CN103044642B - 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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- CN103044642B CN103044642B CN201210564380.2A CN201210564380A CN103044642B CN 103044642 B CN103044642 B CN 103044642B CN 201210564380 A CN201210564380 A CN 201210564380A CN 103044642 B CN103044642 B CN 103044642B
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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, for preparing supramolecular aggregation, provide a clear and definite approach 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 having regular texture functional nanomaterials, in potential using values such as field such as medicine controlled releasing, separation, microelectronics, optics, catalysis.
Because traditional employing realizes the method for self-assembly and prepares nanoassemble aggregate and be limited to its lower concentration, length consuming time toward dripping selective solvent in the solution of segmented copolymer, be difficult to batch production.Addressing this problem strategy is more easily by carrying out the active controllable free-radical polymerisation of vinyl monomer in the selective solvent at macromolecular chain transfer agent, but conventionally all has to 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 organize again (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.].RAFT polymerization is good famous with functional group's tolerance, but the existence of primary amine and secondary amine can make two thioesters inactivations, thereby preparation exists certain challenge containing amino segmented copolymer and self-assembly aggregate thereof.
Summary of the invention
In the present invention, provide a kind of preparation method of surface amino groups decorated nanometer self-assembly aggregate.With poly (glycidyl methacrylate) (PGMA) macromolecular chain transfer agent, in selective solvent, regulate and control reversible addition-fracture chain transfer polymerization of common monomer, and further carry out functionalisation of surfaces and prepare different-shape surface amination self-assembly aggregate.Because the mixed solution of solvent and monomer is the critical solvent of two blocks, system can maintain homogeneous phase under polymerization temperature, and cooling rear block polymer can be separated out.And directly toward system, drip amine and be heated to homogeneous phase after be under agitation cooled to room temperature, can obtain self-assembly aggregate.By controlling the second block chain length, degree of functionalization or solvent composition, can control aggregate pattern.The further functionalized architecture basics that provides that the glycidyl methacrylate GMA unit of reaction or the amino of reaction introducing are self-assembly is provided.
The present invention comprises following steps:
1. macromolecular chain transfer agent is synthetic: GMA, 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 monomer is removed in precipitation purification in 60 ~ 90 ° of C cuts of sherwood oil of 10 ~ 20 times of volumes after dissolution with solvents, obtaining red powder, is macromolecular chain transfer agent.
2. nanoassemble aggregate is synthetic: macromolecular chain transfer agent is dissolved in the mixed solution of vinylbenzene and propyl carbinol; after degassed 3 times of freeze thawing in argon shield and under stirring after 110 ° of C polymerization setting-up times; add amine and also adopt freeze-thaw cycle to remove oxygen, under stirring, be placed in the nanoassemble aggregate that reaction under 60 ~ 110 ° of C obtains surface amination.
In above-mentioned steps 1, by mole when transformation efficiency of regulation and control GMA and CDB, the polymerization degree that makes GMA is 30 ~ 150, and the too low precipitate and separate that is not suitable for is too highly unfavorable for follow-up micella preparation process.
In above-mentioned steps 2, in step 2, in feed intake St and PGMA, the ratio of the mole number of GMA unit is 14 ~ 40, and conversion rate control is 20% ~ 50%.It is excessive that amine consumption is generally, and when especially functionalized with polyamine, only, when needs are controlled GMA transformation efficiency, can adopt monobasic secondary amine in shortage.
Accompanying drawing explanation
The SEM of the micella pattern that accompanying drawing 1: embodiment 1,2,3,4 obtains and (or) TEM figure.
Embodiment
Embodiment 1
1. macromolecular chain transfer agent is synthetic: by GMA(2.6mL, 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 at 65 ° of C polymerizations 4.5 hours, transformation efficiency 94%.Through 60 ~ 90 ° of C cut petroleum ether precipitations, obtain pink powder PGMA, M twice
n(SEC, vs PS)=14700, PDI=1.12,
2. nanoassemble aggregate is synthetic: PGMA macromolecular chain transfer agent (40mg) is dissolved in to St(1ml; 8.4mmol) with the mixed solvent of propyl carbinol (1.5ml) in; through freeze thawing degassed after degassed 3 times of freeze thawing in argon shield and under stirring in 110 ° of C polymerizations 16 hours; obtain purple solution; cooling rear dropping 0.1mL diethylamine; after sealing, be again placed in 110 ° of C oil bath heated and stirred to transparent, under agitation naturally cool to subsequently room temperature.Nuclear-magnetism records the transformation efficiency 37% of St, GMA unit amination degree approximately 60%, and there is globular micelle and vesica in TEM demonstration simultaneously.
Embodiment 2
In step 2, the consumption of diethylamine is 0.2mL, is again placed in 110 ° of C oil bath heated and stirred and maintains 1h after 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, GMA unit amination degree approximately 100%, and TEM is shown as spherical nano-micelle structure.
Embodiment 3
1. macromolecular chain transfer agent is synthetic: by GMA(1.3mL, 1mmol), CDB(54.5mg; 0.2mmol) and AIBN(6.6mg; 0.04mmol)) be dissolved in toluene (0.5ml), after degassed 3 times of freeze thawing under argon shield at 65 ° of C polymerizations 4 hours, transformation efficiency 92%.Through 60 ~ 90 ° of C cut petroleum ether precipitations, obtain pink powder PGMA, M twice
n(SEC, vs PS)=7800, PDI=1.13,
2. nanoassemble aggregate is synthetic: PGMA macromolecular chain transfer agent (40mg) is dissolved in to St(1ml; 8.4mmol) with the mixed solvent of propyl carbinol (1.5ml) in; through freeze thawing degassed after degassed 3 times of freeze thawing in argon shield and under stirring in 110 ° of C polymerizations 16 hours; obtain purple solution; cooling rear dropping 0.2mL diethylamine; after sealing, be again placed in 110 ° of C oil bath heated and stirred to transparent and maintain 1h, under agitation naturally cool to subsequently room temperature.Nuclear-magnetism records the transformation efficiency 32% of St, GMA unit amination degree approximately 100%, and SEM and TEM are shown as nano thread structure.
Embodiment 4
In step 2, PGMA consumption is 30mg, and all the other are with embodiment 3, and nuclear-magnetism records the transformation efficiency 37% of St, GMA unit amination degree approximately 100%, and SEM and TEM are shown as imitated vesicle structure.
Embodiment 5
In step 2, PGMA consumption is 30mg, and the amine of dropping is 0.1mL quadrol, and all the other are with embodiment 3, and nuclear-magnetism records the transformation efficiency 37% of St, GMA unit amination degree approximately 100%, and SEM and TEM are shown as imitated vesicle structure.
Claims (7)
1. a preparation method for surface amino groups decorated nanometer self-assembly aggregate, is characterized in that comprising following steps:
(1) macromolecular chain transfer agent is synthetic: GMA, dithiobenzoic acid cumyl ester CDB and Diisopropyl azodicarboxylate (AIBN) are dissolved in toluene to polymerization under argon shield after degassed 3 times of freeze thawing;
(2) nanoassemble aggregate is synthetic: macromolecular chain transfer agent is dissolved in the mixed solution of vinylbenzene and propyl carbinol, after degassed 3 times of freeze thawing in argon shield and under stirring after 110 ℃ of polymerization setting-up times, add amine and also adopt freeze-thaw cycle to remove oxygen, under stirring, be placed in the nanoassemble aggregate that reaction at 60～110 ℃ obtains surface amination;
In step (2), described amine is a kind of or its mixture in diethylamine, Isopropylamine, morpholine, diethanolamine.
2. the preparation method of a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim 1, it is characterized in that, above-mentioned steps (1) product obtains red powder after monomer is removed in precipitation purification in 60～90 ℃ of cuts of sherwood oil of 10～20 times of volumes after dissolution with solvents, is macromolecular chain transfer agent.
3. the preparation method of a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim 1, is characterized in that, the described polymerization temperature of above-mentioned steps (1) is 65 ℃.
4. the preparation method of a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim 1, is characterized in that, the described polymerization temperature of above-mentioned steps (2) is 110 ℃.
5. the preparation method of a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim 1, is characterized in that in above-mentioned steps (1), mole when transformation efficiency of regulation and control GMA and CDB, and the polymerization degree that makes GMA is 30～150.
6. the preparation method of a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim 1, is characterized in that, in step 2, in feed intake St and PGMA, the ratio of the mole number of GMA unit is 14～40, and conversion rate control is 20%～50%.
7. the preparation method of a kind of surface amino groups decorated nanometer self-assembly aggregate according to claim 1, is characterized in that, in step 2, the temperature of amine and glycidyl methacrylate ring-opening reaction is 60～110 ℃.
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