CN102276762A - Effective and spatial-region selective synthesis method of monohydroxy and dihydroxy cyclodextrin derivatives - Google Patents
Effective and spatial-region selective synthesis method of monohydroxy and dihydroxy cyclodextrin derivatives Download PDFInfo
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Abstract
The invention is a synthetic method of monohydroxy and dihydroxy cyclodextrin derivatives, which has high efficiency and high spatial-region selectivity; 2-, 3-hydroxyls of cyclodextrin are protected by benzyls; the molar ratios of benzyl cyclodextrin, sodium hydride, and an electrophilic reagent are adjusted to be proper; when alkylation of a 'main surface' is performed, one or two hydroxyls are not alkylated and are 'exposed'; cyclodextrin 'main surface' monohydroxy non-alkylated derivatives, that is, monohydroxy cyclodextrin derivatives, or 'main surface' dihydroxy non-alkylated derivatives, that is, dihydroxy cyclodextrin derivatives are obtained by one step with high yield. The invention selects a proper electrophilic reagent and proper raw material ratios, and the yield of the monohydroxy cyclodextrin derivatives is increased to nearly 70%; the invention avoids tedious protection and de-protection steps required for obtaining mono-substituted or di-substituted products, and has certain significance on reaction strategy simplification and reaction green revolution.
Description
Technical field
The present invention relates to the cyclodextrin chemical regions and select the green preparation field of synthetic, concrete must saying is that a kind of area of space about cyclodextrin monohydroxy and dihydroxyl derivative is selected the synthetic method.
Background technology
Cyclodextrin (Cyclodextrins, CDs) be cyclomaltodextrin glucanotransferase (Cyclodextrin Glucosyl Transferase, CGTase) product of degraded starch, it is the ring compound that joins end to end and form by α-1,4 glycosidic link by D-(+)-Glucopyranose of some amount.Represent its glucose unit number with an epsilon traditionally.Wherein modal be α-, β-, γ-Huan Hujing, they have 6,7 and 8 glucose units respectively.The external form of cyclodextrin is frustum-like shape, and glucose structural unit is wherein taked unwrung chair conformation.Result as glucopyranose units 4 C 1 conformation, all primary hydroxyls of cyclodextrin all are seated a side of ring, 6 hydroxyls that are glucose unit have constituted the interarea of cyclodextrin frustum-like shape structure or have claimed interarea (narrow end), and all secondary hydroxyls are located in the opposite side of ring, promptly 2 and 3 hydroxyls have constituted the inferior face of cyclodextrin frustum-like shape structure or have claimed time face (than platyopia), and Fig. 1 has provided the structural representation of alpha-cylodextrin.
Why the modification of cyclodextrin is paid close attention to widely, is because cyclodextrin has certain chemical stability, can carry out solid and modify, and this is very important for supramolecular chemistry.Although mother body cyclodextrin possesses a cavity, can be used as the site of bound substrates or guest molecule, but be used to construct supramolecule, particularly the functionalization supramolecular aggregation then seems unable to do what one wishes, therefore, how to build various supramolecules as skeleton, just become an important topic of cyclodextrin chemistry with cyclodextrin molecular.At present, cyclodextrin still is mainly used in field of food, and is the trend that increases progressively; Next is at field of medicaments, all has every year a large amount of patents and research report to deliver; Makeup, health product, wrapping material and the analytical separation material in addition that relate to other field.Conclusion is got up, and can reach following purpose by modifying: single substitution product of cyclodextrin can increase the solubleness of cyclodextrin in water, thereby can increase cyclodextrin contains the field at medicine bioavailability.Behind biological official's energy single group replacement ground introducing cyclodextrin, can increase its activity on pharmacology.Mono-substituted cyclodextrin derivative also can be used for the synthetic of cyclodextrin dimer and oligomer.And these oligomers have stronger restraint force with respect to monomer to guest molecule.The more important thing is that single substituted cyclodextrin also can be used for manually imitating enzyme and supramolecule transmitter.
Usually, to cyclodextrin optionally modifying method can be divided three classes: (1) is the method for " clever " relatively, uses the shortest time exactly, allows hydroxyl on the direct substitution cyclodextrin of reactant.(2) method of comparison " tediously long " in order to realize optionally replacing, is carried out a series of protections and is gone to protect step hydroxyl.(3) method of " loaded down with trivial details " relatively is substituted with allowing each hydroxyl indistinction on the cyclodextrin, obtains a mixture.Then, isolate target product by the whole bag of tricks.
In the process of modification cyclodextrin, there are two importances to need to consider: the response capacity of the nucleophilicity of hydroxyl and cyclodextrin and reagent.All modifications of cyclodextrin all are to carry out on hydroxyl, because the nucleophilicity of hydroxyl self, the stereoselectivity of leading entire reaction and degree of modification (single replacement, two replacement or polysubstituted).
The present invention utilizes method efficient and that have a high spatial regioselectivity to synthesize monohydroxy and dihydroxyl cyclodextrin derivative.Earlier with benzyl protection cyclodextrin 2-; hydroxyl on the 3-position; again by regulating the molar ratio of suitable benzyl rings dextrin, sodium hydride and electrophilic reagent; to " interarea " hydrocarbylation the time; always have the not hydrocarbylation of one or two hydroxyl; " expose ", once going on foot cyclodextrin " interarea " monohydroxy both monohydroxy cyclodextrin derivative or " interarea " dihydroxyl both dihydroxyl cyclodextrin derivative of hydrocarbylation derivative not of hydrocarbylation derivative not that can obtain higher yields.Through optimizing reaction, select suitable electrophilic reagent and proportioning raw materials, the productive rate of monohydroxy cyclodextrin derivative can increase to nearly 70% thereupon.Because many hydroxyl reaction activity of cyclodextrin are weak, response difference is smaller; the present invention can find has only one or two hydroxyls not participate in the condition of nucleophilic substitution; removed from order to reach single or loaded down with trivial details protection that two substitution products need pass through and go to protect step, had the meaning of certain simplification response strategy and reaction greenization.
If on unsubstituted hydroxyl, connect carbohydrate or amino acid, just can obtain the amphoteric cyclodextrin derivative, increase its application on pharmacological research.If on unsubstituted hydroxyl, connect other ideal activity groups, can increase the application in fields such as its modification, artificial enzyme and molecular recognition at enzyme.
Summary of the invention
The object of the invention provides the area of space of a kind of monohydroxy and dihydroxyl cyclodextrin derivative and selects the synthetic green method, effectively prepares monohydroxy and dihydroxyl cyclodextrin derivative.
Concrete technical scheme of the present invention is as follows:
The present invention is that the area of space of a kind of monohydroxy and dihydroxyl cyclodextrin derivative is selected synthetic method; earlier with benzyl protection cyclodextrin 2-; hydroxyl on the 3-position; again by regulating suitable benzyl rings dextrin; the molar ratio of sodium hydride and electrophilic reagent; to " interarea " hydrocarbylation the time; always have the not hydrocarbylation of one or two hydroxyl; " expose "; once going on foot cyclodextrin " interarea " monohydroxy both monohydroxy cyclodextrin derivative or " interarea " dihydroxyl both dihydroxyl cyclodextrin derivative of hydrocarbylation derivative not of hydrocarbylation derivative not that can obtain higher yields, concrete synthesis step is as follows:
The 1st step: cyclodextrin and sodium hydride drying is crossed, be dissolved in the exsiccant dimethyl sulfoxide (DMSO), stir 30min at normal temperatures; Slowly in reaction solution, add Benzyl Chloride then, make whole reaction system stir one day one night at normal temperatures; In this process, follow the tracks of with thin-layer chromatography, after question response is complete, add entry, with glass rod high degree of agitation reaction solution, suction filtration rotates evaporate to dryness with filtrate; Separate the cyclodextrin product 1 of benzylization with column chromatography, productive rate is 90～94%;
The 2nd step: in exsiccant benzyl cyclodextrin product 1, add diacetyl oxide, reaction system is placed-35 ℃ stir down, get the trifluoromethanesulfonic acid trimethylsilyl group, after the methylene dichloride dilution with equivalent, in 30min, slowly add reaction solution, make reaction system stir 1.5h down, follow the tracks of, after question response is complete with thin-layer chromatography at-35 ℃, pour acetylizad product into saturated sodium bicarbonate, behind dichloromethane extraction, organic layer drying, rotary evaporation, product behind the evaporate to dryness separates with column chromatography, obtain the cyclodextrin product 2 of purified 6 full benzylizations of full acetylated prosposition, productive rate is 80～83%;
The 3rd step: get the cyclodextrin product 2 that the step obtains, to the mixed solution that wherein adds sodium methylate, methylene dichloride, make reaction solution stir 24h at normal temperatures, follow the tracks of, after question response is complete with thin-layer chromatography, the pH value of conditioned reaction liquid is to neutral, then reaction solution is rotated evaporate to dryness, separate, obtain purified 6 full hydroxyls 2 with column chromatography, the cyclodextrin product 3 of 3 full benzylizations, productive rate are 89～92%;
The 4th step: the molar ratio by cyclodextrin product 3, sodium hydride and halohydrocarbon is that 1:10～16:19～26 feed intake, take by weighing exsiccant cyclodextrin product 3 and purity and be 60% sodium hydride, in system, add anhydrous N, dinethylformamide stirs down at 40 ℃, and solid reactant is dissolved fully, in 20min, slowly in reaction system, add halohydrocarbon, make reaction solution stir 24h down, follow the tracks of, see whether reaction is complete with thin-layer chromatography at 40 ℃; After question response is complete, to wherein adding methyl alcohol, reaction solution is rotated evaporate to dryness, separate with column chromatography, obtain purified " interarea " monohydroxy alkyl cyclodextrin derivative 4 and " interarea " dihydroxyl alkyl cyclodextrin derivative 5, " interarea " total hydrocarbon base substituted cyclodextrin derivative 6, productive rate is respectively 65～70%, 18～22%, 10～12%;
The 5th step: to above cyclodextrin product, be NMR, ESI-MS, determine its structure.
Cyclodextrin of the present invention is α--cyclodextrin, β--cyclodextrin or γ-Huan Hujing, preceding recrystallization, the drying of needing of use.
The present invention relates to cyclodextrin 2-, the cyclodextrin of the hydroxyl full guard on the 3-position, protecting group comprises aromatic hydrocarbyl and aliphatic alkyl.
The present invention relates to the alkaline catalysts at the cyclodextrin product of 6 full benzylizations of full hydroxyl prosposition, alkali is sodium hydride, lithium aluminium hydride, sodium alkoxide.
The present invention relates at 6 full hydroxyls 2, hydrobromic ether that the halohydrocarbon of 6 hydroxy alkylene reactions of the cyclodextrin product of 3 full benzylizations is a carbon 1 to the hydrochloric ether of carbon 10 or carbon 1 to carbon 10 or carbon 1 are to the idohydrocarbon of carbon 10, alkyl refers to the straight-chain paraffin base, the alkyl of alkylene and alkynes base and tool hydrocarbyl substituent, alkylene and alkynes base, two keys, three key are in different carbochain positions.
The alkali that the present invention relates to the cyclodextrin product alkaline purification of 6 full benzylizations of full acetylated prosposition is sodium hydroxide, potassium hydroxide or sodium methylate.
The molar ratio that the present invention relates to cyclodextrin product, alkaline catalysts and the halohydrocarbon of 6 full benzylizations of full hydroxyl prosposition is 1:10～16:19～26, can obtain monohydroxy cyclodextrin derivative and dihydroxyl cyclodextrin derivative.
Advantage of the present invention: (1) utilizes method efficient and that have a high spatial regioselectivity directly to synthesize monohydroxy and dihydroxyl cyclodextrin derivative; (2) step is simplified, and by the control reaction ratio, obtains the product of regioselectivity, has removed protection and de-protected loaded down with trivial details step from; (3) obtain three kinds of products simultaneously, and main region optionally product yield is higher; (4) technology is simple grasps easily, belongs to the environmental friendliness technology.
Description of drawings
The structural representation of Fig. 1 alpha-cylodextrin.
Embodiment
Embodiment 1
The 1st step: cyclodextrin and sodium hydride drying is crossed, be dissolved in the exsiccant dimethyl sulfoxide (DMSO), stir 30min at normal temperatures; Slowly in reaction solution, add Benzyl Chloride then, make whole reaction system stir one day one night at normal temperatures; In this process, follow the tracks of with thin-layer chromatography, after question response is complete, add entry, with glass rod high degree of agitation reaction solution, suction filtration rotates evaporate to dryness with filtrate; Separate the cyclodextrin product 1 of benzylization with column chromatography, productive rate is 90～94%.
The 2nd step: in exsiccant benzyl cyclodextrin product 1, add diacetyl oxide, reaction system is placed-35 ℃ stir down; Get the trifluoromethanesulfonic acid trimethylsilyl group, after the methylene dichloride dilution with equivalent, in 30min, slowly add reaction solution, make reaction system stir 1.5h down at-35 ℃; Follow the tracks of with thin-layer chromatography, after question response is complete, pour acetylizad product into saturated sodium bicarbonate; Behind dichloromethane extraction, the organic layer drying, rotary evaporation, the product behind the evaporate to dryness separates with column chromatography, obtains the cyclodextrin product 2 of purified 6 full benzylizations of full acetylated prosposition, and productive rate is 80～83%.
The 3rd step: get the cyclodextrin product 2 that the step obtains,, make reaction solution stir 24h at normal temperatures to the mixed solution that wherein adds sodium methylate, methylene dichloride; Follow the tracks of with thin-layer chromatography, after question response was complete, the pH value of conditioned reaction liquid was to neutral; Then reaction solution is rotated evaporate to dryness, separate with column chromatography, obtain the cyclodextrin product 3 of purified 6 full benzylizations of full hydroxyl prosposition, productive rate is 89～92%.
The 4th step: the molar ratio by cyclodextrin product 3, sodium hydride and halohydrocarbon is that 1:10～16:19～26 feed intake, take by weighing exsiccant cyclodextrin product 3 and purity and be 60% sodium hydride, in system, add anhydrous N, dinethylformamide, stir down at 40 ℃, solid reactant is dissolved fully; In 20min, slowly in reaction system, add halohydrocarbon, make reaction solution stir 24h down at 40 ℃; Follow the tracks of with thin-layer chromatography, see whether reaction is complete.After question response is complete,, reaction solution is rotated evaporate to dryness to wherein adding methyl alcohol; Separate with column chromatography, obtain purified " interarea " monohydroxy alkyl cyclodextrin derivative 4 and " interarea " dihydroxyl alkyl cyclodextrin derivative 5, " interarea " total hydrocarbon base substituted cyclodextrin derivative 6; Productive rate is respectively 65～70%, and 18～22%, 8～12%.
The 5th step: to above cyclodextrin product, be NMR, ESI-MS, determine its structure.
Embodiment 2
Preparation process and method according to embodiment 1.
(1) takes by weighing dry alpha-cylodextrin and the 12g sodium hydride of crossing of 10.0g, be dissolved in 500ml exsiccant dimethyl sulfoxide (DMSO), stir 30min at normal temperatures.In 1h, slowly in reaction solution, add the 35ml Benzyl Chloride, whole reaction system is stirred one day one night down at 35 ℃; In this process, follow the tracks of with thin-layer chromatography, after question response is complete, add 500ml water, with glass rod high degree of agitation reaction solution 10min. suction filtration, filtrate is rotated evaporate to dryness.Separate the product of benzylization with column chromatography, obtain the product 25g of purified benzylization, productive rate is 94%.
(2) take by weighing 10.0g exsiccant benzyl cyclodextrin,, reaction system is placed-35 ℃ stir down to wherein adding the 300ml diacetyl oxide; Get 7.1mL trifluoromethanesulfonic acid trimethylsilyl group, after the dry methylene chloride dilution with equivalent, in 30min, slowly add reaction solution, make reaction system stir 1.5h down at-35 ℃; Follow the tracks of with thin-layer chromatography, after question response is complete, pour acetylizad product into saturated sodium bicarbonate, get dichloromethane layer, and use anhydrous magnesium sulfate drying; Then product is rotated evaporation, the product behind the evaporate to dryness separates with column chromatography, obtains the alpha-cylodextrin product 7g of purified 6 full benzylizations of full acetylated prosposition, and productive rate is 83%.
(3) take by weighing the alpha-cylodextrin product of 6 full benzylizations of full acetylated prosposition of 5g exsiccant,, make reaction solution stir 24h at normal temperatures to wherein adding 430ml 0.05M sodium methylate dichloromethane solution; Follow the tracks of with thin-layer chromatography, after question response was complete, the pH value of conditioned reaction liquid was to neutral; Then reaction solution is rotated evaporate to dryness, separate with column chromatography, obtain alpha-cylodextrin product 4.1 grams of purified 6 full benzylizations of full hydroxyl prosposition, productive rate is 92%.
(4) synthetic by 6 full hydroxyls 2, the molar ratio of the alpha-cylodextrin product of 3 full benzylizations, sodium hydride and 5-bromo-1-amylene is that 1:18:26 is when feeding intake, take by weighing the alpha-cylodextrin product of 6 full benzylizations of full hydroxyl prosposition of 1g exsiccant and 0.21g purity and be 60% sodium hydride; Add the anhydrous N of 137ml in system, dinethylformamide stirs 30min down at 40 ℃, and solid reactant is dissolved fully.In 20min, slowly in reaction system, add 1.5 mL 5-bromo-1-amylenes, make reaction solution stir 24h down at 40 ℃; Follow the tracks of with thin-layer chromatography, after question response is complete,, reaction solution is rotated evaporate to dryness to wherein adding 150ml methyl alcohol; Separate with column chromatography, obtain each 0.6,0.17,0.06 gram of purified monohydroxy cyclodextrin derivative, dihydroxyl cyclodextrin derivative and full substituted cyclodextrin derivative successively, yield respectively is 70%, 19%, 8%.To above cyclodextrin product, be NMR, ESI-MS, determine its structure.
Project is subsidized: state natural sciences fund 30870553; The International Technology collaborative project 2010DFA34370 of the Ministry of Science and Technology.
Claims (7)
1. the area of space of monohydroxy and dihydroxyl cyclodextrin derivative is selected synthetic method; it is characterized in that: earlier with benzyl protection cyclodextrin 2-; hydroxyl on the 3-position; again by regulating suitable benzyl rings dextrin; the molar ratio of sodium hydride and electrophilic reagent; to " interarea " hydrocarbylation the time; always have the not hydrocarbylation of one or two hydroxyl; " expose "; once going on foot cyclodextrin " interarea " monohydroxy both monohydroxy cyclodextrin derivative or " interarea " dihydroxyl both dihydroxyl cyclodextrin derivative of hydrocarbylation derivative not of hydrocarbylation derivative not that can obtain higher yields, concrete synthesis step is as follows:
The 1st step: cyclodextrin and sodium hydride drying is crossed, be dissolved in the exsiccant dimethyl sulfoxide (DMSO), stir 30min at normal temperatures; Slowly in reaction solution, add Benzyl Chloride then, make whole reaction system stir one day one night at normal temperatures; In this process, follow the tracks of with thin-layer chromatography, after question response is complete, add entry, with glass rod high degree of agitation reaction solution, suction filtration rotates evaporate to dryness with filtrate; Separate the cyclodextrin product 1 of benzylization with column chromatography, productive rate is 90～94%;
The 2nd step: in exsiccant benzyl cyclodextrin product 1, add diacetyl oxide, reaction system is placed-35 ℃ stir down, get the trifluoromethanesulfonic acid trimethylsilyl group, after the methylene dichloride dilution with equivalent, in 30min, slowly add reaction solution, make reaction system stir 1.5h down, follow the tracks of, after question response is complete with thin-layer chromatography at-35 ℃, pour acetylizad product into saturated sodium bicarbonate, behind dichloromethane extraction, organic layer drying, rotary evaporation, product behind the evaporate to dryness separates with column chromatography, obtain the cyclodextrin product 2 of purified 6 full benzylizations of full acetylated prosposition, productive rate is 80～83%;
The 3rd step: get the cyclodextrin product 2 that the step obtains, to the mixed solution that wherein adds sodium methylate, methylene dichloride, make reaction solution stir 24h at normal temperatures, follow the tracks of, after question response is complete with thin-layer chromatography, the pH value of conditioned reaction liquid is to neutral, then reaction solution is rotated evaporate to dryness, separate, obtain purified 6 full hydroxyls 2 with column chromatography, the cyclodextrin product 3 of 3 full benzylizations, productive rate are 89～92%;
The 4th step: the molar ratio by cyclodextrin product 3, sodium hydride and halohydrocarbon is that 1:10～16:19～26 feed intake, take by weighing exsiccant cyclodextrin product 3 and purity and be 60% sodium hydride, in system, add anhydrous N, dinethylformamide stirs down at 40 ℃, and solid reactant is dissolved fully, in 20min, slowly in reaction system, add halohydrocarbon, make reaction solution stir 24h down, follow the tracks of, see whether reaction is complete with thin-layer chromatography at 40 ℃; After question response is complete, to wherein adding methyl alcohol, reaction solution is rotated evaporate to dryness, separate with column chromatography, obtain purified " interarea " monohydroxy alkyl cyclodextrin derivative 4 and " interarea " dihydroxyl alkyl cyclodextrin derivative 5, " interarea " total hydrocarbon base substituted cyclodextrin derivative 6, productive rate is respectively 65～70%, 18～22%, 10～12%;
The 5th step: to above cyclodextrin product, be NMR, ESI-MS, determine its structure.
2. the area of space of monohydroxy according to claim 1 and dihydroxyl cyclodextrin derivative is selected synthetic method, it is characterized in that: described cyclodextrin is α--cyclodextrin, β--cyclodextrin or γ-Huan Hujing, preceding recrystallization, the drying of needing of use.
3. the area of space of monohydroxy according to claim 1 and dihydroxyl cyclodextrin derivative is selected synthetic method, it is characterized in that: relate to cyclodextrin 2-, and the cyclodextrin of the hydroxyl full guard on the 3-position, protecting group comprises aromatic hydrocarbyl and aliphatic alkyl.
4. the area of space of monohydroxy according to claim 1 and dihydroxyl cyclodextrin derivative is selected synthetic method, and it is characterized in that: relate to the alkaline catalysts at the cyclodextrin product of 6 full benzylizations of full hydroxyl prosposition, alkali is sodium hydride, lithium aluminium hydride, sodium alkoxide.
5. the area of space of monohydroxy according to claim 1 and dihydroxyl cyclodextrin derivative is selected synthetic method, it is characterized in that: relate at 6 full hydroxyls 2, hydrobromic ether that the halohydrocarbon of 6 hydroxy alkylene reactions of the cyclodextrin product of 3 full benzylizations is a carbon 1 to the hydrochloric ether of carbon 10 or carbon 1 to carbon 10 or carbon 1 are to the idohydrocarbon of carbon 10, alkyl refers to the straight-chain paraffin base, the alkyl of alkylene and alkynes base and tool hydrocarbyl substituent, alkylene and alkynes base, two keys, three key are in different carbochain positions.
6. the area of space of monohydroxy according to claim 1 and dihydroxyl cyclodextrin derivative is selected synthetic method; it is characterized in that: the alkali that relates to the cyclodextrin product alkaline purification of 6 full benzylizations of full acetylated prosposition is sodium hydroxide, potassium hydroxide or sodium methylate.
7. the area of space of monohydroxy according to claim 1 and dihydroxyl cyclodextrin derivative is selected synthetic method, it is characterized in that: relate to 6 full hydroxyls 2, the molar ratio of cyclodextrin product, alkaline catalysts and the halohydrocarbon of 3 full benzylizations is 1:10～16:19～26, can obtain monohydroxy cyclodextrin derivative and dihydroxyl cyclodextrin derivative.
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| CN103275247A (en) * | 2013-05-25 | 2013-09-04 | 浙江大学 | Method for selectively removing trimethylsilyl on site 6 of full trimethylsilyl protected cyclodextrin |
| CN110590973A (en) * | 2019-10-28 | 2019-12-20 | 滕州京腾鑫汇新材料科技有限公司 | Cyclodextrin derivatives and process for producing the same |
| CN114752106A (en) * | 2021-12-23 | 2022-07-15 | 苏州梅克兰循环科技有限公司 | Modified polystyrene foam material and recycling method thereof |
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| CN101519460A (en) * | 2009-03-20 | 2009-09-02 | 南京威尔化工有限公司 | Synthetic method for hydroxypropyl-beta-cyclodextrin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103275247A (en) * | 2013-05-25 | 2013-09-04 | 浙江大学 | Method for selectively removing trimethylsilyl on site 6 of full trimethylsilyl protected cyclodextrin |
| CN103275247B (en) * | 2013-05-25 | 2016-03-02 | 浙江大学 | The method that 6 of the complete trimethyl silicon based guard ring dextrin of a kind of selectively removing are trimethyl silicon based |
| CN110590973A (en) * | 2019-10-28 | 2019-12-20 | 滕州京腾鑫汇新材料科技有限公司 | Cyclodextrin derivatives and process for producing the same |
| CN110590973B (en) * | 2019-10-28 | 2021-11-05 | 淮北云端文化传媒有限公司 | Cyclodextrin derivatives and process for producing the same |
| CN114752106A (en) * | 2021-12-23 | 2022-07-15 | 苏州梅克兰循环科技有限公司 | Modified polystyrene foam material and recycling method thereof |
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