixed solution of vinylbenzene and propyl carbinol; through after degassed 3 times of the freeze thawing in argon shield and under stirring behind 110 ° of C polymerization setting-up times; add amine and adopt freeze-thaw cycle to remove oxygen, stir lower placing and react the nanoassemble aggregate that obtains surface amination under 60 ~ 110 ° of C.
In the above-mentioned steps 1, by mole when transformation efficiency of regulation and control GMA and CDB, so that the polymerization degree of GMA is 30 ~ 150, the too low precipitate and separate that is not suitable for too highly then is unfavorable for follow-up micella preparation process.
In the above-mentioned steps 2, in the step 2, the ratio of the mole number of GMA unit is 14 ~ 40 among feed intake St and the PGMA, and conversion rate control is 20% ~ 50%.It is excessive that the amine consumption is generally, and when especially functionalized with polyamine, only when needs control GMA transformation efficiency, can adopt monobasic secondary amine in shortage.
Description of drawings
The SEM of the micella pattern that accompanying drawing 1: embodiment 1,2,3,4 obtains and (or) TEM figure.
Embodiment
Embodiment 1
1. the macromolecular chain transfer agent is synthetic: with GMA(2.6mL, 2mmol), CDB(54.5mg; 0.2mmol) and AIBN(6.6mg; 0.04mmol)) be dissolved in the toluene (1ml), after degassed 3 times of freeze thawing under argon shield at 65 ° of C polymerizations 4.5 hours, transformation efficiency 94%.Get pink powder PGMA, M twice through 60 ~ 90 ° of C cut petroleum ether precipitations
n(SEC, vs PS)=14700, PDI=1.12,
2. the nanoassemble aggregate is synthetic: PGMA macromolecular chain transfer agent (40mg) is dissolved in St(1ml; 8.4mmol) with the mixed solvent of propyl carbinol (1.5ml) in; through freeze thawing degassed through after degassed 3 times of the freeze thawing in argon shield and under stirring in 110 ° of C polymerizations 16 hours; get purple solution; drip the 0.1mL diethylamine after the cooling; again place 110 ° of C oil bath heated and stirred to transparent after the sealing, under agitation naturally cool to subsequently room temperature.Nuclear-magnetism records the transformation efficiency 37% of St, and amination degree in GMA unit is about 60%, and TEM shows and has simultaneously globular micelle and vesica.
Embodiment 2
The consumption of diethylamine is 0.2mL in the step 2, again places 110 ° of C oil bath heated and stirred to keep 1h after the sealing after transparent, under agitation naturally cools to subsequently room temperature.All the other are with embodiment 1, and nuclear-magnetism records the transformation efficiency 40% of St, and amination degree in GMA unit is about 100%, and TEM is shown as spherical nano-micelle structure.
Embodiment 3
1. the macromolecular chain transfer agent is synthetic: with GMA(1.3mL, 1mmol), CDB(54.5mg; 0.2mmol) and AIBN(6.6mg; 0.04mmol)) be dissolved in the toluene (0.5ml), after degassed 3 times of freeze thawing under argon shield at 65 ° of C polymerizations 4 hours, transformation efficiency 92%.Get pink powder PGMA, M twice through 60 ~ 90 ° of C cut petroleum ether precipitations
n(SEC, vs PS)=7800, PDI=1.13,
2. the nanoassemble aggregate is synthetic: PGMA macromolecular chain transfer agent (40mg) is dissolved in St(1ml; 8.4mmol) with the mixed solvent of propyl carbinol (1.5ml) in; through freeze thawing degassed through after degassed 3 times of the freeze thawing in argon shield and under stirring in 110 ° of C polymerizations 16 hours; get purple solution; drip the 0.2mL diethylamine after the cooling; again place 110 ° of C oil bath heated and stirred to transparent and keep 1h after the sealing, under agitation naturally cool to subsequently room temperature.Nuclear-magnetism records the transformation efficiency 32% of St, and amination degree in GMA unit is about 100%, and SEM and TEM are shown as nano thread structure.
Embodiment 4
The PGMA consumption is 30mg in the step 2, and all the other are with embodiment 3, and nuclear-magnetism records the transformation efficiency 37% of St, and amination degree in GMA unit is about 100%, and SEM and TEM are shown as imitated vesicle structure.
Embodiment 5
The PGMA consumption is 30mg in the step 2, and the amine of dropping is the 0.1mL quadrol, and all the other are with embodiment 3, and nuclear-magnetism records the transformation efficiency 37% of St, and amination degree in GMA unit is about 100%, and SEM and TEM are shown as imitated vesicle structure.
Claims (8)
1. the preparation method of a surface amino groups decorated nanometer self-assembly aggregate is characterized in that comprising following steps:
(1) the macromolecular chain transfer agent is synthetic: GMA, dithiobenzoic acid cumyl ester CDB and Diisopropyl azodicarboxylate (AIBN) are dissolved in the toluene polymerization under argon shield after degassed 3 times of freeze thawing;
(2) the nanoassemble aggregate is synthetic: the macromolecular chain transfer agent is dissolved in the mixed solution of vinylbenzene and propyl carbinol; through after degassed 3 times of the freeze thawing in argon shield and under stirring behind 110 ° of C polymerization setting-up times; add amine and adopt freeze-thaw cycle to remove oxygen, stir lower placing and react the nanoassemble aggregate that obtains surface amination under 60 ~ 110 ° of C.
2. weigh the preparation method of described a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim, it is characterized in that, above-mentioned steps (1) product gets red powder after monomer is removed in the precipitation purification in 60 ~ 90 ° of C cuts of sherwood oil at 10 ~ 20 times of volumes after the dissolution with solvents, be the macromolecular chain transfer agent.
3. weigh the preparation method of described a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim, it is characterized in that, the described polymerization temperature of above-mentioned steps (1) is 65 ° of C.
4. weigh the preparation method of described a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim, it is characterized in that, the described polymerization temperature of above-mentioned steps (2) is 110 ° of C.
5. weigh the preparation method of described a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim, it is characterized in that in the above-mentioned steps (1), the mole of regulation and control GMA and CDB is transformation efficiency when, so that the polymerization degree of GMA is 30 ~ 150.
6. weigh the preparation method of described a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim, it is characterized in that, in step 2, the ratio of the mole number of GMA unit is 14 ~ 40 among feed intake St and the PGMA, and conversion rate control is 20% ~ 50%.
7. weigh the preparation method of described a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim, it is characterized in that, in step 2, described amine is a kind of or its mixture in diethylamine, Isopropylamine, morphine woods, the diethanolamine.
8. weigh the preparation method of described a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim, it is characterized in that, in step 2, the temperature of amine and glycidyl ester ring-opening reaction is 60 ~ 110 ° of C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104548964A (en) * | 2014-12-08 | 2015-04-29 | 重庆市农业科学院 | Star carbon dioxide fixed carrier and preparation method thereof as well as preparation method of separating membrane material |
| CN104513347B (en) * | 2014-12-11 | 2017-06-23 | 山东信合美生物科技有限公司 | The method that soft nanometer coupling technology prepares composite nanometer particle |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2463319A2 (en) * | 2009-08-07 | 2012-06-13 | Sung Chul Hong | Method for preparing olefin-based segmented copolymers |
| CN102516435A (en) * | 2011-11-21 | 2012-06-27 | 浙江大学 | Method for preparing porous material by reversible addition fragmentation chain transfer polymerization of high internal phase emulsion |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2463319A2 (en) * | 2009-08-07 | 2012-06-13 | Sung Chul Hong | Method for preparing olefin-based segmented copolymers |
| CN102516435A (en) * | 2011-11-21 | 2012-06-27 | 浙江大学 | Method for preparing porous material by reversible addition fragmentation chain transfer polymerization of high internal phase emulsion |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104548964A (en) * | 2014-12-08 | 2015-04-29 | 重庆市农业科学院 | Star carbon dioxide fixed carrier and preparation method thereof as well as preparation method of separating membrane material |
| CN104513347B (en) * | 2014-12-11 | 2017-06-23 | 山东信合美生物科技有限公司 | The method that soft nanometer coupling technology prepares composite nanometer particle |
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