CN100549068C - Utilize the method for cyclodextrin separating and purifying different end group polymer - Google Patents
Utilize the method for cyclodextrin separating and purifying different end group polymer Download PDFInfo
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- CN100549068C CN100549068C CNB2006101160291A CN200610116029A CN100549068C CN 100549068 C CN100549068 C CN 100549068C CN B2006101160291 A CNB2006101160291 A CN B2006101160291A CN 200610116029 A CN200610116029 A CN 200610116029A CN 100549068 C CN100549068 C CN 100549068C
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Abstract
A kind of method of utilizing the cyclodextrin separating and purifying different end group polymer of chemical technology field, be specially: with mol ratio is that 1: 99～99: 1 the polymkeric substance with different end group joins in the 1% saturated cyclodextrin soln, make that the mol ratio of polymkeric substance repeated structural unit and cyclodextrin is 10: 1～1: 10, stir, filter out the white precipitate that forms in the recombination process; Wash product with water, remove not compound cyclodextrin and polymkeric substance, obtain crystalline composites; Urea is joined in the hot solution of crystalline composites, destroy the hydrogen bond network of mixture, use dichloromethane extraction then, the polymkeric substance that can purify behind the evaporate to dryness; Repeat said process 1～2 time, just can obtain complete purified polymer.The method of the present invention by kinetic control realized that easily the separation of bulk properties and similar polymerization thing thereof purifies, and the object cyclodextrin that is adopted is nontoxic and can be recycled.
Description
Technical field
The present invention relates to a kind of method of chemical technology field, specifically is a kind of method of utilizing the cyclodextrin separating and purifying different end group polymer.
Background technology
The polymkeric substance that structure is clear and definite has specific physicochemical property, thereby has extensively and important use at aspects such as medicine, biology, industry.To polymer architecture emphasize impel also that people constantly find better to separate with research, the method for purified polymer.
The isolating main method of polymkeric substance all is based on whole polymer chain and exists significant difference to realize that it separates purpose at present.For example: membrane sepn realizes that with the difference that gel permeation chromatography is based on whole polymer chain size it separates; High pressure extraction is based on whole polymer chain polarity difference and realizes its separation; It is different next isolating that gel electrophoresis is based on isoelectric point of protein.
Find that through literature search the separation of the polymkeric substance of different end group is difficulty particularly, has only a small amount of report at present to prior art.Xulin Jiang etc. are at " Journal of Chromatography A " (chromatographic science magazine A, 2003,1018 the volume, 19～27 pages) on delivered " Robust isocratic liquidchromatographic separation of functional poly (methyl methacrylate) " (utilizing critical liquid chromatography effectively to separate the polymethylmethacrylate of different functionality).This article has proposed to utilize critical liquid chromatography technology to separate the polymkeric substance with different end group, concrete grammar is to consider between silicagel column and the polar functional group to have interaction, functional group's number difference, it is also just different to interact, therefore can seek critical condition by the variation that changes moving phase component and proportioning, finally successfully separate the polymethylmethacrylate that end has different hydroxy number (0,1 and 2 hydroxyl).Although this technology can be separated some particular polymers with different end group, the optimization of solvent, pillar, detector and test condition is chosen and is made that still this separation purification is very complicated.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of method of utilizing the cyclodextrin separating and purifying different end group polymer is provided.The difference that the present invention utilizes cyclodextrin and different end group polymer composite power to learn comes separation and purification to contain the polymkeric substance of various ends, cyclodextrin and polymkeric substance form crystallization easily and include mixture, the terminal difference of polymkeric substance, the speed that mixture forms has very big-difference.Therefore, can utilize cyclodextrin to separate polymkeric substance with different end group.Used cyclodextrin nontoxicity among the present invention can be recycled.
The present invention is achieved by the following technical solutions, and concrete grammar of the present invention is:
With mol ratio is that 1: 99～99: 1 the polymkeric substance with different end group joins in the 1% saturated cyclodextrin soln, make that the mol ratio of polymkeric substance repeated structural unit and cyclodextrin is 10: 1～1: 10, stir, filter out the white precipitate that forms in the recombination process;
Wash product with water, remove not compound cyclodextrin and polymkeric substance, obtain crystalline composites;
Urea is joined in the hot solution of crystalline composites, destroy the hydrogen bond network of mixture, use dichloromethane extraction then, the polymkeric substance that can purify behind the evaporate to dryness;
Repeat said process 1～2 time, just can obtain complete purified polymer.
Described extraction with the cyclodextrin soln washed with dichloromethane that produces in its process, is removed remaining polymkeric substance, and solution filters the back evaporate to dryness, the gained solid matter with absolute ethanol washing for several times, the urea that flush away is residual can be realized the recovery of cyclodextrin after the oven dry.Reclaim efficiency of pcr product height, purity height.
Polymkeric substance with different end group of the present invention comprises: the polymkeric substance that molecular structure is identical, molecular weight is identical, end group is different; The polymkeric substance that molecular structure is identical, molecular weight is different, end group is different; Molecular structure difference, the polymkeric substance that molecular weight is identical, end group is different; Molecular structure difference, molecular weight difference, the different polymkeric substance of end group.
The used cyclodextrin of the present invention is a kind of in alpha-cylodextrin, beta-cyclodextrin and the γ-Huan Hujing.
The present invention has utilized cyclodextrin to separate the extremely close polymkeric substance of bulk properties with the difference that the different end group polymer composite power is learned, and principle is clear and definite, simple, widely applicable, is expected to obtain practical application in polymkeric substance separates.Selected object cyclodextrin nontoxicity, can be recycled, also provide reference simultaneously for adopting other Subjective and Objective system to separate similar polymer.
Description of drawings
Fig. 1: the recombination rate figure of different end polymers and cyclodextrin in the example 1.
Fig. 2: resulting crystalline composites (DMSO-d in example 1 purge process
6Make solvent) and purified product (CDCl
3Make solvent)
1H NMR spectrum.
Embodiment
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: with alpha-cylodextrin separate the polyethylene oxide derivant that the purification end group is respectively propionyloxy and carboxyl (PEG, Mn=2000).
Step (a): stir down at 25 ℃, with 0.376g (18.8mmol) end group is that the aqueous solution of the polyethylene oxide derivant (P2C3 and P2COOH) of propionyloxy or carboxyl joins respectively in the aqueous solution of alpha-cylodextrin, adopt spectrophotometer that their turbidity is carried out record, thereby reflect its recombination rate.Fig. 1 is the recombination rate curve that is write down.Then the P2C3 of 0.376g (18.8mmol) and the P2COOH of 0.376g (18.8mmol) are joined (P2C3: P2COOH=1: 1) in the 50mL water.Fully after the dissolving, at room temperature this solution is joined in the aqueous solution of alpha-cylodextrin (alpha-cylodextrin of 3.76g is dissolved in the water of 50mL).Stop after 6 hours stirring, have a large amount of white precipitates to separate out.Filter, wash product with water for several times, remove not compound cyclodextrin and polymkeric substance, thereby obtain the crystalline composites IC1 of PEG derivative.Fig. 2 is resulting a series of products in the purge process
1H NMR spectrogram.Wherein IC1 is that resulting crystalline composites is at DMSO-d
6In
1H NMR.In the drawings, the 4.09ppm place is positioned on the PEG-CH for P2C3
2Triple characteristic peaks of OOC-; And the 3.99ppm place is positioned on the PEG-OCH for P2COOH
2The substance characteristic peak of CO-.Can calculate P2C3 and P2COOH is about 92: 8 in the ratio that this includes in the mixture according to integral area.
Step (b): the crystalline composites 2.01g that obtains is dissolved in the water of 200mL, adds 1g urea down and stirred the hydrogen bond network of destruction mixture 12 hours at 40 ℃ then.Treat to add again behind the solution cool to room temperature HCl of several dilutions, use anhydrous magnesium sulfate drying again for several times with dichloromethane extraction.Organic layer is concentrated the back precipitate with anhydrous diethyl ether, resulting product is the derivative M1 that frees from mixture.M1 among Fig. 2 is that the PEG derivative is at CDCl
3In
1H NMR.4.22ppm and 4.15ppm is respectively P2C3 and P2COOH at CDCl
3In corresponding characteristic peak, hydrogen spectrum data illustrate that also alpha-cylodextrin does not exist in this derivative simultaneously.P2C3 and P2COOH ratio in this derivative still are 92: 8 as can be known according to integral area.
Step (c): the above-mentioned derivative 100mg that obtains is dissolved in the water of 6.7mL, joins then in the aqueous solution of cyclodextrin (alpha-cylodextrin of 0.5g is dissolved in the water of 6.7mL), stop after 6 hours stirring.Can obtain the crystalline composites IC2 of PEG derivative by the purification process similar to step (a).IC2 is that the gained crystalline composites is at DMSO-d among Fig. 2
6In
1H NMR.In the drawings, the substance characteristic peak completely dissolve of the P2COOH of 3.99ppm place only stays the triple characteristic peaks at the P2C3 of 4.09ppm place.Thereby can find out, under kinetic control, realize substantially the separation of different PEG derivatives is purified.
Step (d): O.2g the crystalline composites that will obtain once more is dissolved in the water of 20mL, at 40 ℃ of urea that add 0.1g down, stirs 12 hours then.Adopt and the similar treatment process of step (b), can not contained the pure P2C3 of cyclodextrin and other impurity.M2 is that gained PEG derivative is at CDCl among Fig. 2
3In
1H NMR.In the drawings, triple characteristic peaks of P2C3 are only arranged at the 4.22ppm place, illustrate and have only P2C3a hydrogen spectrum to illustrate that also alpha-cylodextrin comes off fully simultaneously in the purified product.So far, the separation that has realized different end group PEG derivative is fully purified.
With the aqueous solution of the enrichment cyclodextrin of step (b) in the example 1 and step (d) gained for several times, remove remaining PEG derivative, then filtering solution and with the complete evaporate to dryness of water with washed with dichloromethane.The solid matter of gained is removed unnecessary urea with absolute ethanol washing for several times, at last 80 ℃ of oven dry, just can realize the recovery to alpha-cylodextrin.Reclaim productive rate greater than 95%.
Embodiment 2: with alpha-cylodextrin separate the purification polyethylene oxide (PEG, Mn=2000) and end group be the polyethylene oxide derivant (P2C6) of hexylyloxy.
Stir down at 25 ℃, the aqueous solution of the polyethylene oxide derivant (P2C6) that polyethylene oxide (PEG) and the end group of 0.376g (18.8mmol) is hexylyloxy joins respectively in the aqueous solution of alpha-cylodextrin, adopt spectrophotometer that their turbidity is carried out record, thereby reflect its recombination rate.Then the PEG of 0.376g (18.8mmol) and the P2C6 of 0.376g (18.8mmol) are joined (PEG: P2C6=1: 1) in the 50mL water.Fully after the dissolving, at room temperature this solution is joined in the aqueous solution of alpha-cylodextrin (alpha-cylodextrin of 3.76g is dissolved in the water of 50mL).Stir the back a large amount of white precipitates of appearance and separate out, wash product after the filtration with water for several times, remove not compound cyclodextrin and polymkeric substance.The crystalline composites that obtains is dissolved in the 200mL water, adds 1g urea down and stirred the hydrogen bond network of destruction mixture 12 hours at 40 ℃ then.Treat to add again behind the solution cool to room temperature HCl of several dilutions, use anhydrous magnesium sulfate drying again for several times with dichloromethane extraction.Organic layer is concentrated the back precipitate with anhydrous diethyl ether, resulting product is the derivative that frees from mixture.Repeat one time said process, just can obtain purified P2C6.
Embodiment 3: with alpha-cylodextrin separate the polyethylene oxide derivant that the purification end group is respectively propionyloxy and carboxyl (PEG, Mn=6000).
Stir down at 25 ℃, with the 18.8mmol end group is that the aqueous solution of the polyethylene oxide derivant (P6C3 and P6COOH) of propionyloxy or carboxyl joins respectively in the aqueous solution of alpha-cylodextrin, adopt spectrophotometer that their turbidity is carried out record, thereby reflect its recombination rate.Then the P6C3 of 18.8mmol and the P6COOH of 18.8mmol are joined (P6C3: P6COOH=1: 1) in the 50mL water.Fully after the dissolving, at room temperature this solution is joined in the aqueous solution of alpha-cylodextrin (alpha-cylodextrin of 3.76g is dissolved in the water of 50mL).Stir the back a large amount of white precipitates of appearance and separate out, wash product after the filtration with water for several times, remove not compound cyclodextrin and polymkeric substance.The crystalline composites that obtains is dissolved in the 200mL water, adds 1g urea down and stirred the hydrogen bond network of destruction mixture 12 hours at 40 ℃ then.Treat to add again behind the solution cool to room temperature HCl of several dilutions, use anhydrous magnesium sulfate drying again for several times with dichloromethane extraction.Organic layer is concentrated the back precipitate with anhydrous diethyl ether, resulting product is the derivative that frees from mixture.Repeat one time said process, just can obtain purified P6C3.
Claims (2)
1, a kind of method of utilizing the cyclodextrin separating and purifying different end group polymer is characterized in that, concrete grammar is:
With mol ratio is that 1: 99～99: 1 the polymkeric substance with different end group joins in the 1% saturated alpha-cylodextrin solution, make that the mol ratio of polymkeric substance repeated structural unit and alpha-cylodextrin is 10: 1～1: 10, stir, filter out the white precipitate that forms in the recombination process;
The polymkeric substance of described different end group is one of following two kinds of forms:
A) end group is respectively the polyethylene oxide derivant of propionyloxy and carboxyl, and wherein the number-average molecular weight of polyethylene oxide is 2000 or 6000;
B) polyethylene oxide and end group are the polyethylene oxide derivant of hexylyloxy, and wherein the number-average molecular weight of polyethylene oxide is 2000;
Wash product with water, remove not compound cyclodextrin and polymkeric substance, obtain crystalline composites;
Urea is joined in the hot solution of crystalline composites, destroy the hydrogen bond network of mixture, use dichloromethane extraction then, the polymkeric substance that can purify behind the methylene dichloride phase evaporate to dryness;
Repeat said process 1～2 time, just can obtain complete purified polymer.
2, the method for utilizing the cyclodextrin separating and purifying different end group polymer according to claim 1, it is characterized in that, the described dichloromethane extraction of using, it specifically is the cyclodextrin soln washed with dichloromethane that to produce in its process, remove remaining polymkeric substance, solution filters the back evaporate to dryness, and the gained solid matter with absolute ethanol washing for several times, the urea that flush away is residual can be realized the recovery of cyclodextrin after the oven dry.
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