CN104327198A - Maleic acid [beta]-cyclodextrin ester and preparation method thereof - Google Patents
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Abstract
The invention discloses a maleic acid [beta]-cyclodextrin ester and a preparation method thereof. A structure general formula of maleic acid [beta]-cyclodextrin monoester is represented as the formula I and a structure general formula of maleic acid [beta]-cyclodextrin diester is represented as the formula II. The method includes a following step of mixing maleic acid, [beta]-cyclodextrin and a polymerization inhibitor for carrying out an esterification reaction with a phosphate as a catalyst to obtain the maleic acid [beta]-cyclodextrin monoester represented as the formula I and/or the maleic acid [beta]-cyclodextrin diester represented as the formula II. The invention provides the environmental-friendly preparation method. In the method, the phosphate is employed as a catalyst and the polyunsaturated carboxylic acid and the [beta]-cyclodextrin are esterified so that not only is usage amount of an organic solvent is reduced but also an unsaturated degree of [beta]-cyclodextrin esterification derivatives is increased, thereby providing a new approach for the [beta]-cyclodextrin derivatives in high-molecular polymer molecule construction.
Description
Technical field
The invention belongs to chemical field, relate to a kind of ester class material, especially relate to a kind of maleic acid beta-cyclodextrin ester and preparation method thereof.
Background technology
Beta-cyclodextrin (β-cyclodextrin, β-CD) be the one of cyclodextrin, by α-1 by 7 D-Glucopyranoses, the cyclic oligosaccharide that 4 glycosidic links are formed by connecting is hydrophobic inner chamber because beta-cyclodextrin has, desirable binding site can be provided, by a certain size organic molecule inclusion with shape, a kind of novel inclusion material can be formed.Because beta-cyclodextrin inner-cavity structure size is fixed, the stability of inclusion compound depends primarily on polarity and the size of guest molecule.At present, beta-cyclodextrin embedding techniques is mainly used in the preparation research of essential oil, the water not inclusion compound such as soluble drug, volatile substances and microcapsule, but because beta-cyclodextrin forms intramolecular hydrogen bond between C2, C3 hydroxyl, therefore the solubleness in water lower (1.85g/100mL), limits the application of beta-cyclodextrin.In recent years, investigator carries out structural modification to beta-cyclodextrin, has prepared multiple beta-cyclodextrin derivative, and these derivatives have the physico-chemical property different from natural beta-cyclodextrin and clathration and expand the range of application of beta-cyclodextrin.
Because beta-cyclodextrin is when forming high molecular polymer with other molecules, often use a large amount of organic reagents, the security of product can not be protected.If make beta-cyclodextrin have vinyl structure, form the beta-cyclodextrin derivative of vinyl-containing monomers, by free chain reaction, can be easy to prepare beta-cyclodextrin high molecular polymer, and not need to use a large amount of poisonous and harmful reagent.So-called vinyl monomer is the general name that a class contains the organic compound molecule of-CH=CH-structure.Be very important precursor substance or synthetic intermediate in chemical industry synthesis, be widely used in molecular modification, molecule crosslinked, molecule grafting.As the polymkeric substance that polyethylene, polypropylene are exactly ethene, propylene.At present, preparation is containing vinyl structure monomer, and the main carboxylic acid containing vinyl structure that utilizes, as maleic acid, vinylformic acid etc. and alcohols, as methyl alcohol and ethanol etc., forms the ester class containing vinyl structure.But in the process of preparation, often need to use high reactivity, the highly toxic organic reagents such as para Toluic Acid's SULPHURYL CHLORIDE, be difficult to its product application in food, medicine field.At present, the preparation method about maleic acid beta-cyclodextrin ester have not been reported.
Summary of the invention
The object of this invention is to provide a kind of maleic acid beta-cyclodextrin ester and preparation method thereof.
Maleic acid beta-cyclodextrin one ester provided by the invention, its general structure such as formula shown in I,
Present invention also offers maleic acid beta-cyclodextrin diester, its general structure such as formula shown in II,
Shown in the described formula I of preparation provided by the invention, the method for maleic acid beta-cyclodextrin diester shown in maleic acid beta-cyclodextrin one ester and described formula II, comprises the steps:
Take phosphoric acid salt as catalyzer, carry out esterification after maleic acid, beta-cyclodextrin and stopper being mixed in water, react complete and obtain maleic acid beta-cyclodextrin diester shown in maleic acid beta-cyclodextrin one ester shown in described formula I and/or described formula II.
In aforesaid method, described phosphoric acid salt is inferior sodium phosphate, Sodium hexametaphosphate 99, SODIUM PHOSPHATE, MONOBASIC or sodium phosphite;
Described stopper is toluhydroquinone, Tert. Butyl Hydroquinone or 4-methoxyphenol.
The molar ratio of described maleic acid and beta-cyclodextrin is 1-5:1, is specially 1:1,2:1,3:1,4:1,1-4:1,2-5:1,3-5:1,1-2:1 or 3-4:1;
The consumption of described catalyzer be the 0.17-0.67 of the mole dosage of maleic acid doubly, be specially 0.25,0.5,0.4,0.25-0.4,0.4-0.5,0.25-0.5 doubly;
The consumption of described stopper is the 0.5-7% of the quality consumption of maleic acid, be specially 0.75%, 1.7%, 0.75%-1.7%, 2.5%;
The total mass of described beta-cyclodextrin, maleic acid and catalyzer and the mass ratio of water are 1:0.6-1:1.2, are specially 1:0.6;
In described step of esterification, temperature is 90-130 DEG C, is specially 110 DEG C;
Time is 1.5-4.5 hour, be specially 1.5,2.5,3.5,1.5-2.5 hour or 2.5-3.5 hour.
Concrete, described method is method one or method two:
Described method one comprises the steps:
Take phosphoric acid salt as catalyzer, maleic acid, beta-cyclodextrin, stopper and water are mixed in 100-110 DEG C and carry out esterification, the molar ratio of described maleic acid and beta-cyclodextrin is 1-2:1, reacts complete and obtains the ester of maleic acid beta-cyclodextrin one shown in described formula I;
Wherein, the consumption of described catalyzer is 0.17-0.67 times of the mole dosage of maleic acid, is specially 0.5 times;
The consumption of described stopper is the 0.5-7% of the quality consumption of maleic acid, is specially 2.5%;
The total mass of described beta-cyclodextrin, maleic acid and catalyzer and the mass ratio of water are 1:0.6-1:1.2, are specially 1:0.6;
In described step of esterification, the time is 1.5-4.5 hour, is specially 2.5-3.5 hour.
Described method two comprises the steps:
Take phosphoric acid salt as catalyzer, maleic acid, beta-cyclodextrin, stopper and water are mixed in 120-130 DEG C and carry out esterification, the molar ratio of described maleic acid and beta-cyclodextrin is 3-4:1, reacts complete and obtains the diester of maleic acid beta-cyclodextrin shown in described formula II;
Wherein, the consumption of described catalyzer is 0.17-0.67 times of the mole dosage of maleic acid, is specially 0.25-0.4 doubly;
The consumption of described stopper is the 0.5-7% of the quality consumption of maleic acid, is specially 0.75-1.7%;
The total mass of described beta-cyclodextrin, maleic acid and catalyzer and the mass ratio of water are 1:0.6-1:1.2, are specially 1:0.6;
In described step of esterification, the time is 1.5-4.5 hour, is specially 1.5-3.5 hour.
The present invention is directed to when beta-cyclodextrin carries out esterification modification and need use a large amount of poisonous and harmful organic reagent, provide a kind of environmentally friendly preparation method.The method is by using low toxicity or nontoxic phosphoric acid salt as catalyzer, by multi-unsaturated carboxylic acid and beta-cyclodextrin esterification, both the usage quantity of organic reagent can have been reduced, turn increase the degree of unsaturation of beta-cyclodextrin esterified derivative, in optimal conditions, the esterification yield of the method can reach 78.68%, and double bond content can reach 92.27 mequiv./100g CDM; In the method, the usage quantity of organic reagent is few; Can obtain maleic acid beta-cyclodextrin one ester and maleic acid beta-cyclodextrin diester by conditions such as the proportioning of adjustment formula, adjustment temperature of reaction, make the suitability of product wider, there are good using value and market outlook simultaneously.
Accompanying drawing explanation
Fig. 1 is the typical curve of cis-butenedioic acid mono ethyl maleate and two ethyl ester.
Fig. 2 is that catalyst type and consumption are on the impact of double bond content.
Fig. 3 is solid-to-liquid ratio on the impact of double bond content or esterification yield, and wherein, a is the impact of solid-to-liquid ratio on double bond content, and b is the impact of solid-to-liquid ratio on esterification yield.
Fig. 4 is temperature on the impact of double bond content or esterification yield, and wherein, a is the impact of temperature on double bond content, and b is the impact of temperature on esterification yield.
Fig. 5 is stopper kind and stopper consumption on the impact of double bond content or esterification yield, wherein, a be stopper kind and stopper consumption on the impact of double bond content, b is that stopper kind and stopper consumption are on the impact of esterification yield.
Fig. 6 is maleic acid consumption on the impact of double bond content or esterification yield, and wherein, a is the impact of maleic acid consumption on double bond content, and b is the impact of maleic acid consumption on esterification yield.
Fig. 7 is the reaction times on the impact of double bond content or esterification yield, and wherein, a is the impact of reaction times on both shoulders content, and b is the impact of reaction times on esterification yield.
Fig. 8 is the infared spectrum structural characterization of temperature to maleic acid beta-cyclodextrin ester.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
In the present invention, institute's employing instrument is recirculated air heating drying oven.
The reaction vessel adopted in the present invention is high-temperature pressure-proof bottle.
The performance of product is characterized by esterification yield double bond content, and constitutional features is characterized by infared spectrum.The measuring method of esterification yield: respectively with cis-butenedioic acid mono ethyl maleate and diethyl maleate for standard substance, with ultraviolet spectrophotometry production standard curve (Fig. 1).
Utilize following formulae discovery esterification yield.
Wherein: the coefficient (monoesters a=0.1169, dibasic acid esters a=0.1417) that a-is relevant to molecular weight; A-sample is at the absorbance at 210nm place; B-marks bent intercept; K-marks bent slope; W-sample quality; V-sample volume; X-diluted sample multiple; M
wthe molecular weight of-β-CD-MA monoesters (dibasic acid esters)
The measuring method of double bond content is as follows: get dry sample 0.5g in tool plug triangular flask, under the condition of ice territory, add 10ml KBr/KBrO
3mixing solutions (6.960g/L KBrO
3, 30g/L KBr), add 5ml H subsequently
2sO
4(1N), the Br of reaction release
2react with the double bond in sample, excessive Br
2add the KI solution oxide of 10ml20%, the I restored
2iodometry is utilized to measure its content.Double bond content (in equivalent concentration DBC) formulae discovery the following
Wherein,
V
bthe normal sodium thiosulfate volume that-blank group consumes;
V
sthe normal sodium thiosulfate volume that-sample sets consumes; W-is the quality of sample.
Experimental procedure: first weighing 6.81g beta-cyclodextrin and a certain amount of catalyzer are in pressure bottle, mixing; Weigh maleic acid and stopper, add a certain amount of water dissolution, finally add in pressure bottle, sealing, puts into baking oven, heating, after reaction certain hour, take out, 4 DEG C of refrigerators, crystallization, after crystal is separated out, abandoning supernatant, crystal with 95% ethanol 100ml, wash three times, in 60 DEG C of oven for drying, obtained maleic acid beta-cyclodextrin ester.
Embodiment 1
With 0.636g (0.006mol) inferior sodium phosphate (NaH
2pO
2) be catalyzer, by 1.393g (0.012mol) maleic acid, 6.81g (0.006mol) beta-cyclodextrin and 0.0348g (2.8 × 10-
4mol) stopper 4-methoxyphenol (4-Methoxyphenol) carries out esterification 2.5 hours in 110 DEG C after mixing in 5.3g water, after completion of the reaction, crystal with 95% ethanol 100ml, wash three times, in 60 DEG C of oven for drying, obtain the ester of maleic acid beta-cyclodextrin one shown in formula I provided by the invention.
Embodiment 2
With 0.624g (0.004mol) SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
4) be catalyzer, by 0.696g (0.006mol) maleic acid, 6.81g (0.006mol) beta-cyclodextrin and 0.0174g (1.40 × 10
-4mol) toluhydroquinone (Methylhydroquinone) carries out esterification 3.5 hours in 100 DEG C after mixing in 4.9g water, after completion of the reaction, crystal with 95% ethanol 100ml, wash three times, in 60 DEG C of oven for drying, obtain the ester of maleic acid beta-cyclodextrin one shown in formula I provided by the invention.
Embodiment 3
With 0.636g (0.006mol) inferior sodium phosphate (NaH
2pO
2) be catalyzer, by 2.786g (0.024mol) maleic acid, 6.81g (0.006mol) beta-cyclodextrin and 0.0209g (1.68 × 10
-4mol) 4-methoxyphenol (4-Methoxyphenol) carries out esterification 1.5 hours in 120 DEG C after mixing in 6.1g water, after completion of the reaction, after completion of the reaction, crystal with 95% ethanol 100ml, wash three times, in 60 DEG C of oven for drying, obtain the diester of maleic acid beta-cyclodextrin shown in formula I provided by the invention.
Embodiment 4
With 1.248g (0.008mol) SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
4) be catalyzer, by 2.089g (0.018mol) maleic acid, 6.81g (0.006mol) beta-cyclodextrin and 0.0348g (2.09 × 10
-4mol) Tert. Butyl Hydroquinone, esterification is carried out 1.5 hours in 120 DEG C after mixing in 6.1g water, after completion of the reaction, after completion of the reaction, crystal with 95% ethanol 100ml, wash three times, in 60 DEG C of oven for drying, obtain the diester of maleic acid beta-cyclodextrin shown in formula I provided by the invention.
Embodiment 5, catalyst type and consumption are on the impact of double bond content
According to the step of embodiment 1, only do not add stopper, catalyst type is sodium phosphite, inferior sodium phosphate, Sodium hexametaphosphate 99 or SODIUM PHOSPHATE, MONOBASIC;
Wherein, the consumption of sodium phosphite is 0.432g (0.002mol), 0.864g (0.004mol), 1.300g (0.006mol), 1.728g (0.008mol);
The consumption of inferior sodium phosphate is 0.212g (0.002mol), 0.424g (0.004mol), 0.636g (0.006mol), 0.848g (0.008mol);
The consumption of Sodium hexametaphosphate 99 is 1.224g (0.002mol), 2.447g (0.004mol), 3.671g (0.006mol), 4.894g (0.008mol);
The consumption of SODIUM PHOSPHATE, MONOBASIC is 0.312g (0.002mol), 0.624g (0.004mol), 0.936g (0.006mol), 1.248g (0.008mol);
Fig. 2 is that catalyst type and consumption are on the impact of double bond content.
As shown in Figure 2, the catalysis of inferior sodium phosphate is the strongest in all phosphoric acid salt, and along with catalyst levels increase, sample double bond content is larger.Owing to adopting semidrying to prepare ethyl maleate, in order to reduce the residual quantity of salt in product, therefore catalyst levels chooses 0.5mol/mol maleic acid (MA).
Embodiment 6, solid-to-liquid ratio are on the impact of double bond content and esterification yield
According to the step of embodiment 1, only do not add stopper, inferior sodium phosphate chosen by catalyzer, and solid-to-liquid ratio is replaced with 1:0.6,1:0.8,1:1 and 1:1.2,
In Fig. 3, a is that on the impact of double bond content, (maleic acid: 1.393g, beta-cyclodextrin 0.681g, do not add stopper to solid-to-liquid ratio; The temperature of esterification 110 DEG C, reaction times 2.5h, catalyst type and consumption: inferior sodium phosphate 0.636g).
In Fig. 3, b is the impact of solid-to-liquid ratio on esterification yield
As shown in Figure 3, along with the increase of solid-to-liquid ratio, double bond content reduces along with the rising of solid-to-liquid ratio, under the condition of inferior sodium phosphate as catalyzer, the impact of solid-to-liquid ratio on esterification yield is not obvious, but during catalyst-free, esterification yield obviously reduces with the rising esterification yield of solid-to-liquid ratio, therefore to choose solid-to-liquid ratio 1:0.6 be best solid-to-liquid ratio.
Embodiment 7, temperature are on the impact of double bond and esterification yield
According to the step of embodiment 1, only the temperature of esterification is replaced with 90 DEG C, 100 DEG C, 120 DEG C, 130 DEG C;
In Fig. 4, a is that on the impact of double bond content, (maleic acid: 1.393g, beta-cyclodextrin 0.681g, do not add stopper to temperature; The temperature 90-130 DEG C of esterification, reaction times 2.5h, catalyst type and consumption: inferior sodium phosphate 0.636g)
In Fig. 4, b is the impact of temperature on esterification yield
As shown in Figure 4, temperature raises double bond content to be increased gradually, but esterification yield obviously reduces on the contrary along with temperature raises, and particularly temperature is higher than after 110 DEG C, therefore, selects 110 DEG C as optimal reaction temperature.
Embodiment 8, stopper kind and stopper consumption are on the impact of double bond content and esterification yield
According to the step of embodiment 1, stopper is replaced with 4-methoxyphenol, toluhydroquinone or Tert. Butyl Hydroquinone; Catalyst choice inferior sodium phosphate;
Wherein, the consumption of 4-methoxyphenol replaces with 0.007g (5.6 × 10
-5mol), 0.0209g (1.68 × 10
-4mol), 0.0348g (2.80 × 10
-4mol), 0.0488g (3.93 × 10
-4mol);
The consumption of toluhydroquinone replaces with 0.007g (5.6 × 10
-5mol), 0.0209g (1.68 × 10
-4mol), 0.0348g (2.80 × 10
-4mol), 0.0488g (3.93 × 10
-4mol);
The consumption of Tert. Butyl Hydroquinone replaces with 0.007g (4.21 × 10
-5mol), 0.0209g (1.26 × 10
-4mol), 0.0348g (2.09 × 10
-4mol), 0.0488g (2.94 × 10
-4mol);
In Fig. 5, a is that stopper kind and stopper consumption are on impact (maleic acid: 1.393g, the beta-cyclodextrin 0.681g of double bond content; Stopper kind and consumption: 4-methoxyphenol, toluhydroquinone and Tert. Butyl Hydroquinone, consumption is 0.007g-0.0488g; The temperature of esterification 110 DEG C, reaction times 2.5h, catalyst type and consumption: inferior sodium phosphate 0.636g).
In Fig. 5, b is that stopper kind and stopper consumption are on the impact of esterification yield
As shown in Figure 5, stopper does not almost affect esterification yield, but along with the increase of stopper consumption, the double bond content of sample significantly increases, and the effect of 4-methoxyl group phenol is best, therefore, selects 4-methoxyl group phenol as optimum stopper.
Embodiment 9, maleic acid consumption are on the impact of double bond content and esterification yield
According to the step of embodiment 1, only the consumption of maleic acid is replaced with 0.696g (0.006mol), 1.393g (0.012mol), 2.089g (0.018mol), 2.786g (0.024mol), 3.482g (0.030mol); Stopper is 4-methoxyphenol, and catalyzer is inferior sodium phosphate.
In Fig. 6, a be maleic acid consumption on the impact of double bond content (maleic acid: 0.696-3.482g, beta-cyclodextrin 0.681g, stopper is 4-methoxyphenol, and consumption is 2.5% of maleic quality; The temperature of esterification 110 DEG C, reaction times 2.5h, catalyst type: inferior sodium phosphate, consumption is 0.5 times (inferior sodium phosphate consumption 0.318-1.590g) of maleic diene mole dosage.
In Fig. 6, b is the impact of maleic acid consumption on esterification yield
As shown in Figure 6, along with the increase of maleic acid consumption, esterification yield and the double bond content of sample all increase, but after MA:CD=4:1, the trend that double bond content and esterification yield increase starts to slow down, consider from the angle of efficent use of resources, choose the optimum quantum of utilization of MA:CD=4:1 as maleic acid.
Embodiment 10, reaction times are on the impact of double bond content and esterification yield
According to the step of embodiment 1, stopper is 4-methoxyphenol, and consumption is 0.0697g (5.61 × 10
-4), catalyzer is inferior sodium phosphate 1.393g (0.012mol), maleic acid 2.786g (0.024mol), and the reaction times replaces with 1.5 hours, 2.5 hours, 3.5 hours and 4.5 hours;
In Fig. 7, a is that the reaction times, (maleic acid: 2.786g, beta-cyclodextrin 0.681g, do not add stopper on the impact of double bond content; The temperature of esterification 110 DEG C, the reaction times is 1.5-4.5h, catalyst type and consumption: inferior sodium phosphate 1.393g)
In Fig. 7, b is the impact of reaction times on esterification yield
As shown in Figure 7, after 3.5 hr, double bond content no longer increases in reaction, and the reaction times more than 3.5 hours after, the esterification yield of sample starts to decline, and therefore choosing 3.5h is optimum reacting time.
Embodiment 10, temperature of reaction are on the impact of double bond content and esterification yield
According to the step of embodiment 1, stopper is 4-methoxyphenol, and catalyzer is inferior sodium phosphate, temperature of reaction is replaced with 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C or 130 DEG C;
Fig. 8 is the infared spectrum structural characterization of temperature to maleic acid beta-cyclodextrin ester
As seen from the figure, due to when temperature of reaction is lower than 110 DEG C, the absorption peak of carboxyl in maleic acid has been there is in maleic acid beta-cyclodextrin ester at 1706cm-1, the absorption peak of ester bond in cis-butenedioic acid mono ethyl maleate has been there is at 1723cm-1, therefore when temperature of reaction is lower than 110 DEG C, the mainly maleic acid beta-cyclodextrin monoesters of formation; After temperature is higher than 110 DEG C, only, under 1722cm-1, there is the charateristic avsorption band of ester bond in maleic acid ester in maleic acid beta-cyclodextrin ester, thus after temperature is higher than 110 DEG C, and the mainly maleic acid beta-cyclodextrin dibasic acid esters of formation.
Claims (6)
1. the beta-cyclodextrin one of maleic acid shown in formula I ester,
2. the beta-cyclodextrin of maleic acid shown in formula II diester,
3. prepare a method for maleic acid beta-cyclodextrin diester shown in formula II described in beta-cyclodextrin one ester of maleic acid shown in formula I described in claim 1 and/or claim 2, comprise the steps:
Take phosphoric acid salt as catalyzer, carry out esterification after maleic acid, beta-cyclodextrin and stopper being mixed in water, react complete and obtain maleic acid beta-cyclodextrin diester shown in formula II described in maleic acid beta-cyclodextrin one ester shown in described formula I and/or claim 2.
4. method according to claim 3, is characterized in that: described phosphoric acid salt is inferior sodium phosphate, Sodium hexametaphosphate 99, SODIUM PHOSPHATE, MONOBASIC or sodium phosphite;
Described stopper is toluhydroquinone, Tert. Butyl Hydroquinone or 4-methoxyphenol.
5. the method according to claim 3 or 4, is characterized in that: the molar ratio of described maleic acid and beta-cyclodextrin is 1-5:1;
The consumption of described catalyzer is 0.17-0.67 times of the mole dosage of maleic acid;
The consumption of described stopper is the 0.5-7% of the quality consumption of maleic acid;
The total mass of described beta-cyclodextrin, maleic acid and catalyzer and the mass ratio of water are 1:0.6-1:1.2;
In described step of esterification, temperature is 90-130 DEG C;
Time is 1.5-4.5 hour.
6., according to the arbitrary described method of claim 3-5, it is characterized in that: described method is method one or method two:
Described method one comprises the steps:
Take phosphoric acid salt as catalyzer, maleic acid, beta-cyclodextrin, stopper and water are mixed in 100-110 DEG C and carry out esterification, the molar ratio of described maleic acid and beta-cyclodextrin is 1-2:1, reacts complete and obtains the ester of maleic acid beta-cyclodextrin one shown in described formula I;
Wherein, the consumption of described catalyzer is 0.17-0.67 times of the mole dosage of maleic acid, is specially 0.5 times;
The consumption of described stopper is the 0.5-7% of the quality consumption of maleic acid, is specially 2.5%;
The total mass of described beta-cyclodextrin, maleic acid and catalyzer and the mass ratio of water are 1:0.6-1:1.2, are specially 1:0.6;
In described step of esterification, the time is 1.5-4.5 hour, is specially 2.5-3.5 hour.
Described method two comprises the steps:
Take phosphoric acid salt as catalyzer, maleic acid, beta-cyclodextrin, stopper and water are mixed in 120-130 DEG C and carry out esterification, the molar ratio of described maleic acid and beta-cyclodextrin is 3-4:1, reacts complete and obtains the diester of maleic acid beta-cyclodextrin shown in described formula II;
Wherein, the consumption of described catalyzer is 0.17-0.67 times of the mole dosage of maleic acid, is specially 0.25-0.4 doubly;
The consumption of described stopper is the 0.5-7% of the quality consumption of maleic acid, is specially 0.75-1.7%;
The total mass of described beta-cyclodextrin, maleic acid and catalyzer and the mass ratio of water are 1:0.6-1:1.2, are specially 1:0.6;
In described step of esterification, the time is 1.5-4.5 hour, is specially 1.5-3.5 hour.
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| CN111171187A (en) * | 2020-02-12 | 2020-05-19 | 贵州省现代农业发展研究所 | preparation method of butenoic acid- β -cyclodextrin ester |
| CN114133467A (en) * | 2021-12-16 | 2022-03-04 | 科之杰新材料集团浙江有限公司 | Unsaturated esterified monomer and ester low-bleeding polycarboxylate superplasticizer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302275A (en) * | 2008-07-01 | 2008-11-12 | 上海大学 | Method for preparing copolymer aquagel having cyclodextrin structure by electron beam radiation |
| CN101864034A (en) * | 2010-06-06 | 2010-10-20 | 西北大学 | Application of acrylic acid cyclodextrin polymer in dyeing industrial waste water treatment |
| CN102504109A (en) * | 2011-11-15 | 2012-06-20 | 西南石油大学 | Cyclodextrin supported hydrogel and preparation method thereof |
| CN102504526A (en) * | 2011-11-14 | 2012-06-20 | 常州大学 | Preparation method for polyether polyurethane material |
| CN103145256A (en) * | 2013-03-18 | 2013-06-12 | 武汉理工大学 | Preparation method and application of ternary high polymer copolymer scale inhibitor |
-
2014
- 2014-05-15 CN CN201410205821.9A patent/CN104327198B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302275A (en) * | 2008-07-01 | 2008-11-12 | 上海大学 | Method for preparing copolymer aquagel having cyclodextrin structure by electron beam radiation |
| CN101864034A (en) * | 2010-06-06 | 2010-10-20 | 西北大学 | Application of acrylic acid cyclodextrin polymer in dyeing industrial waste water treatment |
| CN102504526A (en) * | 2011-11-14 | 2012-06-20 | 常州大学 | Preparation method for polyether polyurethane material |
| CN102504109A (en) * | 2011-11-15 | 2012-06-20 | 西南石油大学 | Cyclodextrin supported hydrogel and preparation method thereof |
| CN103145256A (en) * | 2013-03-18 | 2013-06-12 | 武汉理工大学 | Preparation method and application of ternary high polymer copolymer scale inhibitor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500631A (en) * | 2017-09-20 | 2017-12-22 | 河南省三门峡黄河大桥高速公路建设有限公司 | Science of bridge building quick setting and rapid hardening ungauged regions self-compacting concrete and preparation method thereof |
| CN109043489A (en) * | 2018-08-28 | 2018-12-21 | 重庆火吉健康产业（集团）有限公司 | A kind of compound drying aid and its application in preparation pyracantha fortuneana fruit powder |
| CN109170663A (en) * | 2018-08-28 | 2019-01-11 | 重庆火吉健康产业（集团）有限公司 | Pyracantha fortuneana fruit powder and preparation method thereof with anticancer function |
| CN110746521A (en) * | 2019-10-28 | 2020-02-04 | 重庆科技学院 | Method for preparing polyrotaxane crosslinking agent based on β cyclodextrin and product |
| CN111171187A (en) * | 2020-02-12 | 2020-05-19 | 贵州省现代农业发展研究所 | preparation method of butenoic acid- β -cyclodextrin ester |
| CN114133467A (en) * | 2021-12-16 | 2022-03-04 | 科之杰新材料集团浙江有限公司 | Unsaturated esterified monomer and ester low-bleeding polycarboxylate superplasticizer and preparation method thereof |
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