CN100528902C - Method for preparing hyper branched polyrotaxane based on cyclodextrin - Google Patents
Method for preparing hyper branched polyrotaxane based on cyclodextrin Download PDFInfo
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- CN100528902C CN100528902C CNB2007100471565A CN200710047156A CN100528902C CN 100528902 C CN100528902 C CN 100528902C CN B2007100471565 A CNB2007100471565 A CN B2007100471565A CN 200710047156 A CN200710047156 A CN 200710047156A CN 100528902 C CN100528902 C CN 100528902C
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Abstract
The present invention discloses a preparation method for cyclodextrin-based hyperbranched poly-rotaxane in the chemical technology field. The present invention takes use of a ''composition fist and polymerization after'' approach to combine the main polyamines monomer with the cyclodextrin in the water and then the product is added with Maikeer addition reagent for polymerization. Petroleum ether is added to get rid of deposit generated in the composition process of the free cyclodextrin. And the product is liquid-separated, cooled and dried to get hyperbranched poly-rotaxane. The hyperbranched poly-rotaxane is of a plurality of cyclodextrins. Each cyclodextrin molecule is locked by the branched point of the hyperbranched polymer to prevent the falling off of the cyclodextrin molecule. The proportion of the cyclodextrin on the polymer chain can be controlled through the adjustment of the amount of cyclodextrin. The hyperbranched poly-rotaxane is of a novel hyper-molecular structure, and can be taken as the basis for the design of other hyper-molecular system as the molecular machine. The present invention can be used in drug control release field, biological sensor field and so on.
Description
Technical field
The present invention relates to a kind of method of chemical technology field, specifically is a kind of preparation method of the hyper branched polyrotaxane based on cyclodextrin.
Background technology
Rotaxane is that a class is enclosed within by a ring molecule on the thread-like molecule of a dumbbell shaped and the inner-lock-type supramolecular system that forms.If comprise a plurality of ring molecules, then become poly-rotaxane.Poly-rotaxane is a kind of novel supramolecular structure, and this class supramolecule inclusion complex is to interact between the research biological entities and a valid model of character.Kai Fa novel intelligent material and molecular device also have the important application prospect on this basis.In addition, this system also is used to biodegradable material, pharmaceutical carrier and release, molecular recognition, chemical sensor, polymkeric substance separates and the research of direction such as molecular simulation, and great application prospect is arranged.
Find through literature search, utilize the system of the poly-rotaxane of cyclodextrin design mainly to be divided into two big classes at present prior art.One class is that simple linear polymer is direct and cyclodextrin is compound, and then carry out end-blocking with macoradical and obtain poly-rotaxane: the Harada etc. of backbone chain type at " J.Org.Chem. " (organic chemistry magazine, 1993,58 volumes, 7524～7528 pages) on delivered " Preparation and Characterization ofPolyrotaxanes Containing Many Threaded Alpha-Cyclodextrins " (synthetic and preparation) with poly-rotaxane of alpha-cylodextrin, this article carries out the polyoxyethylene glycol of alpha-cylodextrin and line style compound earlier, and then with big end-capping reagent, as 2, the 4-dinitrofluorobenzene carries out end-blocking to the accurate poly-rotaxane of macromole, has obtained poly-rotaxane.Another kind of is to obtain poly-rotaxane: the Ritter etc. of side chain type in " Angew.Chem.Int.Ed. " (German applied chemistry by simple linear polymer and the reaction of half rotaxane, nineteen ninety-five, 34 volumes, 309～311 pages) on delivered " Side-chain Polyrotaxanes with a Tandem Structure Based onCyclodextrins and a Polymethacrylate Main Chain " (based on the poly-rotaxane of the tandem type side chain of cyclodextrin and polymethyl acrylic acid main chain), this article has obtained the poly-rotaxane of side chain type by the half rotaxane reaction of line style polymethyl acrylic acid and cyclodextrin.In polymkeric substance, hyperbranched polymer is the novel important polymer of a class, and the poly-rotaxane that can have dissaving structure does not appear in the newspapers so far.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of the hyper branched polyrotaxane based on cyclodextrin is provided.The present invention is the principle of utilization " compound post polymerization earlier ", and elder generation is the compound small molecules pseudorotaxane that obtains in the aqueous solution with polyamine compounds and cyclodextrin, and then obtains hyperbranched polymer with your (Michael) addition reagent polymerization of Mike.Cyclodextrin molecular is limited on the polymer chain by the branch point of hyperbranched polymer, has therefore finally obtained a kind of poly-rotaxane that utilizes hyperbranched topological framework restriction cyclodextrin molecular to come off.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
Step a: polyamine compounds is dissolved in aqueous solution the inside, adds cyclodextrin then, stir, naturally cooling obtains the small molecules complex solution of polyamine compounds and cyclodextrin;
Step b: add Mike's that addition reagent in the above-mentioned small molecules complex solution that obtains, logical nitrogen stirs;
Step c: add excessive sherwood oil in the solution after reaction finishes, continue to stir, to remove in the solution cyclodextrin freely, meeting of free ring dextrin and sherwood oil form the small molecules mixture and produce precipitation, with the centrifugal precipitation of removing of the muddy liquid that obtains, obtain transparent two phase liquid, separatory, keep lower floor's water, lyophilize obtains pulverulent solids again.
Among the step a, described adding cyclodextrin is meant: add greater than 0 cyclodextrin to equimolar amount.
Among the step a, described stirring is meant: stirred 5 hours being higher than under 60 degrees centigrade the condition.
Among the step b, described adding Mike that addition reagent is meant: the Mike's that addition reagent that adds equimolar amount.
Among the step b, described logical nitrogen is meant: lead to and removed air, good seal in nitrogen 10-15 minute.
Among the step b, described stirring is meant: stirred at normal temperatures 3-5 minute, and be heated to 40 degrees centigrade then and continue to stir 120 hours.
Among the step c, described continuation is stirred, and its time is 3-5 hour.
Polyamine compounds of the present invention, comprise: 1-(2-amine ethyl) piperazine, quadrol, hexanediamine, N-ethylethylenediamine, N-methyl-prop diamines, diethyl triamine, triethyl tetramine, tetraethylenepentamine, five ethyl hexamines, and a kind of in other polyamines class monomer.
Mike's that addition reagent of the present invention, comprise: divinylsulfone, N, N-methylene-bisacrylamide, N, N-methylene-bis acrylate, N, N-methylene-bis Methacrylamide, N, N-methylene-bis methacrylic ester, and other diene class monomer, two acrylic monomer or methacrylate class are monomeric a kind of.
The used cyclodextrin of the present invention is a kind of in alpha-cylodextrin, beta-cyclodextrin and the γ-Huan Hujing.
Principle of the present invention is to utilize the small molecule monomer that the cavity of cyclodextrin can compound polyfunctionality, obtain the small molecules pseudorotaxane, obtain hyper branched polyrotaxane with other monomer copolymerizables then, wherein cyclodextrin molecular is pinned by the branch point of hyperbranched polymer and can not come off.
Synthetic hyper branched polyrotaxane of the present invention has novel topological framework.Because the existence of branched structure, the polymerization of this rotaxane of birdsing of the same feather flock together and one step of end-blocking finish.Therefore this type of hyper branched polyrotaxane combines the advantage of rotaxane and hyperbranched polymer, has that preparation simple (preparation and end-blocking are finished simultaneously), structure are easily transferred, rotaxane ratio height (ratio of cyclodextrin and polymkeric substance repeated structural unit can be adjusted to 100% from 0), is dissolvable in water water, has multiple function and yield height characteristics such as (can reach more than 80%).Can further design various supramolecular systems based on this, be expected to be used for fields such as biodegradable material, gene transfection, drug release, molecular recognition.
Description of drawings
Fig. 1 is the nuclear-magnetism carbon spectrum of the hyper branched polyrotaxane of the present invention's preparation.
Fig. 2 is the wide-angle x-ray diffraction figure of the hyper branched polyrotaxane of the present invention's preparation.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Step a: in 100 milliliters reaction flask, add 20 ml deionized water, add 1.297 gram γ-Huan Hujings then and make it dissolving, add 0.1292 gram 1-(2-amine ethyl) piperazine again, stirred 5 hours under 70 degrees centigrade condition, naturally cooling obtains pale yellow solution.
Step b: add 0.1182 gram divinylsulfone in the above-mentioned small molecules solution that obtains, with the sealing of turned welt plug, removed air in logical nitrogen 10-15 minute, good seal stirred 3-5 minute at normal temperatures, was heated to 40 degrees centigrade then and continued to stir 120 hours.
Step c: reaction adds 20 milliliters of sherwood oils in reaction flask after finishing again, continues at normal temperatures stir about 3-5 hour, obtains turbid solution.Centrifugal disgorging obtains limpid two phase liquid.The upper strata is excessive sherwood oil, and lower floor is the light yellow solution of hyper branched polyrotaxane.Separatory is removed excessive sherwood oil, obtains yellow powder powder solid after the aqueous phase solution lyophilize, puts into 70 degrees centigrade of vacuum drying oven oven dry 48 hours again.Productive rate: 34.9%.
Embodiment 2
Step a: add 20 ml deionized water in 100 milliliters reaction flask, add 0.0045 gram beta-cyclodextrin then and make it dissolving, add 0.1162 diamines of restraining oneself again, stirred 5 hours under 70 degrees centigrade condition, naturally cooling obtains pale yellow solution.
Step b: add 0.1542 gram methylene-bisacrylamide in the above-mentioned small molecules solution that obtains, with the sealing of turned welt plug, removed air in logical nitrogen 10-15 minute, good seal stirred 3-5 minute at normal temperatures, was heated to 40 degrees centigrade then and continued to stir 120 hours.
Step c: reaction adds 20 milliliters of sherwood oils in reaction flask after finishing again, continues at normal temperatures stir about 3-5 hour, obtains turbid solution.Centrifugal disgorging obtains limpid two phase liquid.The upper strata is excessive sherwood oil, and lower floor is the light yellow solution of hyper branched polyrotaxane.Separatory is removed excessive sherwood oil, obtains yellow powder powder solid after the aqueous phase solution lyophilize, puts into 70 degrees centigrade of vacuum drying oven oven dry 48 hours again.Productive rate: 85%.
Embodiment 3
Step a: add 20 ml deionized water in 100 milliliters reaction flask, add 0.4635 gram alpha-cylodextrin then, add 0.1292 gram 1-(2-amine ethyl) piperazine again, stirred 5 hours under 70 degrees centigrade condition, naturally cooling obtains pale yellow solution.
Step b: add 0.1542 gram methylene-bisacrylamide in the above-mentioned small molecules solution that obtains, with the sealing of turned welt plug, removed air in logical nitrogen 10-15 minute, good seal stirred 3-5 minute at normal temperatures, was heated to 40 degrees centigrade then and continued to stir 120 hours.
Step c: reaction adds 20 milliliters of sherwood oils in reaction flask after finishing again, continues at normal temperatures stir about 3-5 hour, obtains turbid solution.Centrifugal disgorging obtains limpid two phase liquid.The upper strata is excessive sherwood oil, and lower floor is the light yellow solution of hyper branched polyrotaxane.Separatory is removed excessive sherwood oil, obtains yellow powder powder solid after the aqueous phase solution lyophilize, puts into 70 degrees centigrade of vacuum drying oven oven dry 48 hours again.Productive rate: 54.2%.
The resulting product of the present invention proves its structure and character through one dimension nucleus magnetic hydrogen spectrum, one dimension nuclear-magnetism carbon spectrum, two-dimentional nuclear-magnetism, wide-angle x-ray diffraction, thermogravimetric analysis, differential heat scan and the test of solid carbon spectrum.
Embodiment the results are shown in accompanying drawing.The one dimension nuclear-magnetism carbon spectrogram spectrum of the hyper branched polyrotaxane of corresponding embodiment 1 preparation of Fig. 1, wherein, the peak of 70 to 110ppm correspondences is the carbon atoms on the cyclodextrin, the peak of 50 to 60ppm correspondences is the carbon atoms on the polysulfones amine.This collection of illustrative plates proof cyclodextrin is present in the polymer samples, and polymerisate has dissaving structure.The degree of branching of polymkeric substance can be calculated by quantitative nuclear-magnetism carbon spectrum, and the degree of branching that calculates is 0.31.The wide-angle x-ray diffraction figure of the hyper branched polyrotaxane of the respectively corresponding embodiment 1-3 preparation of Fig. 2 collection of illustrative plates 1-3.A diffuse peaks appears in the wide-angle x-ray diffraction collection of illustrative plates, illustrates that resulting polymkeric substance is an amorphous.The pipe-like or the cage shape characteristic signal that do not have cyclodextrin in the wide-angle x-ray diffraction collection of illustrative plates illustrate that cyclodextrin is a random distribution in polymkeric substance, also proved the existence of hyper branched polyrotaxane simultaneously.
Claims (3)
1. the preparation method based on the hyper branched polyrotaxane of cyclodextrin is characterized in that, may further comprise the steps:
Step a: polyamine compounds is dissolved in aqueous solution the inside, adds cyclodextrin then, stir, naturally cooling obtains the small molecules complex solution of polyamine compounds and cyclodextrin;
Described polyamine compounds is a kind of in 1-(2-amine ethyl) piperazine, quadrol, hexanediamine, N-ethylethylenediamine, N-methyl-prop diamines, diethyl triamine, triethyl tetramine, tetraethylenepentamine, the five ethyl hexamines;
Described adding cyclodextrin is meant: add greater than 0 cyclodextrin to equimolar amount;
Described stirring is meant: stirred 5 hours being higher than under 60 degrees centigrade the condition;
Step b: add Mike's that addition reagent in the above-mentioned small molecules complex solution that obtains, logical nitrogen stirs;
Described adding Mike that addition reagent is meant: the Mike's that addition reagent that adds equimolar amount;
Your addition reagent of described Mike is divinylsulfone, N,N methylene bis acrylamide, N, N-methylene-bis acrylate, N, N-methylene-bis Methacrylamide, N, a kind of in the N-methylene-bis methacrylic ester;
Described stirring is meant: stirred at normal temperatures 3-5 minute, and be heated to 40 degrees centigrade then and continue to stir 120 hours;
Step c: add excessive sherwood oil in the solution after reaction finishes, continue to stir, to remove in the solution cyclodextrin freely, meeting of free ring dextrin and sherwood oil form the small molecules mixture and produce precipitation, with the centrifugal precipitation of removing of the muddy liquid that obtains, obtain transparent two phase liquid, separatory, keep lower floor's water, lyophilize obtains pulverulent solids again;
Described continuation is stirred, and its time is 3-5 hour.
2, the preparation method of the hyper branched polyrotaxane based on cyclodextrin according to claim 1 is characterized in that, described cyclodextrin is a kind of in alpha-cylodextrin, beta-cyclodextrin and the γ-Huan Hujing.
3, the preparation method of the hyper branched polyrotaxane based on cyclodextrin according to claim 1 is characterized in that among the step b, described logical nitrogen is meant: removed air, good seal in logical nitrogen 10-15 minute.
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| CN101367993B (en) * | 2008-10-09 | 2011-04-13 | 上海交通大学 | Method for improving thermostability of propylene carbonate with cyclodextrin |
| JP5329241B2 (en) * | 2009-01-08 | 2013-10-30 | リンテック株式会社 | Crosslinked polymer and method for producing crosslinked polymer |
| CN103539951B (en) * | 2013-09-29 | 2015-10-14 | 北京化工大学 | A kind of water-soluble ultrabranching fluorescent polymer and preparation method thereof and application |
| CN115417999B (en) * | 2022-08-24 | 2023-07-07 | 浙江大学杭州国际科创中心 | One-dimensional polyrotaxane constructed based on coordination boron-nitrogen bond, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454100A (en) * | 2000-07-03 | 2003-11-05 | 株式会社日本组织工程 | Base materials for tissue regeneration, transplant materials and process for producing the same |
| WO2004059058A1 (en) * | 2002-12-23 | 2004-07-15 | Kimberly-Clark Worldwide, Inc. | High strength nonwoven web from a biodegradable aliphatic polyester |
| US6828378B2 (en) * | 2000-04-28 | 2004-12-07 | Center For Advanced Science And Technology Incubation, Ltd. | Compound comprising crosslinked polyrotaxane |
| WO2007026879A1 (en) * | 2005-09-02 | 2007-03-08 | The University Of Tokyo | Polyrotaxane-containing solution and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6828378B2 (en) * | 2000-04-28 | 2004-12-07 | Center For Advanced Science And Technology Incubation, Ltd. | Compound comprising crosslinked polyrotaxane |
| CN1454100A (en) * | 2000-07-03 | 2003-11-05 | 株式会社日本组织工程 | Base materials for tissue regeneration, transplant materials and process for producing the same |
| WO2004059058A1 (en) * | 2002-12-23 | 2004-07-15 | Kimberly-Clark Worldwide, Inc. | High strength nonwoven web from a biodegradable aliphatic polyester |
| WO2007026879A1 (en) * | 2005-09-02 | 2007-03-08 | The University Of Tokyo | Polyrotaxane-containing solution and use thereof |
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