CN103483514B - Amphiphilic acrylate copolymers and preparation method thereof - Google Patents
Amphiphilic acrylate copolymers and preparation method thereof Download PDFInfo
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- CN103483514B CN103483514B CN201310425582.3A CN201310425582A CN103483514B CN 103483514 B CN103483514 B CN 103483514B CN 201310425582 A CN201310425582 A CN 201310425582A CN 103483514 B CN103483514 B CN 103483514B
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Abstract
The invention belongs to the field of functional polymer materials, and particularly relates to amphiphilic acrylate block copolymers and a preparation method of the amphiphilic acrylate block copolymers. Under the environment of polystyrene macromolecular initiators and organic solvents, acrylate cadmium and butyl methacrylate react to generate amphiphilic acrylate block copolymers. The amphiphilic acrylate block copolymers are clear in polymer metal complex structure, kinds and content of metal ions in the polymers are certain, the formed polymers are amphiphilic and can be assembled automatically to form stable structures, and the amphiphilic acrylate block copolymers and the preparation method of the amphiphilic acrylic acid salt block copolymers are used for the biological fields of drug delivery and the like.
Description
Technical field
The invention belongs to functional high polymer material field, particularly one utilize atom transfer radical polymerization (ATRP) legal system standby there is amphipathic acrylate based block copolymer.
Background technology
To be a class to couple together by covalent linkage the polymkeric substance formed to block polymer by two or more different polymer segment, because multiple inconsistent polymer segment can be connected on same macromolecular chain by segmented copolymer, thus show the character of some uniquenesses, be widely used.As there is potential application prospect the preparation of the removing of the conveying of molecular recognition, medicine and other materials, gene therapy, aqueous coating, pollutent, nano composite material, catalyzer and sensor aspect.Certain block copolymers shows two kinds of affinities, is called amphipathic nature block polymer.Amphipathic nature block polymer, being only in the selective solvent of good solvent to a wherein segment, self-assembly can form micella.The form of micella and size depend on the character etc. of the character of two segments, the composition of multipolymer, concentration, solvent.Amphipathic nature block polymer can be used as stablizer, emulsifying agent, dispersion agent, drug delivery etc., in nanoparticle and microreactor etc., also have application.Therefore, the research of the synthesis of amphipathic nature block polymer and the self-assembly behavior in selective solvent thereof is quite concerned in recent years.
At present, in the research of amphipathic nature block polymer, common hydrophilic segment has polyoxyethylene, polyvinyl ether, polyvinyl alcohol and polymine, polyacrylic acid etc., and hydrophobic segment has polyoxypropylene, polystyrene and polysiloxane etc.Wherein, (methyl) vinylformic acid or a kind of conventional monomer preparing polymer metal complex compound, this kind of monomer to introduce target metal ions after other monomer copolymerizations and can prepare corresponding polymer metal complex compound, but synthesis step is more, and in polymer metal complex compound, metal ion content is uncertain.
Summary of the invention
Technical problem to be solved by this invention is: in prior art, and prepare the monomer of polymer metal complex compound, synthesis step is more, and in polymer metal complex compound, metal ion content is uncertain.
For solving this technical problem, the technical solution used in the present invention is:
The invention provides the amphipathic multipolymer of a kind of Acrylates, multipolymer is polystyrene-b-poly-(butyl methacrylate-co-vinylformic acid cadmium), and structural formula is
Wherein, x=80-120, y=110-200.
Present invention also offers the preparation method of the amphipathic multipolymer of a kind of aforesaid propylene Barbiturates, preparation manipulation is as follows:
The Kolle flask of drying is full of nitrogen except after air, adds cuprous bromide and 2, after 2 '-dipyridyl, pat and make its complexing, form black powder, add polystyrene macromolecular initiator and vinylformic acid cadmium subsequently, vacuumize-Tong nitrogen, inject butyl methacrylate and solvent, be put in after sealing in oil bath pan after reaction 12-14h, product with methylalcohol precipitates, after suction filtration, dry in vacuum drying oven
Above-mentioned solvent is selected from DMF, and the ratio of polystyrene macromolecular initiator amount and solvent is 0.1-0.4g/ml; The volume ratio of butyl methacrylate and solvent is 1:10-6:5; The mol ratio of vinylformic acid cadmium consumption and butyl methacrylate is 1%-11%,
Oil bath temperature is set as 80-100 DEG C.
Wherein, polystyrene macromolecular initiator can be prepared by the following method: after the Kolle flask of drying being vacuumized-Tong nitrogen 3 times, add cuprous bromide, 2, 2 '-dipyridyl, pat and make its complexing, Kolle flask is sealed, vacuumize-inflated with nitrogen 3 times again, inject the alpha-brominated ethyl isobutyrate of initiator and vinylbenzene, react 6 hours in 120 degrees Celsius of constant temperature oil baths after sealing, after end, Kolle flask is placed on cooling in cryosel bath, system is solidified, termination reaction, parlkaline alumina column after dissolving with tetrahydrofuran (THF), removing cupric ion wherein, use methanol/water (1:1 again, v/v) precipitate, after suction filtration, pressed powder puts into 40 degrees Celsius of vacuum drying oven dryings, keep in Dark Place with for subsequent use,
Vinylformic acid cadmium can be prepared by the following method: put by vinylformic acid and at room temperature dissolve, cadmium hydroxide is ground to finely powdered, cadmium hydroxide, vinylformic acid and deionized water are joined in flask, react 12-14 hours, product washing with acetone, put into vacuum drying oven Air drying after suction filtration, obtain white powder monomeric acrylic cadmium, sealing cryopreservation.
The amphipathic nature block polymer of the present invention's synthesis, can select suitable solvent, make it that self-assembly behavior occur, and forms imitated vesicle structure.
Such as: the self-assembly in aqueous of vinylformic acid cadmium multipolymer:
By the acrylate copolymer of above-mentioned preparation, be dissolved in tetrahydrofuran solution, being mixed with concentration is 3-5mg/ml polymers soln, then the solution microsyringe prepared slowly is squeezed in the round-bottomed flask that 20ml deionized water is housed, stop when the aqueous solution presents blue light, stir and obtain micellar solution in 24 hours, above-mentioned micellar solution is joined in 100ml deionized water, micella is solidified, obtains the solution that test needs.
Have such as: the vinylformic acid cadmium multipolymer self-assembly in aqueous after sulfuration:
By the acrylate copolymer of above-mentioned preparation, be dissolved in tetrahydrofuran solution, being mixed with concentration is 3-5mg/ml polymers soln, then joins in polymers soln by sulfuration ammonia, stirs and makes its sulfuration.Then the solution will vulcanizated, slowly squeezes into microsyringe in the round-bottomed flask that 20ml deionized water is housed, and stops when the aqueous solution presents blue light, stir and obtain micellar solution in 24 hours, micellar solution is joined in a large amount of deionized waters, micella is solidified, obtain the solution that test needs.
During sample preparation, drip test soln on TEM copper mesh, blot surplus liquid after 10 minutes with filter paper, copper mesh is drying at room temperature under ventilated environment, at least proposes a few days ago sample preparation to ensure that the moisture in TEM sample fully volatilizees.
Metal content in polymer-metal complex prepared by the present invention can be measured by plasma emission spectrometer.Concrete operations are as follows: a certain amount of polymkeric substance of accurate weighing in crucible, by its calcination, is made into the solution of different concns gradient after a series of process by remaining residue, test cadmium content wherein by plasma emission spectrometer.
The invention has the beneficial effects as follows: first the present invention has synthesized vinylformic acid cadmium, then is polymerized, form the polymer-metal complex that structure is clear and definite, the species of metal ion in polymkeric substance and content are determined.The polymkeric substance formed has amphipathic, can carry out self-assembly and form rock steady structure, for biological fields such as drug conveying.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of acrylate analog copolymer of the present invention.
Fig. 2 be the embodiment of the present invention provide when reacted between for 12h time, the infrared spectrum of polymkeric substance prepared by (" A, B, C, D, E " in figure represents polymkeric substance prepared by embodiment 1-5 respectively) during different vinylformic acid cadmium content.
Fig. 3 is the shape appearance figure of vinylformic acid cadmium multipolymer in aqueous after self-assembly after the vinylformic acid cadmium multipolymer prepared of the embodiment of the present invention 5 and sulfuration.Wherein, the left side is unvulcanized shape appearance figure; The right be the shape appearance figure after sulfuration.
Fig. 4: in the present invention, prepared by each embodiment, the thermal weight loss test pattern of vinylformic acid cadmium multipolymer.Wherein: curve A represents the thermogravimetric curve of polystyrene macromolecular initiator; Curve B represents the thermal weight loss situation of the vinylformic acid cadmium multipolymer of preparation in embodiment 2; Curve C represents embodiment 3; Curve D represents embodiment 4.
Fig. 5: the structural formula of acrylate analog copolymer of the present invention.
Embodiment
Below by specific embodiment, the present invention is further illustrated, but cited embodiment is not the restriction to technical solution of the present invention:
Embodiment 1
(1) preparation of vinylformic acid cadmium:
Vinylformic acid is put and at room temperature dissolves, take a certain amount of cadmium hydroxide, with mortar grinder to finely powdered.The 12ml vinylformic acid measured and 20ml deionized water are joined in flask, adds above-mentioned levigate cadmium hydroxide 12g, react 12 hours under room temperature.Product washing with acetone, puts into vacuum drying oven Air drying after suction filtration, just obtain white powder monomeric acrylic cadmium, sealing cryopreservation.
(2) preparation of polystyrene macromolecular initiator:
After the Kolle flask of drying being vacuumized-Tong nitrogen 3 times, add 0.1248g cuprous bromide successively, 0.4077g2, 2 '-dipyridyl, pat and make its complexing, seal with seal strip, vacuumize-inflated with nitrogen 3 times again, the 128 alpha-brominated ethyl isobutyrate of μ l initiator and 10ml vinylbenzene are injected successively with syringe, react 6 hours in 120 degrees Celsius of constant temperature oil baths after sealing, after end, Kolle flask is placed on cooling in cryosel bath, system is solidified, termination reaction, parlkaline alumina column after dissolving with tetrahydrofuran (THF), with removing cupric ion wherein, use methanol/water (1:1 again, v/v) precipitate, after suction filtration, pressed powder puts into 40 degrees Celsius of vacuum drying ovens dry 24 hours, keep in Dark Place with for subsequent use.
Tested known by GPC, the molecular weight of the polystyrene macromolecular initiator of this step synthesis is 10600, PDI is 1.14.
(3) preparation of vinylformic acid cadmium multipolymer:
The Kolle flask of drying is full of nitrogen except after air, repeatable operation three times, add 2 of 0.0116g cuprous bromide and 0.0378g, after 2 '-dipyridyl, pat and make its complexing, form black powder, add the vinylformic acid cadmium prepared in polystyrene macromolecular initiator and 0.02g step (1) prepared by 1g step (2) subsequently, after vacuumizing-Tong nitrogen 3 times, the N of 1.2ml butyl methacrylate and 5ml is injected successively with syringe, dinethylformamide, be put in after reacting 12h in 80 degrees Celsius of thermostatical oil baths after sealing, product with methylalcohol precipitates, after suction filtration, dry in vacuum drying oven, obtain vinylformic acid cadmium multipolymer.
GPC method of testing is used to measure the polymerization degree: by the vinylformic acid cadmium multipolymer of above-mentioned preparation, be dissolved in tetrahydrofuran (THF), be mixed with the solution of 5 ‰, above-mentioned solution is filtered to remove the solid impurity in solution with the injection needle tube of band filter, the filtrate sealing obtained is preserved, differential refraction/multiple angle laser light scattering instrument/bridge-type capillary viscosity three is used to detect the gel permeation chromatography (GPC of coupling, waters717 type) measure the molecular mass and distribution of vinylformic acid cadmium multipolymer, test condition is: column temperature 35 DEG C, moving phase is THF, flow velocity 1mL/min, sample size 100 μ L.The measured polymerization degree be x=102, y=114(structural formula as shown in Figure 5).
Embodiment 2:
In the present embodiment, the preparation method of vinylformic acid cadmium and polystyrene macromolecular initiator, shown in embodiment 1.
The Kolle flask of drying is full of nitrogen except after air, repeatable operation three times, add 2 of 0.0166g cuprous bromide and 0.0478g, after 2 '-dipyridyl, pat and make its complexing, form black powder, add 1g polystyrene macromolecular initiator and 0.057g vinylformic acid cadmium subsequently, after vacuumizing-Tong nitrogen 3 times, the N of 1.2ml butyl methacrylate and 5ml is injected successively with syringe, dinethylformamide, be put in after reacting 12h in 90 degrees Celsius of thermostatical oil baths after sealing, product with methylalcohol precipitates, after suction filtration, drying 24 hours in 40 degrees Celsius of vacuum drying ovens, obtain vinylformic acid cadmium multipolymer.
Use GPC method of testing to measure the polymerization degree: means of testing as shown in Example 1, the polymerization degree recorded be x=102, y=125(structural formula as shown in Figure 5).
Embodiment 3:
In the present embodiment, the preparation method of vinylformic acid cadmium and polystyrene macromolecular initiator, shown in embodiment 1.
The Kolle flask of drying is full of nitrogen except after air, repeatable operation three times, add 2 of 0.0186g cuprous bromide and 0.0568g, after 2 '-dipyridyl, pat and make its complexing, form black powder, add 1g polystyrene macromolecular initiator and 0.095g vinylformic acid cadmium subsequently, after vacuumizing-Tong nitrogen 3 times, the N of 1.2ml butyl methacrylate and 5ml is injected successively with syringe, dinethylformamide, be put in after reacting 12h in 100 degrees Celsius of thermostatical oil baths after sealing, product with methylalcohol precipitates, after suction filtration, drying 24 hours in 40 degrees Celsius of vacuum drying ovens, obtain vinylformic acid cadmium multipolymer.
Use GPC method of testing to measure the polymerization degree: means of testing as shown in Example 1, the polymerization degree recorded be x=102, y=140(structural formula as shown in Figure 5).
Embodiment 4:
In the present embodiment, the preparation method of vinylformic acid cadmium and polystyrene macromolecular initiator, shown in embodiment 1.
The Kolle flask of drying is full of nitrogen except after air, repeatable operation three times, add 2 of 0.0209g cuprous bromide and 0.0628g, after 2 '-dipyridyl, pat and make its complexing, form black powder, add 1g polystyrene macromolecular initiator and 0.133g vinylformic acid cadmium subsequently, after vacuumizing-Tong nitrogen 3 times, the N of 1.2ml butyl methacrylate and 5ml is injected successively with syringe, dinethylformamide, be put in after reacting 12h in 90 degrees Celsius of thermostatical oil baths after sealing, product with methylalcohol precipitates, after suction filtration, drying 24 hours in 40 degrees Celsius of vacuum drying ovens, obtain vinylformic acid cadmium multipolymer.
Use GPC method of testing to measure the polymerization degree: means of testing as shown in Example 1, the polymerization degree recorded be x=102, y=162(structural formula as shown in Figure 5).
Embodiment 5:
In the present embodiment, the preparation method of vinylformic acid cadmium and polystyrene macromolecular initiator, shown in embodiment 1.
The Kolle flask of drying is full of nitrogen except after air, repeatable operation three times, add 2 of 0.0220g cuprous bromide and 0.0706g, after 2 '-dipyridyl, pat and make its complexing, form black powder, add 1g polystyrene macromolecular initiator and 0.181g vinylformic acid cadmium subsequently, after vacuumizing-Tong nitrogen 3 times, 1.2ml butyl methacrylate and 5mlN is injected successively with syringe, dinethylformamide, be put in after reacting 12h in 90 degrees Celsius of thermostatical oil baths after sealing, product with methylalcohol precipitates, after suction filtration, drying 24 hours in 40 degrees Celsius of vacuum drying ovens, obtain vinylformic acid cadmium multipolymer.
Use GPC method of testing to measure the polymerization degree: means of testing as shown in Example 1, the polymerization degree recorded be x=102, y=176(structural formula as shown in Figure 5).
The self-assembly in aqueous of vinylformic acid cadmium multipolymer:
By the acrylate copolymer of above-mentioned preparation, be dissolved in tetrahydrofuran solution, being mixed with concentration is 4mg/ml polymers soln, then the solution microsyringe prepared slowly is squeezed in the round-bottomed flask that 20ml deionized water is housed, stop when the aqueous solution presents blue light, stir and obtain micellar solution in 24 hours, micellar solution is joined in a large amount of deionized waters, micella is solidified, obtains the solution that test needs.
During sample preparation, drip test soln on TEM copper mesh, blot surplus liquid after 10 minutes with filter paper, copper mesh is drying at room temperature under ventilated environment, at least proposes a few days ago sample preparation to ensure that the moisture in TEM sample fully volatilizees.
Self-assembly shape appearance figure as shown in Figure 3.
Vinylformic acid cadmium multipolymer self-assembly in aqueous after sulfuration:
By the acrylate copolymer of above-mentioned preparation, be dissolved in tetrahydrofuran solution, being mixed with concentration is 4mg/ml polymers soln, then joins in this polymers soln of 10ml by 3ml sulfuration ammonia, stirs and makes its sulfuration.Then the solution will vulcanizated, slowly squeezes into microsyringe in the round-bottomed flask that 20ml deionized water is housed, and stops when the aqueous solution presents blue light, stir and obtain micellar solution in 24 hours, micellar solution is joined in a large amount of deionized waters, micella is solidified, obtain the solution that test needs.
During sample preparation, drip test soln on TEM copper mesh, blot surplus liquid after 10 minutes with filter paper, copper mesh is drying at room temperature under ventilated environment, at least proposes a few days ago sample preparation to ensure that the moisture in TEM sample fully volatilizees.
Self-assembly shape appearance figure as shown in Figure 3.
Embodiment 6:
In the present embodiment, the preparation method of vinylformic acid cadmium and polystyrene macromolecular initiator, shown in embodiment 1.
The Kolle flask of drying is full of nitrogen except after air, repeatable operation three times, add 2 of 0.0232g cuprous bromide and 0.0756g, after 2 '-dipyridyl, pat and make its complexing, form black powder, add 1g polystyrene macromolecular initiator and 0.209g vinylformic acid cadmium subsequently, after vacuumizing-Tong nitrogen 3 times, the N of 1.2ml butyl methacrylate and 5ml is injected successively with syringe, dinethylformamide, be put in after reacting 12h in 90 degrees Celsius of thermostatical oil baths after sealing, product with methylalcohol precipitates, after suction filtration, drying 24 hours in 40 degrees Celsius of vacuum drying ovens, obtain vinylformic acid cadmium multipolymer.
Use GPC method of testing to measure the polymerization degree: means of testing as shown in Example 1, the polymerization degree recorded be x=102, y=185(structural formula as shown in Figure 5).
A certain amount of polymkeric substance of accurate weighing in crucible, by its calcination, is made into the solution of different concns gradient after a series of process by remaining residue, test cadmium content wherein by plasma emission spectrometer.Rapid determination of content of cadmium element in polymkeric substance prepared by the present embodiment is that 0.82%(and theoretical value are close after measured).
Claims (6)
1. a preparation method for the amphipathic multipolymer of Acrylates, is characterized in that:
Described multipolymer is polystyrene-b-poly-(butyl methacrylate-co-vinylformic acid cadmium), and structural formula is
Wherein, x=80-120, y=110-200;
The concrete steps of described method are
The Kolle flask of drying is full of nitrogen except after air, add cuprous bromide and 2, after 2 '-dipyridyl, pat and make its complexing, form black powder, add polystyrene macromolecular initiator and vinylformic acid cadmium subsequently, vacuumize-Tong nitrogen, inject butyl methacrylate and solvent, be put in after reacting 12-14h in oil bath pan after sealing, product with methylalcohol precipitates, after suction filtration, dry in vacuum drying oven.
2. the preparation method of the amphipathic multipolymer of Acrylates as claimed in claim 1, is characterized in that: described solvent is selected from DMF.
3. the preparation method of the amphipathic multipolymer of Acrylates as claimed in claim 1, is characterized in that: described polystyrene macromolecular initiator amount and the ratio of solvent are 0.1-0.4g/ml.
4. the preparation method of the amphipathic multipolymer of Acrylates as claimed in claim 1, is characterized in that: described butyl methacrylate and the volume ratio of solvent are 1:10-6:5.
5. the preparation method of the amphipathic multipolymer of Acrylates as claimed in claim 1, is characterized in that: described vinylformic acid cadmium consumption and the mol ratio of butyl methacrylate are 1%-11%.
6. the preparation method of the amphipathic multipolymer of Acrylates as claimed in claim 1, is characterized in that: described oil bath temperature is set as 80-100 DEG C.
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| CN101134801A (en) * | 1998-07-10 | 2008-03-05 | 埃勒夫阿托化学有限公司 | Polymerisation particles, entirety of the polymerisation particles or mixture and rubber latex |
| CN101454395A (en) * | 2006-05-25 | 2009-06-10 | 阿科玛股份有限公司 | Amphiphilic block copolymers |
| CN101636424A (en) * | 2007-01-19 | 2010-01-27 | 罗地亚运作公司 | Diblock copoplymer including units derived from styrene and units derived from acrylic acid |
| CN102838773A (en) * | 2012-09-26 | 2012-12-26 | 华东理工大学 | Preparation method for porous material based on water-in-oil type high internal phase emulsion with stable polymer nanoparticles |
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| US8362179B2 (en) * | 2008-11-19 | 2013-01-29 | Wisconsin Alumni Research Foundation | Photopatternable imaging layers for controlling block copolymer microdomain orientation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101134801A (en) * | 1998-07-10 | 2008-03-05 | 埃勒夫阿托化学有限公司 | Polymerisation particles, entirety of the polymerisation particles or mixture and rubber latex |
| CN101454395A (en) * | 2006-05-25 | 2009-06-10 | 阿科玛股份有限公司 | Amphiphilic block copolymers |
| CN101636424A (en) * | 2007-01-19 | 2010-01-27 | 罗地亚运作公司 | Diblock copoplymer including units derived from styrene and units derived from acrylic acid |
| CN102838773A (en) * | 2012-09-26 | 2012-12-26 | 华东理工大学 | Preparation method for porous material based on water-in-oil type high internal phase emulsion with stable polymer nanoparticles |
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