CN101774917B - Method for preparing methyl acetylricinolate - Google Patents
Method for preparing methyl acetylricinolate Download PDFInfo
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- CN101774917B CN101774917B CN 201010106843 CN201010106843A CN101774917B CN 101774917 B CN101774917 B CN 101774917B CN 201010106843 CN201010106843 CN 201010106843 CN 201010106843 A CN201010106843 A CN 201010106843A CN 101774917 B CN101774917 B CN 101774917B
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Abstract
The invention relates to a method for preparing methyl acetylricinolate, which is processed according to the following steps: (1) under the normal pressure condition, adding an ionic liquid catalyst into a mixed liquor of methyl ricinoleate and acetic anhydride, stirring the mixture to carry out acetolysis, wherein the acetolysis temeprature is between the room temperature and 130 DEG C, the reaction time is between 0.1 and 10 hours, the mole ratio of the methyl ricinoleate to acetic anhydride is 1:1.5-2.5, the usage amount of the ionic liquid catalyst occupies more than or equal to 0.1 perent of the methyl ricinoleate by mass, and the ionic liquid catalyst is an alkyl sulfonic acid pyridine ionic liquid with the -SO3H functional group; (2) standing the reaction liquid of the step (1) to separate out the product on the upper layer as the crude methyl acetylricinolate, wherein the catalyst on the lower layer and a small quantity of acetic anhydride can be not processed, but be recycled; and (3) after carrying out reduced pressure distillation on the crude methyl acetylricinolate of step (2), washing to obtain the refined methyl acetylricinolate. The invention has the advantages of simple method, easy operation, short response time, high yield, low corrosion to the equipment and low cost.
Description
Technical field
The present invention relates to a kind of preparation method of methyl acetylricinolate, relating in particular to the ricinolic acid methyl esters is raw material, and ionic liquid is made the method for Preparation of Catalyst methyl acetylricinolate.
Background technology
Methyl acetylricinolate is kind of a faint yellow transparent thick liquid, and is water insoluble, is soluble in ether, ethanol, benzene and grease etc.Can be used as the cold resistant plasticizer of polyvinyl chloride, natural rubber, synthetic rubber, polyvinyl acetate (PVA) etc., improve that they are crisp at low temperatures, hard, be difficult for shortcomings such as softening.Especially it also has advantages such as nontoxic, nonflammable, degradable, can give derivative good performance.Can be used in industries such as the processing various wrapping material that contact with food, toy and medicine equipments, so the development space of methyl acetylricinolate is wide.
At present, the acylation reaction of ricinolic acid methyl esters and aceticanhydride prepares methyl acetylricinolate, is under than higher temperature, does not add catalyzer and reacts [National University of the Inner Mongol's journal, 2006,21 (1): 39-40].Zheng Shunji etc. have reported acetylation (Shaanxi Tech Univ's journal of lanolin (main component is fatty acid triglycercide); 2003; 21 (1): 31～34), adopt no catalysis high temperature (140 ℃) lanolin and aceticanhydride to carry out acetylization reaction, transformation efficiency 84.7%.Because the generation of alkoxide and dehydration reaction at high temperature can take place hydroxyl bond in the ricinolic acid methyl esters, the purity of product is descended; Contain in the ricinolic acid methyl esters molecule one unsaturated two strong, the processing of need decolouring of polymerization reaction take place easily at high temperature, and influence yield and the color and luster of reactor product, product; Owing to react under than higher temperature, energy consumption is bigger.
Therefore above-mentioned deficiency still has is worth improved place.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art; a kind of reaction efficiency height is provided; temperature of reaction is low; the method of the catalysis ricinolic acid methyl esters acetylization reaction of environmental friendliness, high reactivity, catalyzer reusable edible; it is non-volatile, can be recycled and advantage such as can modify flexibly; overcome the severe corrosive of other catalyzer and the shortcoming of contaminate environment, realized the object of the invention.
The acetylize chemical equation of ricinolic acid methyl esters of the present invention and aceticanhydride is as follows:
The object of the invention realizes, selects to adopt band-SO
3The alkylsulphonic acid pyridines ionic liquid of H functional group is made catalyzer, the method for catalytic preparation methyl acetylricinolate, and described side carries out successively as follows:
(1) in condition of normal pressure, ionic-liquid catalyst is joined in the mixed solution of ricinolic acid methyl esters and aceticanhydride, stir, carry out the acetyl reaction; Temperature of reaction is room temperature～130 ℃, and preferable reaction temperature is 60-80 ℃; Reaction times 0.1-10h, reaction pressure is normal pressure;
The mol ratio 1 of wherein said acyl ricinolic acid methyl esters and aceticanhydride: 1.5-2.5; Wherein said ionic-liquid catalyst usage quantity accounts for the ricinolic acid methyl esters in mass 〉=0.1%; Preferably be 0.5-1.5% in mass, wherein said band-SO
3The alkylsulphonic acid pyridines ionic liquid of H functional group, its structural formula is respectively:
Alkyl R in the following formula ionic-liquid catalyst wherein
0Alkyl carbon chain long be 1-10 carbon atom, R
1-R
5The long 0-20 of an alkyl carbon chain carbon atom, R
0-R
5Middle carbon atom surpasses 10, and then catalytic performance descends, and does not have practical use.Negatively charged ion X in the ionic-liquid catalyst
-Be HSO
4 -
Preferred ion liquid catalyst molecular formula is as follows:
N-ethylpyridine hydrosulfate ionic liquid:
N-propyl group pyridine hydrosulfate ionic liquid:
N-butyl-pyridinium hydrosulfate ionic liquid:
N-pentyl pyridine hydrosulfate ionic liquid
(2) with the reaction solution standing demix of above-mentioned steps (1), telling the upper strata product is thick methyl acetylricinolate, and lower floor's catalyzer and a small amount of aceticanhydride can be handled, and reuse;
(3) the thick methyl acetylricinolate of step (2) is carried out underpressure distillation after, wash again refining methyl acetylricinolate.
Reaction raw materials is same as the prior art, can be the ricinolic acid methyl esters that adopts usually.
Advantage of the present invention is:
1, the present invention adopts alkylsulphonic acid pyridines ionic liquid as catalyzer, and catalyst consumption is few, can catalyzer and product phase-splitting automatically after reaction finishes, after ionic liquid reclaims, can handle and can reuse, activity slightly descends, and can replenish the small amount of ionic liquid body.
2, catalyzer can fully contact with reactant in the reaction process, has reduced the acetylize temperature to a certain extent.Because do not need too high-temperature, avoided hydroxyl bond in the ricinolic acid methyl esters that the generation of alkoxide and dehydration reaction at high temperature takes place, can also improve the purity of product.
3, after the thick methyl acetylricinolate underpressure distillation that makes goes out unreacted aceticanhydride, washing, after the dehydration, product color is bright, the processing of needn't decolouring.
4, the inventive method is simple, easy handling, and the reaction times is short, and the yield height is little to equipment corrosion, both can reduce the energy, can reduce cost again.The acetylization reaction temperature that its outstanding advantage is the ricinolic acid methyl esters is reduced to 60-80 ℃ from 140 ℃, has reduced energy consumption, and the color and luster of product is improved
The interval value that the present invention provides not is the accurate end value of mathematical concept, and test and Selection has association when interval, and suitably departing from end value is not cannot.
Description of drawings
Fig. 1 is ionic-liquid catalyst repeated experiment result of the present invention.
Embodiment
The comparative example: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2), do not add catalyzer, reacted 2 hours down at 140 ℃, transformation efficiency is 83.4%.
Embodiment 1: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2), catalyst n-propyl group pyridine-sulfonic acid hydrosulfate ionic liquid add-on is 1.5%, reacts 1 hour down at 70 ℃, and transformation efficiency reaches 93.37%
Embodiment 2: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2), catalyst n-propyl group pyridine-sulfonic acid hydrosulfate ionic liquid add-on is 0.5%, reacts 2 hours down at 80 ℃, and transformation efficiency reaches 96.21%
Embodiment 3: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2), catalyst n-propyl group pyridine-sulfonic acid hydrosulfate ionic liquid add-on is 1%, reacts 3 hours down at 60 ℃, and transformation efficiency reaches 90.36%
Embodiment 4: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2.5), catalyst n-butyl-pyridinium sulfonic acid hydrosulfate ionic liquid add-on is 1%, reacts 1 hour down at 70 ℃, and transformation efficiency reaches 93.64%
Embodiment 5: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2.5), catalyst n-propyl group pyridine-sulfonic acid hydrosulfate ionic liquid add-on is 0.5%, reacts 2 hours down at 60 ℃.Transformation efficiency reaches 90.31%
Embodiment 6: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 2.5), catalyst n-propyl group pyridine-sulfonic acid hydrosulfate ionic liquid add-on is 1.5%, reacts 3 hours down at 80 ℃.Transformation efficiency reaches 96.35%
Embodiment 7: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 1.5), catalyst n-pentyl pyridine hydrosulfate ionic liquid add-on is 0.5%, reacts 1 hour down at 60 ℃.Transformation efficiency reaches 85.59%
Embodiment 8: in the 0.25L reactor, add ricinolic acid methyl esters and diacetyl oxide (molar mass was than 1: 1.5), catalyst n-ethylpyridine hydrosulfate ionic liquid add-on is 1%, reacts 2 hours down at 70 ℃.Transformation efficiency reaches 90.39%
Embodiment 9: except for the following differences, all the other are identical with above-mentioned example 6, investigate catalyzer repeated experiment result.After as can be seen from the figure ionic liquid reclaims, can handle and can reuse, activity slightly descends, and can replenish the small amount of ionic liquid body and improve its activity.
Claims (1)
1. method for preparing methyl acetylricinolate is characterized in that being undertaken by following step:
(1) in condition of normal pressure, ionic-liquid catalyst is joined in the mixed solution of ricinolic acid methyl esters and aceticanhydride, stir, carry out the acetyl reaction; Reaction times 0.1-10h; Temperature of reaction is 60-80 ℃;
The mol ratio 1:1.5-2.5 of wherein said ricinolic acid methyl esters and aceticanhydride;
(2) with the reaction solution standing demix of above-mentioned steps (1), telling the upper strata product is thick methyl acetylricinolate, and lower floor's catalyzer and a small amount of aceticanhydride can be handled, and reuse;
(3) the thick methyl acetylricinolate of step (2) is carried out underpressure distillation after, wash again refining methyl acetylricinolate;
Wherein said ionic-liquid catalyst usage quantity accounts for the ricinolic acid methyl esters and is 0.5-1.5% in mass; The ionic-liquid catalyst molecular formula is as follows: N-ethylpyridine hydrosulfate ionic liquid:
Perhaps N-propyl group pyridine hydrosulfate ionic liquid:
Perhaps N-butyl-pyridinium hydrosulfate ionic liquid:
Perhaps N-pentyl pyridine hydrosulfate ionic liquid
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| CN102382015B (en) * | 2011-08-02 | 2013-10-30 | 常州大学 | Method for preparing sulfated methyl ester by ionic liquid catalysis method |
| CN105481690A (en) * | 2015-12-01 | 2016-04-13 | 江苏怡达化学股份有限公司 | Benzoyl ricinoleic acid binary alcohol ether ester and synthetic method thereof |
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| CN113234394B (en) * | 2021-06-08 | 2023-03-14 | 仲恺农业工程学院 | Polyester-based hydrogenated rosin, preparation method and application thereof |
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Address after: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee after: Jiangsu Polytechnic University Address before: 213016 Baiyun District, Changzhou, Jiangsu Patentee before: Jiangsu Polytechnic University |
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