CN103772714A - Starlike segmented copolymer and preparation method thereof - Google Patents
Starlike segmented copolymer and preparation method thereof Download PDFInfo
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- CN103772714A CN103772714A CN201410034883.8A CN201410034883A CN103772714A CN 103772714 A CN103772714 A CN 103772714A CN 201410034883 A CN201410034883 A CN 201410034883A CN 103772714 A CN103772714 A CN 103772714A
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Abstract
The invention belongs to the technical field of macromolecular materials, and specifically relates to a starlike segmented copolymer and a preparation method thereof. The method specifically comprises the following step: through a Huisgen cycloaddition reaction, successively connecting polystyrene and polylactic acid or polyoxyethylene to the same core molecule to form an A2B type three-arm starlike segmented copolymer. The three-arm starlike segmented copolymer prepared by the invention has a precise and controllable molecular chain structure, can be used for self-assembly in liquor to form a core-shell nano-micelle, and can be further used for microphase separation under heating to form a regular and ordered nanophase separated structure which is further prepared to a nano organic porous material with a regular porous structure and high specific surface area. The starlike segmented copolymer has a wide prospect in the fields such as drug sustained release and nano separation.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of star block copolymer and preparation method thereof.
Background technology
So-called star polymer, refers to, containing distinguishing more than three chains and each chain dereliction side chain, all be connected to chemical bond-linking the star-shape polymer that same point is formed, and has three-dimensional flakes structure, is the special branched polymer of a class.The preparation method of radial copolymer has at present, two kinds of technology of core first and arm first.The former refers to and adopts multifunctional initiator trigger monomer polymerization or on main chain, generate the polymerization of free radical trigger monomer, form radial copolymer, and the latter first synthesizes the active linear high polymer of simple function, pre-synthesis arm reacts and obtains or receive on main chain by the reaction between macromole with multi-functional coupling agent.
Core first can adopt the technology such as controlled ring-opening polymerization, atom transfer radical polymerization, active ion polymerization, reversible addition-fracture chain transfer polymerization to prepare.For example, the people such as Ishizu, by Transfer Radical Polymerization, have obtained star polymethyl acrylate (J. Appl. Polym. Sci. 2006,100,3340).The arm number that obtains star polymer by this method is controlled, and its arm number is determined by initiator group number, but shortcoming is: must be pre-synthesis because of multifunctional initiator, prepare more difficult; When polymerization, there is side reaction; In the time stirring, cause that core size variation and arm number disperse, and will cause several core to link together formation macronucleus.
Arm first is the effective ways of synthetic star polymer.The reactive polymer of first synthetic line style, its molecular weight and molecualr weight distribution can accurately be tested, and this evaluation for final star polymer has brought convenience.The synthesis method adopting is at present the methods such as esterification, etherificate, amidate action.For example, the people such as Song, by Williamson etherificate and hydroboration progressively, have prepared peripheral " softness " the tree core star polymer (Bull. Korean Chem. Soc. 2007,28,10,1771-1776) that is polystyrene, core and is ehter bond.In addition, the people such as Roovers utilize silane coupling agent to prepare arm number up to 200 and 270 star polyhutadiene (Macromolecules, 1989,22,1897).But coupling efficiency is too low, and product contains the shortcomings such as a certain amount of linear macromolecule, structure be imperfect.The appearance of click-reaction, make this technology also can be as arm first accurately controlled radial copolymer of synthetic molecules chain structure.
The present invention has adopted efficient click-reaction, thereby can obtain the multipolymer of non-structure defect, and obtains three arm star block copolymers with high yield.Three arm radial copolymers prepared by the present invention, there is accurately controlled molecular chain structure, be used in self-assembly in solution and form core-shell type nano-micelles, can also be used for the orderly nanophase isolating construction of microphase-separated formation rule under heating, and be further prepared into the nanometer organic porous material with regular pore structure and high-specific surface area, have broad application prospects in fields such as medicament slow release, nanometer separation.
Summary of the invention
The object of the present invention is to provide a kind of star block copolymer and preparation method thereof.
Star block copolymer provided by the present invention, the three arm star block copolymers that described star block copolymer is made up of two polystyrene chains and poly(lactic acid) or polyoxyethylene chain, wherein: the molecular weight of described polystyrene chain is 1000 ~ 50000, the molecular weight of described polylactic acid chain is 10000 ~ 40000.
In the present invention, the molecular weight of described polyoxyethylene chain is 10000 ~ 30000.
The preparation method of a kind of star block copolymer provided by the invention, concrete steps are as follows:
Two alkynyls on the polystyrene of a nitrine terminal group that contains 1.0 ~ 2.0 equivalents and 0.5 ~ 1.0 equivalent compd A, under the catalysis of 1.0 ~ 5.0 equivalent sodium ascorbate/1.0 ~ 5.0 equivalent copper sulfate systems or 1.0 ~ 5.0 equivalent five methyl diethylentriamine/1.0 ~ 5.0 equivalent cuprous bromide systems, 25 ℃ ~ 45 ℃ reactions 10 ~ 40 hours, obtain the two arm polystyrene of central point with a hydroxyl; Under 2.0 ~ 10 equivalent DMAP catalytic conditions, the hydroxyl of central point and 2.0 ~ 10 equivalent 4-pentynoic acids are changed into alkynyl by esterification; Finally; under the catalysis of 2.0 ~ 10 equivalent sodium ascorbate/2.0 ~ 10 equivalent copper sulfate systems or 2.0 ~ 10 equivalent five methyl diethylentriamine/2.0 ~ 10 equivalent cuprous bromide systems; by the alkynyl of central point and the poly(lactic acid) or the polyoxyethylene that contain a nitrine terminal group; under nitrogen protection, within 10 ~ 40 hours, react 30 ~ 60 ℃ of reactions; concentrated solvent; with methanol extraction, filter and vacuum-drying, obtain three described arm star block copolymers.
In the present invention, the structural formula of described compd A is as follows:
In the present invention, the molecular weight of the described polystyrene that contains a nitrine terminal group is 1000 ~ 50000.
In the present invention, the molecular weight of the described poly(lactic acid) that contains a nitrine terminal group is 10000 ~ 40000.
In the present invention, the molecular weight of the described polyoxyethylene that contains a nitrine terminal group is 10000 ~ 30000.
The invention has the advantages that: adopted efficient click-reaction, thereby can obtain the multipolymer of non-structure defect, and obtained three arm star block copolymers with high yield.Three arm radial copolymers prepared by the present invention, there is accurately controlled molecular chain structure, be used in self-assembly in solution and form core-shell type nano-micelles, can also be used for the orderly nanophase isolating construction of microphase-separated formation rule under heating, and be further prepared into the nanometer organic porous material with regular pore structure and high-specific surface area, have broad application prospects in fields such as medicament slow release, nanometer separation.
Accompanying drawing explanation
Fig. 1: the structural representation of three arm star block copolymers prepared by the present invention;
Fig. 2: the three arm star block copolymers of preparing for embodiment 1
1h-NMR collection of illustrative plates.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for the present invention is described.The implementation condition adopting in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
embodiment 1
Take molecular weight and be 10000 the polystyrene 8.0g that contains a nitrine terminal group, compd A 86.5mg, sodium ascorbate 0.45g, copper sulfate 1.05g, is dissolved in the mixed solvent of tetrahydrofuran (THF)/water composition normal-temperature reaction 24 hours, remove organic solvent under reduced pressure, with methanol extraction, filter and vacuum-drying, obtain the two arm polystyrene of central point with a hydroxyl; This central point is dissolved in methylene dichloride with two arm polystyrene of a hydroxyl, adds 0.5g DMAP and 0.3g 4-pentynoic acid, normal-temperature reaction 10 hours.Remove methylene dichloride under reduced pressure, with methanol extraction, filter and vacuum-drying, obtain the two arm polystyrene of central point with an alkynyl; Get the two arm polystyrene of this central point with an alkynyl; molecular weight is 15000 the poly(lactic acid) that contains a nitrine terminal group; be dissolved in tetrahydrofuran solvent; under nitrogen protection, react 24 hours at 40 ℃; concentrated solvent, with methanol extraction, filters and vacuum-drying; obtain the three arm star block copolymers containing two polystyrene chains and a polylactic acid chain, its molecular weight is 35000.
embodiment 2
Take molecular weight and be 20000 the polystyrene 6.0g that contains a nitrine terminal group, compd A 32.4mg, sodium ascorbate 0.23g, copper sulfate 0.53g, is dissolved in the mixed solvent of tetrahydrofuran (THF)/water composition normal-temperature reaction 36 hours, remove organic solvent under reduced pressure, with methanol extraction, filter and vacuum-drying, obtain the two arm polystyrene of central point with a hydroxyl; This central point is dissolved in methylene dichloride with two arm polystyrene of a hydroxyl, adds 0.32g DMAP and 0.21g 4-pentynoic acid, normal-temperature reaction 24 hours.Remove methylene dichloride under reduced pressure, with methanol extraction, filter and vacuum-drying, obtain the two arm polystyrene of central point with an alkynyl; Get the two arm polystyrene of this central point with an alkynyl; molecular weight is 23000 the poly(lactic acid) that contains a nitrine terminal group; be dissolved in tetrahydrofuran solvent; under nitrogen protection, react 20 hours at 60 ℃; concentrated solvent, with methanol extraction, filters and vacuum-drying; obtain the three arm star block copolymers containing two polystyrene chains and a poly(lactic acid), its molecular weight is 63000.
embodiment 3
Take molecular weight and be 15000 the polystyrene 10.0g that contains a nitrine terminal group, compd A 72.0mg, sodium ascorbate 0.43g, copper sulfate 0.98g, is dissolved in the mixed solvent of tetrahydrofuran (THF)/water composition, 40 ℃ of reactions 20 hours, remove organic solvent under reduced pressure, with methanol extraction, filter and vacuum-drying, obtain the two arm polystyrene of central point with a hydroxyl; This central point is dissolved in methylene dichloride with two arm polystyrene of a hydroxyl, adds 0.75g DMAP and 0.68g 4-pentynoic acid, normal-temperature reaction 36 hours.Remove methylene dichloride under reduced pressure, with methanol extraction, filter and vacuum-drying, obtain the two arm polystyrene of central point with an alkynyl; Get the two arm polystyrene of this central point with an alkynyl; molecular weight is 12000 the polyoxyethylene that contains a nitrine terminal group; be dissolved in tetrahydrofuran solvent; under nitrogen protection, react 32 hours at 50 ℃; concentrated solvent, with methanol extraction, filters and vacuum-drying; obtain the three arm star block copolymers containing two polystyrene chains and a polyoxyethylene, its molecular weight is 42000.
embodiment 4
Take molecular weight and be 18000 the polystyrene 5.0g that contains a nitrine terminal group, compd A 30mg, sodium ascorbate 0.63g, copper sulfate 1.25g, is dissolved in the mixed solvent of tetrahydrofuran (THF)/water composition, 35 ℃ of reactions 36 hours, remove organic solvent under reduced pressure, with methanol extraction, filter and vacuum-drying, obtain the two arm polystyrene of central point with a hydroxyl; This central point is dissolved in methylene dichloride with two arm polystyrene of a hydroxyl, adds 0.65g DMAP and 0.96g 4-pentynoic acid, normal-temperature reaction 18 hours.Remove methylene dichloride under reduced pressure, with methanol extraction, filter and vacuum-drying, obtain the two arm polystyrene of central point with an alkynyl; Get the two arm polystyrene of this central point with an alkynyl; molecular weight is 20000 the polyoxyethylene that contains a nitrine terminal group; be dissolved in tetrahydrofuran solvent; under nitrogen protection, react 42 hours at 35 ℃; concentrated solvent, with methanol extraction, filters and vacuum-drying; obtain the three arm star block copolymers containing two polystyrene chains and a polyoxyethylene, its molecular weight is 56000.
Above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations that spirit is done according to the present invention or modification, within all should being encompassed in protection scope of the present invention.
Claims (6)
1. a star block copolymer, is characterized in that: the three arm star block copolymers that described star block copolymer is made up of two polystyrene chains and poly(lactic acid) or polyoxyethylene chain; Wherein: the molecular weight of described polystyrene chain is 1000 ~ 50000, the molecular weight of described polylactic acid chain is 10000 ~ 40000, and the molecular weight of described polyoxyethylene chain is 10000 ~ 30000.
2. the preparation method of a star block copolymer as claimed in claim 1, it is characterized in that concrete steps are as follows: two alkynyls on the polystyrene of a nitrine terminal group that contains 1.0 ~ 2.0 equivalents and 0.5 ~ 1.0 equivalent compd A, under the catalysis of 1.0 ~ 5.0 equivalent sodium ascorbate/1.0 ~ 5.0 equivalent copper sulfate systems or 1.0 ~ 5.0 equivalent five methyl diethylentriamine/1.0 ~ 5.0 equivalent cuprous bromide systems, 25 ℃ ~ 45 ℃ reactions 10 ~ 40 hours, obtain the two arm polystyrene of central point with a hydroxyl; Under 2.0 ~ 10 equivalent DMAP catalytic conditions, the hydroxyl of central point and 2.0 ~ 10 equivalent 4-pentynoic acids are changed into alkynyl by esterification; Finally; under the catalysis of 2.0 ~ 10 equivalent sodium ascorbate/2.0 ~ 10 equivalent copper sulfate systems or 2.0 ~ 10 equivalent five methyl diethylentriamine/2.0 ~ 10 equivalent cuprous bromide systems; by the alkynyl of central point and the poly(lactic acid) or the polyoxyethylene that contain a nitrine terminal group; under nitrogen protection, within 10 ~ 40 hours, react 30 ~ 60 ℃ of reactions; concentrated solvent; with methanol extraction, filter and vacuum-drying, obtain three described arm star block copolymers.
3. the preparation method of a kind of segmented copolymer according to claim 2, is characterized in that the structural formula of described compd A is as follows:
4. the preparation method of a kind of segmented copolymer according to claim 2, is characterized in that the molecular weight of the described polystyrene that contains a nitrine terminal group is 1000 ~ 50000.
5. the preparation method of a kind of segmented copolymer according to claim 2, is characterized in that the molecular weight of the described poly(lactic acid) that contains a nitrine terminal group is 10000 ~ 40000.
6. the preparation method of a kind of segmented copolymer according to claim 2, is characterized in that the described polyoxyethylated molecular weight that contains a nitrine terminal group is 10000 ~ 30000.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104672138A (en) * | 2015-02-13 | 2015-06-03 | 中国科学院长春光学精密机械与物理研究所 | Red light emission type cationic framework two-dimensional crystalline state organic porous material and preparation method thereof |
| WO2020006721A1 (en) * | 2018-07-04 | 2020-01-09 | 南通纺织丝绸产业技术研究院 | High-grafting density cyclic comb shaped polymer and preparation method therefor |
| CN114656651A (en) * | 2022-03-17 | 2022-06-24 | 西安交通大学 | Multi-arm star-shaped polymer assembled micelle and preparation method thereof |
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| CN102634032A (en) * | 2012-03-02 | 2012-08-15 | 中国科学院上海有机化学研究所 | Polymethylene-based star polymer, preparation method and application of polymethylene-based star polymer |
| US20130030120A1 (en) * | 2011-07-25 | 2013-01-31 | Zhiqun Lin | Amphiphilic multi-arm copolymers and nanomaterials derived therefrom |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672138A (en) * | 2015-02-13 | 2015-06-03 | 中国科学院长春光学精密机械与物理研究所 | Red light emission type cationic framework two-dimensional crystalline state organic porous material and preparation method thereof |
| WO2020006721A1 (en) * | 2018-07-04 | 2020-01-09 | 南通纺织丝绸产业技术研究院 | High-grafting density cyclic comb shaped polymer and preparation method therefor |
| US11905378B2 (en) | 2018-07-04 | 2024-02-20 | Soochow University | High-grafting density cyclic comb shaped polymer and preparation method therefor |
| CN114656651A (en) * | 2022-03-17 | 2022-06-24 | 西安交通大学 | Multi-arm star-shaped polymer assembled micelle and preparation method thereof |
| CN114656651B (en) * | 2022-03-17 | 2024-05-07 | 西安交通大学 | Multi-arm star polymer assembled micelle and preparation method thereof |
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