CN102627774A - Segmented copolymer of polyalkyl thiophene and polyoxyethylene and preparation method thereof - Google Patents
Segmented copolymer of polyalkyl thiophene and polyoxyethylene and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of functional high-molecular material, and in particular provides a segmented copolymer of polyalkyl thiophene and polyoxyethylene and preparation method thereof. Polythiophene has advantages of high charge transfer rate, narrow energy band gap, good environmental stability and easiness for moulding; and polyoxyethylene has good biocompatibility, crystallinity and processability. According to the segmented copolymer of polyalkyl thiophene and polyoxyethylene provided by the invention, the two blocks are connected together through a triazole unit, and the segmented copolymer has characteristics of one rigid end and one flexible end. Therefore, the segmented copolymer retains respective merits of the two segmented copolymer components, also has its own characteristics, such aswater-solubility, a variety of self-assembled nanostructures and low temperature workability, and has high application value in fields of solar cell, photoelectric sensor and biomedicine. The preparation method with simple process, provided by the invention can be used for preparing a similar block copolymers and has popularization and application prospect.
Description
Technical field
The invention belongs to the functional high molecule material technical field, be specifically related to a kind of segmented copolymer that gathers alkylthrophene and polyoxyethylene and preparation method thereof.
Background technology
Conductive polymers is one of heat subject of scientific research field, utilizes the polymer body heterojunction solar cell of its structure to have light weight, flexibility, low cost and other advantages, thereby has started the research and development upsurge of opto-electronic device.Conjugated polymer as conductive polymers typical case representative receives the extensive concern of domestic and international research group in recent decades, and the photoelectric properties of regulation and control conjugated polymer also become the focus that the scientific research personnel attractes attention.The photoelectric properties of conjugated polymer remove with self chemical constitution mutually outside the Pass, also receive the influence of film condensed state structure.One of important means of regulation and control film condensed state structure is that conjugated polymer is introduced block copolymer system as block, utilizes the microphase-separated of segmented copolymer and self-assembly behavior to regulate and control its structure.Thereby researcher both domestic and external accumulates in preparation and regulation and control novel block conjugated polymer and condensed state structure with sight, in the hope of obtaining best photoelectric properties.
Segmented copolymer is meant a kind of particular polymer that the polymer segment of two or more different in kind is linked to each other and forms through covalent linkage, and it can combine the advantageous property of multiple polymers, obtains relatively graceful function polymer materials of performance.In addition, owing to have the segment of two kinds of different in kinds, and connect by chemical bond, make segmented copolymer that being separated on the microcosmic can only be taken place.Utilize the microphase-separated characteristic of segmented copolymer can be self-assembled into colourful phase morphology, it is being had wide practical use aspect preparation nanoparticle, biomedicine, the drug release.Based on this, conjugated polymer is introduced block copolymer system, utilize the microphase-separated characteristic of segmented copolymer to obtain the abundant conjugated polymer condensed state of structure, and then its photoelectric properties of optimising and adjustment.
Di-block copolymer is the most basic research model in the segmented copolymer family.Mainly be divided into two kinds of rigidity-rigidity full conjugate segmented copolymer and rigid-flexible segmented copolymers based on the di-block copolymer of conjugated polymer.The method of synthesis of conjugate segmented copolymer is divided from macroscopic view and is mainly contained two kinds of macromole evocating agent method and coupling methods.The macromole evocating agent method is the domestic method for preparing the rigid-flexible segmented copolymer at present; Promptly at first through the synthetic macromole evocating agent of grignard reagent method with end group modification; And then utilizing active end group to cause another kind of monomer polymerization, the latter's typical representative reaction comprises anionoid polymerization, the regulation and control of nitrogen oxygen radical polymerization, ATRP and the reversible transferring free-radical polymerization etc. that fragmentates that adds.In addition; The coupling method that utilizes the reaction between the characteristic group who has greater activity in the basic organic chemistry that the different polymer segment is coupled together; In recent years because simple to operate, reactive behavior is high, applied range, the design and the block conjugated polymer of synthesizing new on also embody advantage gradually.Point striking (click method) is typical case's representative wherein; It can utilize, and the pass cyclization couples together two homopolymer between nitrine and the alkynyl; It is being used widely aspect preparation synthesizing new segmented copolymer, this kind method is introduced in the design of conjugation segmented copolymer also becoming irresistible trend.
At present; Lot of domestic and international research group has carried out based on the research work that gathers 3-alkylthrophene segmented copolymer; In a large number based on the block copolymer system that gathers alkylthrophene as gathering 3-hexyl thiophene-POLYACTIC ACID, gather 3-hexyl thiophene-PS, gathering successfully preparation such as 3-hexyl thiophene-polymethylmethacrylate; The preparation method mainly utilizes the macromole evocating agent method, and it is less relatively to utilize coupling method to prepare the research work of conjugation segmented copolymer.The present invention is connected the conjugated polymer Polythiophene through a striking with flexible hydrophilic high mol polyoxyethylene, be prepared into soluble conjugated segmented copolymer, has significantly improved the solvability and the structure regulating property of conjugated polymer.
Summary of the invention
The object of the present invention is to provide and a kind ofly can significantly improve the solvability of conjugated polymer and segmented copolymer that gathers alkylthrophene and polyoxyethylene of structure regulating property and preparation method thereof.
The segmented copolymer that gathers alkylthrophene and polyoxyethylene provided by the invention, number-average molecular weight are in the 6000-120000 scope, and it has following general structure:
Wherein, R is the carbon atom number greater than 3 alkyl chain, and Polythiophene block number-average molecular weight is in the 3000-20000 scope, and the molecular weight of polyoxyethylene block is in the 3000-100000 scope.
The preparation method who gathers the segmented copolymer of alkylthrophene and polyoxyethylene provided by the invention, its reaction process is as follows:
Preparing method's concrete steps are following:
(1) preparation of polyoxyethylene a (being the compound a in the above-mentioned reaction formula):
Have different molecular weight, the end capped polyoxyethylene of mono methoxy prepare according to conventional methods (can be referring to document R. Jing, G. Wang, Y. Zhang, J. Huang,
Macromolecules.
2011, 44,805);
(2) preparation of polymkeric substance b (being the compound b in the above-mentioned reaction formula):
Prepared polyoxyethylene a in the step (1) fully is dissolved in the organic solvent, and adding molar weight is the 1-10 triethylamine doubly of polyoxyethylene a, places ice-water bath; Under agitation condition, in above-mentioned solution, dropwise add the α-bromine isobutyl acylbromide with the triethylamine equivalent, stirring reaction 30 minutes to 24 hours; After reaction finished, the organic solvent water repeatedly washed, and concentrated back sedimentation in ether and obtained white polymer b;
(3) preparation of polymkeric substance c (being the compound c in the above-mentioned reaction formula):
Polymkeric substance b prepared in the step (2) is dissolved in N, and in the dinethylformamide, adding molar weight is the 1-10 sodiumazide doubly of polymkeric substance b, the above reaction of room temperature 30 minutes to 24 hours; After reaction finished, underpressure distillation removed and desolvates, and uses the organic solvent dissolution residue, and water repeatedly washs again, collected organic phase, concentrated back sedimentation in ether and obtained white polymer c;
(4) preparation of 2-bromo-5-iodo-3-hexyl thiophene (being the compound d in the above-mentioned reaction formula):
By ordinary method preparation (can be referring to document A. Yokoyama, R. Miyakoshi, T. Yokozawa,
Macromolecules.
2004, 37,1169);
(5) preparation of polymkeric substance e (being the Verbindung in the above-mentioned reaction formula):
Under protection of inert gas; Compound d is dissolved in the anhydrous tetrahydro furan; Add isopropylmagnesium chloride solution with the compound d equimolar amount; After stirring 10 minutes to 1 hour under the ice-water bath condition, rise to room temperature, be transferred to then and be equipped with 1,3-two (diphenylphosphino) propane Nickel Chloride [Ni (dppp) Cl
2] flask in, reacted 10-30 minute; And then adding the 0.1-5 ethynyl bromination magnesium doubly that molar weight is a compound d, stirring reaction is 5 minutes to 3 hours under the room temperature; Reaction is poured sedimentation in the methyl alcohol into after finishing, and sedimentation gained solid matter gets product obtains black through methyl alcohol and normal hexane washing polymkeric substance e after the filtration;
(6) preparation of target segmented copolymer:
Under protection of inert gas; Compound c that step (3) and step (5) is prepared and Verbindung are by the mixed of 1:1-10:1 and be dissolved in the THF; Adding molar weight is the cuprous bromide of the 1%-50% of polymkeric substance e; And with the pentamethyl-diethylenetriamine of cuprous bromide equivalent, 50-100 ℃ of heated and stirred reaction 1-24 hour; Crude product separates through semi-permeable membranes removes impurity, promptly obtains the black objects polymkeric substance.
Advantages such as Polythiophene has the charge mobility height, band gap is narrow, environmental stability good, preparation is easy, easy machine-shaping; Polyoxyethylene has excellent biological compatibility, crystallinity and workability.The segmented copolymer that gathers alkylthrophene and polyoxyethylene provided by the invention; Wherein two blocks are to link together through the triazole unit; Have the flexible characteristics of an end rigidity, an end, thereby, remaining with the bi-block copolymer component separately on the basis of advantage; Also have some its distinctive characteristics, but as have advantages such as water-soluble, multiple self-assembled nano structures and machining at low temperature.Study its self-assembly pattern, thermodynamics and photoelectric property in different solvents, being illustrated in solar cell, photo-sensor and biomedical sector all has very high using value.In addition, preparation method provided by the invention, technology is simple, can be used for preparing similar segmented copolymer, has popularizing application prospect.
Embodiment
Embodiment 1:Number-average molecular weight is 14730 segmented copolymer
1Synthetic, wherein the Polythiophene number-average molecular weight is 7990, the polyoxyethylene number-average molecular weight is 4970.
Step 1: number-average molecular weight is the preparation of 4970 the end capped polyoxyethylene of mono methoxy:
Subject polymer according to literature method (R. Jing, G. Wang, Y. Zhang, J. Huang,
Macromolecules.
2011, 44,805) and preparation.
Step 2: an end is with the preparation of mono methoxy end-blocking one end with acylbromide end-blocking polyoxyethylene:
In the round-bottomed flask of 250 mL, adding 15 g, to count the prepared number-average molecular weight of step 1 be 4970 monohydroxy end-blocking polyoxyethylene (3 mmol) and 100 mL toluene, with the water trap stirring toluene steamed with azeotropic water removing under 150 ℃ of conditions.After treating that solution is cooled to room temperature,, polyoxyethylene is fully dissolved, add 4.3 mL (30 mmol) triethylamine then to wherein adding anhydrous methylene chloride 150 mL.In ice-water bath, in above-mentioned solution, dropwise add 2-bromine isobutyl acylbromide 3.7 mL (30 mmol), add in 30 minutes, and stirred 24 hours.The reaction after-filtration is removed insolubles, and organic phase is collected organic phase with water washing 3 times, revolves to steam to be concentrated into sticky shape, and deposition is 3 times in anhydrous diethyl ether, can get white solid 13.7 g, productive rate: 91%.
Step 3: an end is with the preparation of mono methoxy end-blocking one end with nitrine end-blocking polyoxyethylene:
Polymkeric substance prepared in the step 2 10 g (2 mmol) and sodiumazide 1.3 g (20 mmol) are dissolved in 100 mL N, and in the dinethylformamide, the lucifuge reaction is 24 hours under 50 ℃ of conditions.Reaction finishes the back and under 55 ℃ of conditions, removes solvent under reduced pressure, adds chloroform, uses water washing then 3 times.Collect organic phase, concentrate the back and in ether, precipitate 3 times, obtain white product 8.4 g, productive rate 84%, product is to photaesthesia.
The preparation of step 4:2-bromo-5-iodo-3-hexyl thiophene:
According to literature method (A. Yokoyama, R. Miyakoshi, T. Yokozawa,
Macromolecules.
2004, 37,1169) and preparation.
Step 5: the alkynyl end-blocking gathers the preparation of hexyl thiophene:
Under nitrogen protection, two mouthful round-bottomed flasks of two 150 mL are connected, add 2-bromo-5-iodo-3-hexyl thiophene 2.15 mL (10 mmol), adding anhydrous tetrahydro furan 120 mL.Above-mentioned solution is cooled off in ice-water bath; To wherein adding isopropylmagnesium chloride 5 mL (10 mmol); Rise to 35 ℃ at 0 ℃ after down stirring half a hour, and pour into and 0.1084 g (0.2 mmol) 1 is housed, 3-two (diphenylphosphino) propane Nickel Chloride [Ni (dppp) Cl
2] round bottom prop up in mouthful flask, reacted 10 minutes.Ethynyl bromination magnesium 10 mL (5 mmol) that add 0.5 M afterwards stir after 5 minutes under the room temperature and pour sedimentation in the 1000 mL methyl alcohol into, and cross and filter product, and with a large amount of methyl alcohol and normal hexane drip washing.Obtain subject polymer 1.5 g, productive rate 40% is black solid, and number-average molecular weight is 7990.
Step 6: segmented copolymer
1Preparation:
Polymkeric substance 1 g (0.125 mmol) that takes by weighing step 5 preparation places single mouth reaction flask with polymkeric substance 1.9 g (0.375 mmol) that step 3 prepares, and adds cuprous bromide 0.1 g (0.7 mmol), pentamethyl-diethylenetriamine 0.15 mL (0.7 mmol) and THF 40 mL successively.After removing oxygen, under nitrogen protection, be heated to 70 ℃, stirring reaction 24 hours.After reaction finishes, revolve to steam to remove and desolvate, use the dissolved in chloroform residuals, with water washing 3 times, collection chloroform phase with the anhydrous magnesium sulfate drying after-filtration and revolve steaming and remove chloroform, obtains crude product.Crude product is dissolved in methyl alcohol and uses the semi-permeable membranes of molecular weight cut-off 20,000 to separate remove that to obtain number-average molecular weight behind the impurity be 14730 target segmented copolymer 1.4 g.
Embodiment 2, number-average molecular weight are 19240 segmented copolymer
2Synthetic, wherein the Polythiophene number-average molecular weight is 14020, the polyoxyethylene number-average molecular weight is 4970.
Step 1: number-average molecular weight is the preparation of 4970 the end capped polyoxyethylene of mono methoxy:
Subject polymer according to literature method (R. Jing, G. Wang, Y. Zhang, J. Huang,
Macromolecules.
2011, 44,805) and preparation.
Step 2: an end is with the preparation of mono methoxy end-blocking one end with acylbromide end-blocking polyoxyethylene:
The prepared number-average molecular weight of adding 15 g steps 1 is 4970 monohydroxy end-blocking polyoxyethylene (3 mmol) and 100 mL toluene in the round-bottomed flask of 250 mL, with the water trap stirring toluene is steamed with azeotropic water removing under 150 ℃ of conditions.After treating that solution is cooled to room temperature,, polyoxyethylene is fully dissolved, add 4.3 mL (30 mmol) triethylamine then to wherein adding anhydrous methylene chloride 150 mL.In ice-water bath, in above-mentioned solution, dropwise add 2-bromine isobutyl acylbromide 3.7 mL (30 mmol), add in 30 minutes, and stirred 24 hours.The reaction after-filtration is removed insolubles, and organic phase is collected organic phase with water washing 3 times, revolves to steam to be concentrated into sticky shape, and deposition is 3 times in anhydrous diethyl ether, can get white solid 13.7 g, productive rate: 91%.
Step 3: an end is with the preparation of mono methoxy end-blocking one end with nitrine end-blocking polyoxyethylene:
Polymkeric substance 10 g (2 mmol) and sodiumazide 1.3 g (20 mmol) that step 1 among the embodiment 1 is prepared are dissolved in 100 mL N, and in the dinethylformamide, the lucifuge reaction is 24 hours under 50 ℃ of conditions.Reaction finishes the back and under 55 ℃ of conditions, removes solvent under reduced pressure, adds chloroform, uses water washing then 3 times.Collect organic phase, concentrate the back and in ether, precipitate 3 times, obtain white product 8.4 g, productive rate 84%, product is to photaesthesia.
Step 4: the alkynyl end-blocking gathers the preparation of hexyl thiophene:
Under nitrogen protection, two mouthful round-bottomed flasks of two 150 mL are connected, add 2-bromo-5-iodo-3-hexyl thiophene 2.15 mL (10 mmol), adding anhydrous tetrahydro furan 120 mL.Above-mentioned solution is cooled off in ice-water bath; To wherein adding isopropylmagnesium chloride 5 mL (10 mmol); Rise to 35 ℃ at 0 ℃ after down stirring half a hour, and pour into and 0.0650 g (0.12 mmol) 1 is housed, 3-two (diphenylphosphino) propane Nickel Chloride [Ni (dppp) Cl
2] round bottom prop up in mouthful flask, reacted 10 minutes.Ethynyl bromination magnesium 10 mL (5 mmol) that add 0.5 M afterwards stir after 5 minutes under the room temperature and pour sedimentation in the 1000 mL methyl alcohol into, and cross and filter product, and with a large amount of methyl alcohol and normal hexane drip washing.Obtain subject polymer 1.6 g, productive rate 43% is black solid, and number-average molecular weight is 14020.
Step 5: segmented copolymer
2Preparation:
Polymkeric substance 1 g (0.071 mmol) that takes by weighing step 4 preparation places single mouth reaction flask with polymkeric substance 1.1 g (0.22 mmol) that step 3 prepares, and adds cuprous bromide 0.1 g (0.7 mmol), pentamethyl-diethylenetriamine 0.15 mL (0.7 mmol) and THF 40 mL successively.After removing oxygen, under nitrogen protection, be heated to 70 ℃, stirring reaction 24 hours.After reaction finishes, revolve to steam to remove and desolvate, use the dissolved in chloroform residuals, with water washing 3 times, collection chloroform phase with the anhydrous magnesium sulfate drying after-filtration and revolve steaming and remove chloroform, obtains crude product.Crude product with a large amount of methyl alcohol drip washing, is obtained number-average molecular weight and is 19240 segmented copolymer 1.3 g.
Claims (2)
1. segmented copolymer that gathers alkylthrophene and polyoxyethylene is characterized in that number-average molecular weight is 6000-120000, and has following general structure:
Wherein, R is the alkyl that length surpasses propyl group, and Polythiophene block number-average molecular weight is 3000-20000, and the molecular weight of polyoxyethylene block is 3000-100000.
2. compound method of segmented copolymer according to claim 1 is characterized in that synthetic route is as follows:
The concrete steps of preparation are:
(1) polyoxyethylene is the preparation of the compound a in the above-mentioned reaction formula:
According to conventional methods the preparation have different molecular weight, the end capped polyoxyethylene of mono methoxy;
(2) preparation of compound b in the above-mentioned reaction formula:
Polyoxyethylene prepared in the step (1) fully is dissolved in the organic solvent, and adding molar weight is the 1-10 triethylamine doubly of polyoxyethylene, places ice-water bath; Under agitation condition, in above-mentioned solution, dropwise add the α-bromine isobutyl acylbromide with the triethylamine equivalent, stirring reaction 30 minutes to 24 hours; After reaction finished, the organic solvent water repeatedly washed, and concentrated back sedimentation in ether and obtained white polymer b;
(3) preparation of the compound c in the above-mentioned reaction formula:
Prepared compound b in the step (2) is dissolved in N, and in the dinethylformamide, adding molar weight is the 1-10 sodiumazide doubly of compound b, the above reaction of room temperature 30 minutes to 24 hours; After reaction finished, underpressure distillation removed and desolvates, and uses the organic solvent dissolution residue, and water repeatedly washs again, collected organic phase, concentrated back sedimentation in ether and obtained white compound c;
(4) 2-bromo-5-iodo-3-hexyl thiophene is the preparation of the compound d in the above-mentioned reaction formula:
Prepare 2-bromo-5-iodo-3-hexyl thiophene by ordinary method;
(5) preparation of the Verbindung in the above-mentioned reaction formula:
Under protection of inert gas; Compound d is dissolved in the anhydrous tetrahydro furan; Add isopropylmagnesium chloride solution with the compound d equimolar amount; After stirring 10 minutes to 1 hour under the ice-water bath condition, rise to room temperature, be transferred to then and be equipped with 1,3-two (diphenylphosphino) propane Nickel Chloride [Ni (dppp) Cl
2] flask in, reacted 10-30 minute; And then adding the 0.1-5 ethynyl bromination magnesium doubly that molar weight is a compound d, stirring reaction is 5 minutes to 3 hours under the room temperature; Reaction is poured sedimentation in the methyl alcohol into after finishing, and sedimentation gained solid matter filters, and products therefrom promptly obtains the Verbindung of black with methyl alcohol and normal hexane washing;
(6) preparation of target segmented copolymer:
Under protection of inert gas; The compound c that step (3) and step (5) is prepared and Verbindung mix by the part by weight of 1:1-10:1 and are dissolved in the THF; Adding molar weight is the cuprous bromide of the 1%-50% of polymkeric substance e; And with the pentamethyl-diethylenetriamine of cuprous bromide equivalent, the heated and stirred reaction is 1-24 hour more than 50-100 ℃; Crude product separates through semi-permeable membranes removes impurity, promptly obtains the black objects segmented copolymer.
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| CN105980494A (en) * | 2013-12-13 | 2016-09-28 | 阿科玛法国公司 | Method allowing the creation of nanometric structures by self-assembly of block copolymers |
| CN110137515A (en) * | 2019-04-15 | 2019-08-16 | 中山大学 | A kind of intelligent zinc-air battery of multiple response and preparation method thereof |
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| CN101104654A (en) * | 2007-07-05 | 2008-01-16 | 复旦大学 | Polymer containing multiple functional groups at end of the same and preparation method thereof |
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| CN105980494A (en) * | 2013-12-13 | 2016-09-28 | 阿科玛法国公司 | Method allowing the creation of nanometric structures by self-assembly of block copolymers |
| CN110137515A (en) * | 2019-04-15 | 2019-08-16 | 中山大学 | A kind of intelligent zinc-air battery of multiple response and preparation method thereof |
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Application publication date: 20120808 |