CN106632919A - Redox response type block copolymer vesica and preparation method thereof - Google Patents
Redox response type block copolymer vesica and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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Abstract
The invention relates to a redox response type block copolymer vesica and a preparation method thereof. According to the vesica, a ferrocenyl-containing amphiphilic block copolymer serves as an object, the ferrocene group is subjected to chemical oxidation-reduction, the hydrophilicity and hydrophobicity distribution of the system is changed for design and preparation, and the vesica is a redox response type vesica based on the ferrocenyl-containing amphiphilic block copolymer. The vesica is specifically PFCn-b-PEO-b-PFCn.
Description
Technical field
The application is related to a kind of redox response type block copolymer vesicles and preparation method thereof, more particularly to a kind of tool
There are amphipathic redox response type block copolymer vesicles and preparation method thereof.
Background technology
Develop the important topic that all kinds of novel environmental response type assemblies are always Macromolecular self-assembly field.Pass through at present
The modes such as temperature, light, pH value, solvent polarity, Subjective and Objective molecular recognition, enzyme, redox are preparing environmental response type assembly
Obtain fast development.
In recent years, the report for preparing stimuli responsive type assembly by oxidation or redox regulatory mode starts to cause
The concern of people.Cardinal principle is that sulfur-bearing, the isotope of redox-sensitive group containing selenium, purpurine, ferrocene etc. are incorporated into macromolecular
In self-assembly system, macromolecular assemblies are regulated and controled by the change of these groups hydrophilic and hydrophobic in different redox environments
Accumulation shape, so as to prepare novel oxidized or redox response type assembly.For example, Hubbell etc. synthesizes one
Class sulfur-bearing amphipathic nature block polymer polyethylene glycol-b- polypropylene sulfides-b- polyethylene glycol (PEO-b-PPS-b-PEO), passes through
The oxidation of hydrogen peroxide, polypropylene sulfide part is oxidized to sulfone formula structure, and hydrophily is improved, and aggregation is tied from the vesica of reduction-state
Vermiculate glues of the allosteric transformation into oxidation state.It is the key factor for affecting molecular assembly pattern that molecule is amphipathic, if can be with
The dynamically hydrophilic and hydrophobic of Molecular regulator in the solution, then can be to realize the assembling of dynamic control assembly in the way of.And for example, Yuan Jin
Grain husks etc. are prepared for a kind of novel redox response supermolecule vesica body by introducing ferrocene group, and this kind of assembly is by two kinds
Homopolymers utilizes the orthogonal connection of non-covalent bond, the polystyrene homopolymer (PS- of one section of beta-schardinger dextrin (β-CD) that has been end modified
β-CD), the PEO (PEO-Fc) of the other end ferrocenyl (Fc) that has been end modified, the two passes through terminal functional groups
Host-guest interaction formed non-covalent bond block copolymer (PS- β-CD/PEO-Fc), carry out classification again afterwards and be assembled in water
Supermolecule vesica is formed in solution.The host -guest inclusion complex of β-CD and Fc can be adjusted by redox mode.
Apply an appropriate position on schedule in situ in the solution, can be terminal oxidized for positively charged Fc by neutral Fc+；And Fc+
Due to powered, its electrostatic screen effect and hydrophily are greatly improved, and can be dissociateed from the hydrophobic internal cavities of β-CD and, and are caused
The de-assembly of PS- β-CD/PEO-Fc vesicas.It is interesting that can be by applying an appropriate negative direction reduction in solution
Voltage and reversible regulation and control, cause vesica to re-assembly.Research finds, in the case where positive negative potential repeatedly stimulates, the group of this kind of vesica
The invertibity of dress and de-assembly is good[7].In oxidation-reduction process, ferrocene group is different from sulfur-bearing, containing groups such as selenium
It is that its own structure does not change, simply there occurs electron exchange, so as to have impact on its hydrophilic and hydrophobic, this process is several
Completely reversibility.This interesting property cause ferrocene group be expected to be incorporated into other as redox response group it is controllable
Self-assembly system, the experiment fully also show application potential of the ferrocene group in novel environmental response type assembly field.
The content of the invention
The application (adds redox with a kind of amphiphilic block copolymer containing ferrocenyl as research object by chemistry
Reagent) redox ferrocene group, change the close and distant water distribution of system, study block copolymer aggregation in aqueous
Formation, structure change and reversible condition, design, prepare a kind of oxidation based on ferrocenyl amphiphilic block copolymer also
Former response type vesica.
To solve above-mentioned technical problem：The application proposes a kind of redox response type block copolymer vesicles, the capsule
Bubble, by chemistry redox ferrocene group, changes the close and distant of system with amphiphilic block copolymer containing ferrocenyl as object
Water distribution, is designed and prepares, and the vesica is based on the redox response type capsule of ferrocenyl amphiphilic block copolymer
Bubble.
It may be preferred that the vesica is triblock copolymer.
It may be preferred that the vesica is specially：PFCn-b-PEO-b-PFCn；Wherein, n is to synthesize altogether in this case
The block copolymer of three kinds of difference n values, i.e., 10,17,28, it is also possible to regulated and controled by changing the amount of monomer, b is block's
Write a Chinese character in simplified form, the meaning of block, PFC is polymethylacrylic acid ferrocene hendecane base ester), PEO is polyethylene glycol.
A kind of redox response type block copolymer vesicles, arbitrary described vesica copolymer vesica as described above,
With following structure：
Wherein, n is to synthesize the block copolymer of three kinds of difference n values in this case altogether, i.e., 10,17,28, it is also possible to by change
The amount of monomer is regulated and controled), b writes a Chinese character in simplified form for block's, the meaning of block, and PFC is polymethylacrylic acid ferrocene undecyl
Ester), PEO is polyethylene glycol.
It may be preferred that synthesize the reagent selected by the vesica being：Molecular weight is 20,000 polyethylene glycol (PEO), 2-
Bromo isobutyl acylbromide (>98%), N, N, N ', N ", N "-PMDETA (PMDETA, 99%), cuprous bromide
(CuBr), triethylamine (TEA), dichloromethane, toluene, pure, other reagents of analysis are the pure, experimental water of analysis.
It may be preferred that the molecular weight for 20,000 polyethylene glycol (PEO) in trace moisture by subtracting with toluene
Pressure azeotropic distillation is removed；The cuprous bromide (CuBr) using it is front be washed till with glacial acetic acid it is colourless, then respectively with absolute methanol, anhydrous
Ether is washed three times, vacuum drying, is preserved in nitrogen atmosphere；The triethylamine (TEA) is flowed back with p-methyl benzenesulfonic acid acyl chlorides, distillation,
CaH2In the presence of store；The dichloromethane is pure for analysis, is washed with 5% sodium carbonate liquor, is washed with water and washs, then with anhydrous
Calcium chloride is dried, and 40～41 DEG C of cut is collected in distillation, in being stored in brown bottle；The toluene is pure for analysis, using front using sodium
Silk backflow eliminating water, air-distillation；Described other reagents are analyzes pure, using front drying, distillation；The experimental water is height
Pure water, Millipore purifiers process Millipore：A kind of brand of the water-purifying apparatus of purified water, resistivity >=
18.2MΩ。
It may be preferred that its synthetic route is：
Wherein, two-step reaction is divided into, first step raw molecule amount is 20000 ethylene glycol, 2- bromo isobutyl acylbromides, triethylamine
In toluene reaction, product is macromole evocating agent Br-PEO20000-Br；Second step is macromole evocating agent Br-PEO20000-
Br, monomer methacrylic acid ferrocene hendecane base ester and catalyst cuprous bromide, N, N, N ', N ", N " and-pentamethyl divinyl
Triamine reacts in toluene, obtains final product PFCn-b-PEO-b-PFCn.
A kind of preparation method of the vesica arbitrary as described above, it is characterised in that：Comprise the steps：
(1) at room temperature, a certain amount of macromole evocating agent Br-PEO20000-Br and catalyst CuBr are added into applying argon gas
5mL Schlenk bottles in；
(2) sealed with rubber plug with overlapped mouth, vacuumize deoxygenation, the syringe crossed with argon purge adds the toluene 2mL dissolvings of degassing big
Initiator molecule, (3) add the degassed monomer methacrylic acid ferrocene hendecane base ester that ratio is measured by the design degree of polymerization,
Liquid nitrogen frozen-vacuumize-applying argon gas thaw, and circulate three deoxygenations, and the syringe crossed with argon purge adds a certain amount of matching somebody with somebody
Body PMDETA；
(4) immersion is previously heated in 80 DEG C of oil bath, reacts 6h, the reaction of liquid nitrogen frozen Quick stop；
(5) reaction system is concentrated, adds petroleum ether：Ethyl acetate=4:1 mixed solvent dissolving, crosses post, by unreacted list
After body is washed out, then crude product is eluted with THF+5% triethylamine mixed solvents；
(6) crude product is dissolved in a small amount of dichloromethane, the repeated precipitation in a large amount of n-hexanes, obtains pure three block and be total to
Polymers PFCn-b-PEO-b-PFCn, is dried under vacuum to constant weight.
It may be preferred that the macromole evocating agent Br-PEO20000-Br and catalyst CuBr in the step (1)
By 1:2 mol ratio is added in the 5mL Schlenk bottles of applying argon gas.
It may be preferred that the metering that part PMDETA is added in the step (3) is 2 times of macromole evocating agent meter.
Description of the drawings
Fig. 1 PFCn-b-PEO-b-PFCn triblock copolymer schematic diagrames.
The synthetic route schematic diagram of Fig. 2 PFCn-b-PEO-b-PFCn triblock copolymers.
Fig. 3 is dependence linearity curve of the equilibrium surface tension of PFCn-b-PEO-b-PFCn to concentration.
Fig. 4 schemes (C=1.0g/L) for the SEM of block copolymer M28-b-E454-b-M28 aggregations.
Fig. 5 schemes (C=1.0g/L) for the TEM of block copolymer M28-b-E454-b-M28 aggregations.
Fig. 6 is the aqueous solution (C=1.0g/L) the state of aggregation change of size figure of M10-b-E454-b-M10.
Fig. 7 is the aqueous solution (C=1.0g/L) the state of aggregation change of size figure of M17-b-E454-b-M17.
Fig. 8 is the aqueous solution (C=1.0g/L) the state of aggregation change of size figure of M28-b-E454-b-M28.
Specific embodiment
The application is described in further detail below in conjunction with the accompanying drawings, it is necessary to it is pointed out here that, implement in detail below
Mode is served only for being further detailed the present invention, it is impossible to be interpreted as limiting the scope of the invention, the field
Technical staff can make some nonessential modifications and adaptations to the application according to the description below.
As shown in figure 1, for the application PFCn-b-PEO-b-PFCn triblock copolymer structure wherein, n be this case in
Synthesize the block copolymer of three kinds of difference n values altogether, i.e., 10,17,28, it is also possible to regulated and controled by changing the amount of monomer, b is
Block's writes a Chinese character in simplified form, the meaning of block), PFC is polymethylacrylic acid ferrocene hendecane base ester), PEO is polyethylene glycol).
Synthesizing the reagent selected by the vesica is：Molecular weight is 20,000 polyethylene glycol (PEO), 2- bromo isobutyl acylbromide
(>98%), N, N, N ', N ", N "-PMDETA (PMDETA, 99%), cuprous bromide (CuBr), triethylamine
(TEA), dichloromethane, toluene, pure, other reagents of analysis are the pure, experimental water of analysis.
The molecular weight for 20,000 polyethylene glycol (PEO) in trace moisture by removing with toluene decompression co-boiling distiling
Go；The cuprous bromide (CuBr) is washed till colourless using front with glacial acetic acid, then is washed three times with absolute methanol, absolute ether respectively,
Vacuum drying, preserves in nitrogen atmosphere；The triethylamine (TEA) is flowed back with p-methyl benzenesulfonic acid acyl chlorides, distillation, CaH2In the presence of store up
Deposit；The dichloromethane is pure for analysis, is washed with 5% sodium carbonate liquor, is washed with water and washs, and is then dried with anhydrous calcium chloride,
40～41 DEG C of cut is collected in distillation, in being stored in brown bottle；The toluene is pure for analysis, using front use sodium silk backflow eliminating water,
Air-distillation；Described other reagents are analyzes pure, using front drying, distillation；The experimental water is high purity water,
The process of Millipore purifiers, Millipore：A kind of brand of the water-purifying apparatus of purified water), resistivity >=18.2M
Ω。
Fig. 2 show PFCn-b-PEO-b-PFCnThe synthetic route of triblock copolymer.
Polymerisation detailed process：At room temperature, by a certain amount of macromole evocating agent Br-PEO20000-Br and catalysis
Agent CuBr (presses 1:2 mol ratio) it is added to the 5mL Schlenk bottles of applying argon gas, sealed with rubber plug with overlapped mouth, deoxygenation is vacuumized,
The syringe crossed with argon purge adds the toluene 2mL dissolving macromole evocating agents of degassing, adds by design degree of polymerization metering ratio
Degassed monomer methacrylic acid ferrocene hendecane base ester, liquid nitrogen frozen-vacuumize-applying argon gas thaws, circulation three
Secondary deoxygenation, the syringe crossed with argon purge adds a certain amount of part PMDETA (to add metering for macromole evocating agent meter 2
Times).Immersion is previously heated in 80 DEG C of oil bath, reacts 6h, the reaction of liquid nitrogen frozen Quick stop.Reaction system is concentrated, plus
Enter petroleum ether：Ethyl acetate=4:1 mixed solvent dissolving, crosses post (wash-out and solvent：Oily ether/ethyl acetate=4/1), will
After unreacted monomer is washed out, then crude product is eluted with THF+5% triethylamine mixed solvents.Crude product is dissolved in into a small amount of two
In chloromethanes, the repeated precipitation in a large amount of n-hexanes obtains pure triblock copolymer PFCn-b-PEO-b-PFCn, vacuum
It is dried to constant weight.
Fig. 3 is dependence linearity curve of the equilibrium surface tension of PFCn-b-PEO-b-PFCn to concentration, can be calculated from figure
Go out M10-b-E454-b-M10CMC (critical micelle concentration) be 0.06g/L；M17-b-E454-b-M17CMC be 0.07g/L；M28-
b-E454-b-M28CMC be 0.11g/L.As a result the CMC of three kinds of block copolymers is shown closely.With M28-b-E454-b-M28
As a example by, its state of aggregation photo directly perceived is as shown in Figure 4 and Figure 5；From TEM and SEM photograph, it can be seen that block copolymer defines ball
Shape imitated vesicle structure.M10-b-E454-b-M10And M17-b-E454-b-M17Also form similar imitated vesicle structure.
Three kinds of block polymer concentration of aqueous solution are 1g/L, and its vesicle size is distributed as shown in Fig. 6, Fig. 7, Fig. 8.Can see
Go out, M10-b-E454-b-M10The vesica average grain diameter of formation is 142nm, M17-b-E454-b-M17The vesica average grain diameter of formation is
164nm, M28-b-E454-b-M28The vesica average grain diameter of formation is 190nm.With polymethylacrylic acid ferrocene undecyl
The increase of ester block, vesicle diameter gradually increases.
In order to further study its vesica Changing Pattern, we have carried out chemical method redox to three kinds of polymer,
The change of its vesica is inquired into.M10-b-E454-b-M10Before and after chemistry redox, its vesica change of size is distributed such as Fig. 6 institutes
Show.It can be seen that when ferrocene is in original reduction-state, average grain diameter is 142nm, the sulphur of 1.1 times of moles is added
After sour iron is fully oxidized, from faint yellow transformation au bleu, average grain diameter increases to 164nm to solution colour, it is presumed that ferrocene
After oxidation, become hydrophilic radical, vesica is further swelling caused.For above-mentioned system, we continuously add somewhat excessively has
The ascorbic acid (Vc) of reproducibility, vesica particle diameter is reduced to particle diameter during 122nm, slightly less than original reduction-state again, this explanation, gathers
Compound M10-b-E454-b-M10Ferrocene group be in hydrophobic contraction state again, the color of system also transforms back into faint yellow.On
Result explanation is stated, we can successfully pass the self assembly form of chemistry redox adjustment and control system.
Study Polymer Melts M17-b-E454-b-M17And M28-b-E454-b-M28When, it has been found that similar rule.It is concrete next
Say, for M17-b-E454-b-M17Before and after chemistry redox, its vesica change of size distribution is as shown in Figure 7.Original reduction-state
When average grain diameter be 164nm, vesica particle diameter increases to 190nm after oxidation, and 140nm is returned to after reduction；For M28-b-E454-b-
M28Before and after chemistry redox, its change of size distribution is as shown in Figure 8.Average grain diameter is 190nm during original reduction-state, after oxidation
Vesica increases to 220nm, and 164nm is returned to after reduction；In sum, we are successfully found that a class redox response type
Block copolymer vesicles.
Amphipathic PFCn-b-PEO-b-PFCn triblock copolymers can form imitated vesicle structure in water.Can be by chemistry
Redox regulatory vesicle size.A kind of redox response type capsule based on ferrocenyl amphiphilic block copolymer is invented
Bubble.
Herein described triblock copolymer can be with the polymethylacrylic acid ferrocene undecyl of the copolymer
The increase of ester block, vesicle diameter gradually increases.And redox reaction is can adapt to, possesses good invertibity, meanwhile,
The hydrophily of copolymer is substantially increased, and possesses hydrophobicity, can be adjusted in the hydrophilic and hydrophobic of easy middle dynamic regulation molecule
The assembling morphology of overall system, changes particle size, possesses good adaptability.
Claims (10)
1. a kind of redox response type block copolymer vesicles, the vesica is right with amphiphilic block copolymer containing ferrocenyl
As by chemistry redox ferrocene group, changing the close and distant water distribution of system, it is characterised in that：The vesica be based on
The redox response type vesica of ferrocenyl amphiphilic block copolymer.
2. vesica as claimed in claim 1, it is characterised in that：The vesica is triblock copolymer.
3. vesica as claimed in claim 2, it is characterised in that：The vesica is specially：PFCn-b-PEO-b-PFCn；Wherein,
N is block copolymer, and b is block, and PFC is polymethylacrylic acid ferrocene hendecane base ester, and PEO is polyethylene glycol.
4. a kind of redox response type block copolymer vesicles, it is characterised in that：The vesica has following structure：
Wherein, n is block copolymer, and b is block, and PFC is polymethylacrylic acid ferrocene hendecane base ester, and PEO is poly- second two
Alcohol.
5. vesica as claimed in claim 4, it is characterised in that：Synthesizing the reagent selected by the vesica is：Molecular weight is 20,
000 polyethylene glycol (PEO), 2- bromo isobutyl acylbromides (>98%), N, N, N ', N ", N " and-PMDETA
(99%) PMDETA, cuprous bromide (CuBr), triethylamine (TEA), dichloromethane, toluene, analyzes pure, other reagents and is point
Analyse pure, experimental water.
6. vesica as claimed in claim 5, it is characterised in that：The molecular weight be 20,000 polyethylene glycol (PEO) in trace
The moisture of amount with toluene decompression co-boiling distiling by removing；The cuprous bromide (CuBr) using it is front be washed till with glacial acetic acid it is colourless,
Washed three times with absolute methanol, absolute ether respectively again, be vacuum dried, preserved in nitrogen atmosphere；The triethylamine (TEA) with to first
Benzene sulfonic acid acyl chlorides flows back, distillation, CaH2In the presence of store；The dichloromethane is pure for analysis, is washed with 5% sodium carbonate liquor,
It is washed with water and washs, be then dried with anhydrous calcium chloride, 40～41 DEG C of cut is collected in distillation, in being stored in brown bottle；The first
Benzene is pure for analysis, using front use sodium silk backflow eliminating water, air-distillation；Described other reagents are analyzes pure, using front drying, steaming
Evaporate；The experimental water is high purity water, the process of Millipore purifiers, and Millipore is a kind of purified water, resistivity
≥18.2MΩ。
7. vesica as claimed in claim 5, it is characterised in that：Its synthetic route is：
Wherein, two-step reaction is divided into, first step raw molecule amount is 20000 ethylene glycol, 2- bromo isobutyl acylbromides, triethylamine
In toluene reaction, product is macromole evocating agent Br-PEO20000-Br；Second step is macromole evocating agent Br-PEO20000-
Br, monomer methacrylic acid ferrocene hendecane base ester and catalyst cuprous bromide, N, N, N ', N ", N " and-pentamethyl divinyl
Triamine reacts in toluene, obtains final product PFCn-b-PEO-b-PFCn.
8. a kind of preparation method of the vesica as described in claim 1-7 is arbitrary, it is characterised in that：Comprise the steps：
(1) at room temperature, a certain amount of macromole evocating agent Br-PEO20000-Br and catalyst CuBr are added into applying argon gas
5mL Schlenk bottles in；
(2) sealed with rubber plug with overlapped mouth, vacuumize deoxygenation, the syringe crossed with argon purge adds the toluene 2mL dissolvings of degassing big
Initiator molecule, (3) add the degassed monomer methacrylic acid ferrocene hendecane base ester that ratio is measured by the design degree of polymerization,
Liquid nitrogen frozen-vacuumize-applying argon gas thaw, and circulate three deoxygenations, and the syringe crossed with argon purge adds a certain amount of matching somebody with somebody
Body PMDETA；
(4) immersion is previously heated in 80 DEG C of oil bath, reacts 6h, the reaction of liquid nitrogen frozen Quick stop；
(5) reaction system is concentrated, adds petroleum ether：Ethyl acetate=4:1 mixed solvent dissolving, crosses post, by unreacted list
After body is washed out, then crude product is eluted with THF+5% triethylamine mixed solvents；
(6) crude product is dissolved in a small amount of dichloromethane, the repeated precipitation in a large amount of n-hexanes, obtains pure three block and be total to
Polymers PFCn-b-PEO-b-PFCn, is dried under vacuum to constant weight.
9. a kind of preparation method as claimed in claim 8, it is characterised in that：The macromole evocating agent in the step (1)
Br-PEO20000-Br and catalyst CuBr presses 1:2 mol ratio is added in the 5mL Schlenk bottles of applying argon gas.
10. a kind of preparation method as claimed in claim 8, it is characterised in that：The meter that part PMDETA is added in the step (3)
Measure as 2 times of macromole evocating agent meter.
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| CN107641182A (en) * | 2017-11-02 | 2018-01-30 | 东莞理工学院 | Ferrocenyl amphipathic nature block polymer, ultracapacitor and preparation method |
| CN107641182B (en) * | 2017-11-02 | 2019-09-06 | 东莞理工学院 | Ferrocenyl amphipathic nature block polymer, supercapacitor and preparation method |
| CN108925396A (en) * | 2018-06-26 | 2018-12-04 | 常州市蒽盗钟情生物科技有限公司 | A kind of road flower nursery special environment protection contains soil material |
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