CN108034010A - A kind of environment-friendly preparation method thereof of hydroxypropyl cyclodextrin - Google Patents
A kind of environment-friendly preparation method thereof of hydroxypropyl cyclodextrin Download PDFInfo
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- CN108034010A CN108034010A CN201711472902.5A CN201711472902A CN108034010A CN 108034010 A CN108034010 A CN 108034010A CN 201711472902 A CN201711472902 A CN 201711472902A CN 108034010 A CN108034010 A CN 108034010A
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- cyclodextrin
- hydroxypropyl
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- hydroxypropyl cyclodextrin
- friendly preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
Abstract
This application involves a kind of preparation method of hydroxypropyl cyclodextrin, the etherification derivative preparing technical field of category organic high molecular compound cyclodextrin.The technical problems to be solved by the invention are to provide the preparation method of a kind of efficient and environmentally friendly hydroxypropyl cyclodextrin, this method operating time is short, high income, cost are low, pollute small, suitable for industrial production application, the hydroxypropyl cyclodextrin impurity content of preparation is low, substitution value narrow range, suitable for food, medicine, cosmetics, agricultural, environmental protection and industrial application.
Description
Technical field
The present invention relates to a kind of preparation method of hydroxypropyl cyclodextrin.Belong to the etherificate of organic high molecular compound cyclodextrin
Derivative preparing technical field.
Background technology
The supramolecular chemistry of host-guest interaction is studied, the Nobel Prize was competed for a championship in twice at past 30 years, is presented strong
The growth momentum of strength.1987, Nobel chemistry Prize authorize J.M.Lehn (Strasbourg, FRA university),
Tri- chemists of C.J.Pedersen, D.J.Cram, with their initiatives in terms of the basic theory of supramolecular chemistry of commendation
Work；2016, Nobel chemistry Prize was presented to J.P.Sauvagen (Strasbourg, FRA university), J.F.Stoddart
(Northwestern Univ USA), B.L.Feringa (Groningen ,Holland university), with their molecule machines in host-guest chemistry of commendation
The outstanding contribution in field.Cyclodextrin is raw as one of supramolecular chemistry host molecule, affordable naturally extensive with its source
Thing is compatible good, inclusion scope it is wide, be oversubscription subdomains generally acknowledge be most hopeful agent structure.
The mother body cyclodextrin of technical scale metaplasia production at present has three kinds of α, β, gamma-cyclodextrin, respectively by 6,7,8 D- pyrans
Glucose unit joins end to end cyclic and obtains.Hydroxypropyl cyclodextrin is the etherification derivative of cyclodextrin.The introducing of hydroxypropyl is opened
Hydrogen bond in cyclodextrin molecular, forms amorphous mixture, while retainer body cavity structure, water solubility greatly improves.
Solubility is low in water and has haemocylolysis for the beta-cyclodextrin of production scale maximum at present, thus limit its using hydroxypropyl-
The dissolved solution degree ＞ 50% of beta-cyclodextrin, as its concentration ＜ 40%, good fluidity is not sticky；To light and thermally stable, it is resistant to
By 80 DEG C, 4500lux illumination 10 days；Its aqueous solution hot pressing sterilizes, and stablizes in alkaline medium；Small toxicity, the base in human body
This metabolism that is not decomposed, does not accumulate, and the oral overwhelming majority is excreted with excrement, and parenterai administration is substantially all to discharge with urine
In vitro；Hydroxypropyl-β-cyclodextrin is lower than beta-cyclodextrin hemolytic activity, and use is safer.Hydroxyproply-α-cyclodextrin and hydroxypropyl-
The dissolved solution degree ＞ 50% of gamma-cyclodextrin is significantly larger than simple alpha-cyclodextrin and gamma-cyclodextrin, and again can be with by inclusion compound
Generate crystalline deposit.
Hydroxyproply-α-cyclodextrin, molecular formula C36H60O30(C3H6O)X, molecular weight 973+58X (X is substitution value), chemistry knot
Structure formula is as follows：
Hydroxypropyl-β-cyclodextrin, molecular formula C42H70O35(C3H6O)X, molecular weight 1135+58X (X is substitution value), chemistry knot
Structure formula is as follows：
Hydropropyl-y-cyclodextrin, molecular formula C48H80O40(C3H6O)X, molecular weight 1297+58X (X is substitution value), chemistry
Structural formula is as follows：
The average of substituted hydroxyl is referred to as substitution value (DS) in hydroxypropyl cyclodextrin molecule, is evaluation product quality
An important indicator.To enter《Chinese Pharmacopoeia》Hydroxypropyl-β-cyclodextrin exemplified by, at present research think that average substitution degree exists
When between 4.0-6.0, its best results as pharmaceutic adjuvant application.Substitution value scope is narrower, illustrate generation hydroxy propyl-Beta-
The property of cyclodextrin is more close, and quality is more stable.
PithaJosef etc. reports hydroxypropyl in open publication (CarbohydrateResearch1990,200,429.)
Cyclodextrin synthetic method.Use the NaOH aqueous solutions of 1.5%-30%, H2SO4Neutralize, after 95% ethanol removes neutralization
Na2SO4 salt.Which uses a large amount of organic solvent ethanol, it is uneconomical also not environmentally.
Hao Aiyou etc. delivers a hydroxypropyl-β-cyclodextrin synthesis in open publication (chemical reagent 1995,17,161)
The article of method.This method is reacted using 1.5%NaOH aqueous solutions cyclodextrin and propylene oxide, in HCl and NaOH, N, N- bis-
Methylformamide dissolves desalination mode.This method requires reaction condition control difficulty big, and uses a large amount of organic solvent N, N- bis-
Methylformamide dissolves.
Zhao Yulin etc. reports a kind of preparation method in open publication (Yunnan chemical 2005,9.).It is water-soluble using NaOH
Liquid, epoxychloropropane are reacted with cyclodextrin, prepared by ethanol dissolving desalination mode.This method uses more expensive raw material epoxy chloropropionate
Alkane, and use a large amount of organic solvent ethanol, it is uneconomical also not environmentally.
Li Ping is in University Of Tianjin's academic dissertation (master, University Of Tianjin, 2007), with 30%NaOH aqueous solutions, epoxy third
Alkane and cyclodextrin ice-water bath conditioned response, HCl are neutralized, prepared by n,N-Dimethylformamide dissolving desalination.The big energy of this method temperature difference
Consumption is high, and it is more to produce organic solvent.
Yuan is superfine, and in open publication (Food Science 2007,147.), with 18%NaOH solution reactions, hydrochloric acid neutralizes,
It is prepared by dialysis desalination mode.This method yield is very low, and only 61.8%.
The method disclosed in Chinese patent (CN101481428A and CN101519460A) such as Li Qinghua, in autoclave
Middle 0-0.6Mpa, cyclodextrin, propylene oxide, basic catalyst and water feed intake in proportion, 50-90 DEG C reaction, after neutralize, mistake
Filter.Ethanol washs, acetone extract, dialyses and hydroxypropyl-β-cyclodextrin is made.This method is high using high-pressure bottle security risk, makes
It is low with a large amount of ethanol, acetone and other organic solvent, environmental-friendly degree.
Zheng Li just waits a kind of hydroxypropyl-β-cyclodextrin of substitution value 4-6 disclosed in Chinese patent (CN102558394B)
Production method, using water as solvent, NaOH or KOH are aqueous slkali, and beta-cyclodextrin is reacted with propylene oxide.After, hydrochloric acid neutralizes,
Nanofiltration removes inorganic salts.Being used this method avoid organic solvent has very big productive potentialities, but nanofiltration process can actually consume
A large amount of pure water, and produce a large amount of high-salt wastewaters.
A kind of substitution value 4.8-5.0 hydroxy propyl-Betas disclosed in Chinese patent (CN102040675B) such as Hu Limin-ring paste
Refined Preparation Method, including six etherificate neutralization, decoloration, nanofiltration, purifying resin, spray drying steps.In further having refined
Method in state's patent (CN102558394B).Shortcoming is still that nanofiltration consumes a large amount of pure water, produces a large amount of high-salt wastewaters.Environmental protection
Processing pressure is big.
For Li Yuntao etc. in open publication (China's brewing 2012,65), optimization process obtains 30 DEG C of technological reaction temperature, anti-
40h, NaOH concentration 10% between seasonable, the substitution value that HP- β-CD are made in technological parameter accordingly is 4.1090, yield 81.29%.Receive
Rate is relatively low.
Fan Baomin etc. is in open publication (Beijing University of Chemical Technology's journal (natural science edition) 2014,41,53) with epoxy third
Alkane synthesize hydroxypropyl-β-cyclodextrin slurry for raw material in alkaline environment, and using absolute ethyl alcohol to its desalination, using third under normal pressure
Acrylamide high hydroscopic resin carries out underflow dehydration cycle to substitute original decompression water removal device, obtains solid after dry, produces
Rate is 65.23%.This method yield is relatively low, and consumes a large amount of absolute ethyl alcohols, is unfavorable for amplification production.
The preparation basic process for hydroxypropyl cyclodextrin such as document above, patent is：1st, NaOH or KOH bucks system ring
Dextrin and propylene oxide react, and in 2, inorganic acid hydrochloric acid or sulfuric acid and NaOH or KOH, produce by-product inorganic salts, 3, organic solvent,
Resin, dialysis, nanofiltration remove inorganic salts, 4, dehydrate to obtain product.Also other similar to this process document patent, no longer
Repeat one by one.How efficiently the removal inorganic salts of environmental protection, be to mass produce the key that hydroxypropyl derives cyclodextrin.
Wang Lei etc. discloses a kind of spherex loaded calcium hydroxide catalysis system in Chinese patent (CN102633911B)
The method of standby hydroxypropyl-β-cyclodextrin.First CaOH2 is loaded in spherex, shallow lake is directly filtered to isolate after the completion of reaction
Powder microballoon, is spray-dried to obtain solid.This method has jumped out the alkali scope of NaOH or KOH, does not neutralize and produces unnecessary inorganic salts, is made
Purity 99%, the product of yield 95%.This method does not produce a large amount of high-salt wastewaters, high income.But 0.5-5MPa pressure is used, is deposited
In security risk.In addition spherex, which has a small amount of sugar unit and comes off, is dissolved in system, also has certain solubility in CaOH2 water
(1.66g/L, 20 DEG C), causes purity to be affected.
The content of the invention
The technical problems to be solved by the invention are to provide the preparation method of a kind of efficient and environmentally friendly hydroxypropyl cyclodextrin,
This method operating time is short, high income, cost are low, and pollution is small, suitable for industrial production application, the hydroxypropyl cyclodextrin impurity of preparation
Content is low, substitution value narrow range, suitable for food, medicine, cosmetics, agricultural, environmental protection and industrial application.
Problem of the present invention is realized by following technical scheme.
A kind of preparation method of hydroxypropyl cyclodextrin, carries out as follows：
(1) react：By calcium hydroxide or calcium oxide, water, cyclodextrin according to 1.6：100：10-25 mass ratioes are uniformly mixed,
Suspension is obtained, solution temperature control is slowly added dropwise 1, the 2- propylene oxide of 20-36% cyclodextrin mass fractions, was added dropwise to 20-30 DEG C
By temperature control at 20-30 DEG C in journey, when time for adding 8-36 is small, continue after being added dropwise stir 2-24 it is small when, gained reaction
Liquid is spare；
Why calcium hydroxide or calcium oxide, water, cyclodextrin are selected into aforementioned proportion, reason is as follows：Hydrogen in the case of water 100
Calcium oxide dissolution degree about 0.16, it is excessive 10 times to go 1.6 here, and cyclodextrin solubility about 10 in water, work as ring in the case
Dextrin amount continues to increase the increase of dosage system viscosity quickly after reaching 25, is unfavorable for stirring reaction.Therefore cyclodextrin 10-2 is taken；
(2) neutralize：It is added dropwise into reaction solution obtained by step (1) and is passed through carbon dioxide adjusting pH value to 6.5~8.5, makes life
Into precipitation of calcium carbonate, resulting solution standing 24 fully precipitates when small；
(3) filter：Filtering in precipitation solution will be contained obtained by step (2) and remove insoluble matter；
(4) it is dry：Feed liquid obtained by step (3) is drying to obtain white amorphous powder hydroxypropyl cyclodextrin；
The drying means to import in spray dryer, at 180-210 DEG C or using rotation steamed by inlet air temperature control
Transmitting apparatus deviates from moisture；
Preferably, calcium hydroxide or calcium oxide in the step (1)：Water：Cyclodextrin：The mass ratio ratio of 1,2- propylene oxide
For 1.6：100：15：4.2.
Above-mentioned preparation method, preferred 23-25 DEG C of the temperature of dropwise addition process in the step (1).
Above-mentioned preparation method, step (1) cyclodextrin can be alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin.
Above-mentioned preparation method, carbon dioxide adjusts the preferred 7.2-7.5 of pH value in the step (2).
Preparation method of the present invention, the hydroxypropyl cyclodextrin substitution value of generation is prepared in 4.8- according to optimum condition
Between 5.0
Hydroxypropyl cyclodextrin synthesis mechanism is cyclodextrin and propylene oxide under the catalytic action of alkali, with SN2Mechanism carries out
Nucleophilic substitution, specific mechanism are as follows：
Alkali is only to play catalytic action.Hydroxyl generation alcoxyl anion under base catalysis on cyclodextrin, then attack
The less side of propylene oxide steric hindrance, generates new alcoxyl anion, and new alcoxyl anion recaptures proton and generates alcohol hydroxyl
Base.Wherein, the first step is rate determining step.
2-OH is easiest to dissociation in known cyclodextrin, its pKa=12.2 dissociated, can be according to formula：Log (dissociation
Concentration/do not dissociate concentration)=pH-pKa calculating.Although CaOH2 is very low in water-soluble dissolubility, only 20 DEG C of 1.66g/L, saturation at this time
PH value of solution is still up to 12.65.During pH12.65, (dissociation concentration/do not dissociate concentration)=2.72, alcoxyl anion cyclodextrin at this time
It has been primarily present form.
CaOH2Relative to KOH and NaOH, because of solubility minor issue, production is also brought to control the advantages of simple, CaOH2Only
Want addition supersaturated concentration, unnecessary CaOH2System pH is not influenced completely then.Reaction is set to be carried out under stable pH.
After the completion of reaction, CaOH2Usable carbon dioxide is neutralized into the CaCO for being practically insoluble in water3(0.0014g/L), can
Direct precipitation removes.
In addition raw materials of Ca O more cheap and easy to get, running into water can immediate response generation CaOH2,Phase same-action can be played.
Stable pH can bring substitution value more to concentrate.
Scope is relatively narrow, and nature difference is small between batch, stable quality；PH value 7.2~7.5 is adjusted using carbon dioxide, can be
Excessive calcium hydroxide is sufficiently converted into calcium carbonate, and precipitation removes；Drying time has been substantially shorter using spray drying process, has been carried
High production efficiency.Product substitution value narrow range that the preparation method of hydroxypropyl cyclodextrin of the present invention obtains, impurity contain
Measure low, raw material dosage is few, and yield reproduces few up to more than 95%, and cost is low, suitable for industrial production application.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
(1) react：In 1000ml round-bottomed flasks, 8g calcium hydroxides, 500ml deionized waters, 50g (after giving money as a gift) β-ring are added
Dextrin is quickly uniformly mixed, and obtains milky suspension.18g1,2- propylene oxide, drop is slowly added dropwise to 30 DEG C in solution temperature control
During adding by temperature control below 30 DEG C, when time for adding 8 is small, continue after being added dropwise stirring 12 it is small when, gained reaction
Liquid is spare；
(2) neutralize：It is added dropwise into reaction solution obtained by step (1) and is passed through carbon dioxide to adjusting pH value to 7.5, gained
Solution left standstill 24 fully precipitates when small；
(3) filter：Filtering in precipitation solution will be contained obtained by step (2) and remove insoluble matter；
(4) it is dry：Feed liquid obtained by step (3) is imported into Rotary Evaporators, less than 80 DEG C are evaporated, and obtain white amorphous powder
Hydroxypropyl-β-cyclodextrin 64g.Substitution value 6.3, beta-cyclodextrin residual 0.02%, 1,2-PD 0.2%, residue on ignition
0.01%.
Embodiment 2
(1) in 1000ml round-bottomed flasks, 8g calcium hydroxides, 500ml deionized waters, 75g (after giving money as a gift) alpha-cyclodextrin are added
Quickly it is uniformly mixed, obtains milky suspension.To 30 DEG C 18g1 is slowly added dropwise, 2- propylene oxide, was added dropwise in solution temperature control
In journey by temperature control below 30 DEG C, when time for adding 8 is small, continue after being added dropwise stirring 12 it is small when, gained reaction solution is standby
With；
(2) neutralize：It is added dropwise into reaction solution obtained by step (1) and is passed through carbon dioxide to adjusting pH value to 7.5, gained
Solution left standstill 24 fully precipitates when small；
(3) filter：Filtering in precipitation solution will be contained obtained by step (2) and remove insoluble matter；
(4) it is dry：Feed liquid obtained by step (3) is imported into Rotary Evaporators, less than 80 DEG C are evaporated, and obtain white amorphous powder
Hydroxyproply-α-cyclodextrin 86g.Substitution value 3.7, alpha-cyclodextrin residual 0.01%, 1,2-PD 0.1%, residue on ignition
0.01%.
Embodiment 3
(1) react：In 1000ml round-bottomed flasks, addition 8g calcium hydroxides, 500ml deionized waters, 100g (after giving money as a gift) γ-
Cyclodextrin is quickly uniformly mixed, and obtains shallow white suspension.30g1 is slowly added dropwise to 30 DEG C in solution temperature control, 2- propylene oxide,
During dropwise addition by temperature control below 30 DEG C, when time for adding 8 is small, continue after being added dropwise stirring 12 it is small when, gained is anti-
Answer liquid spare；
(2) neutralize：It is added dropwise into reaction solution obtained by step (1) and is passed through carbon dioxide to adjusting pH value to 7.5, gained
Solution left standstill 24 fully precipitates when small；
(3) filter：Filtering in precipitation solution will be contained obtained by step (2) and remove insoluble matter；
(4) it is dry：Feed liquid obtained by step (3) is imported into Rotary Evaporators, less than 80 DEG C are evaporated, and obtain white amorphous powder
Hydropropyl-y-cyclodextrin 120.5g.Substitution value 6.0, gamma-cyclodextrin residual 0.01%, 1,2-PD 0.3%, residue on ignition
0.01%.
Embodiment 4
(1) react：In 1000L reaction kettles, 1.2kg calcium oxide, 750L deionized waters, 110kg (after giving money as a gift) β-ring are added
Dextrin, is uniformly mixed when quickly stirring 1 is small.To 25-30 DEG C 30kg1 is slowly added dropwise, 2- propylene oxide, was added dropwise in solution temperature control
In journey by temperature control below 30 DEG C, when time for adding 24 is small, continue after being added dropwise stirring 8 it is small when, gained reaction solution is standby
With；
(2) neutralize：It is added dropwise into reaction solution obtained by step (1) and is passed through carbon dioxide to adjusting pH value to 7.5, gained
Solution left standstill 24 fully precipitates when small；
(3) filter：Filtering in precipitation solution will be contained obtained by step (2) and remove insoluble matter；
(4) feed liquid obtained by step (3) is imported into spray dryer machine, adjusts 190~210 DEG C of inlet air temperature, leaving air temp
80~90 DEG C, obtain white amorphous powder hydroxypropyl-β-cyclodextrin 130.3kg.Substitution value 4.9, dry matter conversion yield 95%.
Require testing result as follows according to hydroxypropyl-β-cyclodextrin in Chinese Pharmacopoeia 2015 editions：
The hydroxypropyl-β-cyclodextrin of this method production removes inorganic salts step without nanofiltration, and products obtained therefrom remains to meet
Relevant regulations in Chinese Pharmacopoeia 2015 editions.
Above-described embodiment is only technical solution and the example enumerated to clearly illustrate in the present invention, is not to the present invention
The restriction of protection domain.
Claims (6)
1. a kind of environment-friendly preparation method thereof of hydroxypropyl cyclodextrin, it is characterised in that carry out as follows：
(1) react：By calcium hydroxide or calcium oxide, water, cyclodextrin according to 1.6：100：10-25 mass ratioes are uniformly mixed, and are obtained mixed
To 20-30 DEG C 1, the 2- propylene oxide of 20-36% cyclodextrin mass fractions is slowly added dropwise, during dropwise addition in suspension, solution temperature control
By temperature control at 20-30 DEG C, when time for adding 8-36 is small, continue after being added dropwise stir 2-24 it is small when, gained reaction solution is standby
With；
(2) neutralize：It is added dropwise into reaction solution obtained by step (1) and is passed through carbon dioxide adjusting pH value to 6.5~8.5, makes generation carbon
Sour calcium precipitate, resulting solution standing 24 fully precipitate when small；
(3) filter：Filtering in precipitation solution will be contained obtained by step (2) and remove insoluble matter；
(4) it is dry：Feed liquid obtained by step (3) is drying to obtain white amorphous powder hydroxypropyl cyclodextrin.
2. the environment-friendly preparation method thereof of hydroxypropyl cyclodextrin as claimed in claim 1, it is characterised in that described in step (4)
Dry, to import in spray dryer, inlet air temperature is controlled at 180-210 DEG C drying means；Or taken off using rotary evaporating device
Go out moisture.
3. the environment-friendly preparation method thereof of hydroxypropyl cyclodextrin as claimed in claim 1, it is characterised in that hydrogen in the step (1)
Calcium oxide or calcium oxide：Water：Cyclodextrin：The mass ratio ratio of 1,2- propylene oxide is 1.6：100：15：4.2.
4. the environment-friendly preparation method thereof of hydroxypropyl cyclodextrin as claimed in claim 1, it is characterised in that drop in the step (1)
The temperature for adding process is 23-25 DEG C.
5. the environment-friendly preparation method thereof of hydroxypropyl cyclodextrin as claimed in claim 1, it is characterised in that step (1) middle ring
Dextrin is selected from alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin.
6. the environment-friendly preparation method thereof of hydroxypropyl cyclodextrin as claimed in claim 1, it is characterised in that two in the step (2)
It is 7.2-7.5 that carbonoxide, which adjusts pH value,.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808299A (en) * | 2020-07-02 | 2020-10-23 | 山东滨州智源生物科技有限公司 | Preparation method of hydroxypropyl betacyclodextrin aqueous solution |
| CN112334494A (en) * | 2018-06-29 | 2021-02-05 | 罗盖特公司 | Novel hydroxypropyl-beta-cyclodextrin and method for producing the same |
| CN113845607A (en) * | 2021-10-26 | 2021-12-28 | 波托菲诺(海南)实业有限公司 | Preparation method of hydroxypropyl-gamma-cyclodextrin |
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| US5935941A (en) * | 1997-10-24 | 1999-08-10 | Pitha; Josef | Alkylations of cyclodextrins leading to derivatives which have a ridgidly extended cavity |
| CN102558394A (en) * | 2010-12-07 | 2012-07-11 | 石药集团中奇制药技术（石家庄）有限公司 | Preparation method of hydroxypropyl-beta-cyclodextrin |
| CN102633911A (en) * | 2012-04-19 | 2012-08-15 | 陕西科技大学 | Method for preparing hydroxypropyl-beta-cyclodextrin by catalysis of starch microsphere supported calcium hydroxides |
| CN104271605A (en) * | 2012-02-15 | 2015-01-07 | 锡德克斯药物公司 | Manufacturing process for cyclodextrin derivatives |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5935941A (en) * | 1997-10-24 | 1999-08-10 | Pitha; Josef | Alkylations of cyclodextrins leading to derivatives which have a ridgidly extended cavity |
| CN102558394A (en) * | 2010-12-07 | 2012-07-11 | 石药集团中奇制药技术（石家庄）有限公司 | Preparation method of hydroxypropyl-beta-cyclodextrin |
| CN104271605A (en) * | 2012-02-15 | 2015-01-07 | 锡德克斯药物公司 | Manufacturing process for cyclodextrin derivatives |
| CN102633911A (en) * | 2012-04-19 | 2012-08-15 | 陕西科技大学 | Method for preparing hydroxypropyl-beta-cyclodextrin by catalysis of starch microsphere supported calcium hydroxides |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112334494A (en) * | 2018-06-29 | 2021-02-05 | 罗盖特公司 | Novel hydroxypropyl-beta-cyclodextrin and method for producing the same |
| JP2021529243A (en) * | 2018-06-29 | 2021-10-28 | ロケット フレールＲｏｑｕｅｔｔｅ Ｆｒｅｒｅｓ | A novel hydroxypropyl-β-cyclodextrin and a method for producing it |
| CN111808299A (en) * | 2020-07-02 | 2020-10-23 | 山东滨州智源生物科技有限公司 | Preparation method of hydroxypropyl betacyclodextrin aqueous solution |
| CN111808299B (en) * | 2020-07-02 | 2022-05-31 | 山东滨州智源生物科技有限公司 | Preparation method of hydroxypropyl betacyclodextrin aqueous solution |
| CN113845607A (en) * | 2021-10-26 | 2021-12-28 | 波托菲诺(海南)实业有限公司 | Preparation method of hydroxypropyl-gamma-cyclodextrin |
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