CN101774917B - Method for preparing methyl acetylricinolate - Google Patents

Method for preparing methyl acetylricinolate Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
ionic liquid
acetylricinolate
reaction
methyl
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN 201010106843
Other languages
Chinese (zh)
Other versions
CN101774917A (en
Inventor
李为民
邱玉华
姚超
李成燕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liyang Chang Technology Transfer Center Co., Ltd.
Original Assignee
Jiangsu Polytechnic University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Polytechnic University filed Critical Jiangsu Polytechnic University
Priority to CN 201010106843 priority Critical patent/CN101774917B/en
Publication of CN101774917A publication Critical patent/CN101774917A/en
Application granted granted Critical
Publication of CN101774917B publication Critical patent/CN101774917B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

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

A kind of method for preparing methyl acetylricinolate
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:
Figure GSA00000022161500021
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:
Figure GSA00000022161500022
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:
Figure GSA00000022161500023
N-propyl group pyridine hydrosulfate ionic liquid:
Figure GSA00000022161500024
N-butyl-pyridinium hydrosulfate ionic liquid:
Figure GSA00000022161500025
N-pentyl pyridine hydrosulfate ionic liquid
Figure GSA00000022161500031
(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:
Figure 2010101068431100001DEST_PATH_IMAGE001
Perhaps N-propyl group pyridine hydrosulfate ionic liquid:
Figure 764385DEST_PATH_IMAGE002
Perhaps N-butyl-pyridinium hydrosulfate ionic liquid:
Figure DEST_PATH_IMAGE003
Perhaps N-pentyl pyridine hydrosulfate ionic liquid
Figure 556892DEST_PATH_IMAGE004
CN 201010106843 2010-02-05 2010-02-05 Method for preparing methyl acetylricinolate Active CN101774917B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010106843 CN101774917B (en) 2010-02-05 2010-02-05 Method for preparing methyl acetylricinolate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010106843 CN101774917B (en) 2010-02-05 2010-02-05 Method for preparing methyl acetylricinolate

Publications (2)

Publication Number Publication Date
CN101774917A CN101774917A (en) 2010-07-14
CN101774917B true CN101774917B (en) 2013-07-17

Family

ID=42511534

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010106843 Active CN101774917B (en) 2010-02-05 2010-02-05 Method for preparing methyl acetylricinolate

Country Status (1)

Country Link
CN (1) CN101774917B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408335A (en) * 2010-09-21 2012-04-11 中国科学院福建物质结构研究所 Synthetic method of p-fluorophenyl acetate
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
CN110692572B (en) * 2019-11-22 2021-09-21 中山市农业科技推广中心 Float automatic dispensing equipment of formula full angle fish fodder
CN110999839B (en) * 2019-12-18 2021-11-05 淮北泽兰科技有限责任公司 Pond feeding and throwing equipment
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

Also Published As

Publication number Publication date
CN101774917A (en) 2010-07-14

Similar Documents

Publication Publication Date Title
CN101774917B (en) Method for preparing methyl acetylricinolate
CN100531904C (en) Catalyst used for catalytic synthesis for dimethyl carbonate directly from methanol and carbon dioxide, and preparation and using method thereof
WO1985003504A3 (en) Process for making substituted carboxylic acids and derivatives thereof
CN101429356A (en) General adhesion promoter for paint and method of producing the same
CN102993246A (en) Method for synthesizing isopropyl-beta-D-thiogalactoside
US4675434A (en) Process for producing phthalic acid esters
AU2019299299B2 (en) Method for lowering iodine value of glyceride
CN1307188C (en) Method for extracting sucrose fatty acid ester
CN105254503A (en) Preparation method of dioctyl terephthalate
CN102633640B (en) Integrated production technique of acetyl tributyl citrate (ATBC)
CN109569579B (en) Method for preparing tributyl citrate from attapulgite clay immobilized tungsten oxide
CN102382148A (en) Production technology of bis(triphenylphosphine) palladium chloride
US20110077426A1 (en) Method for synthesis of o-diphenylphosphinobenzoic acid
CN101177396A (en) Method for synthesizing ester in dodecyl benzene sulfonic acid reverse micro emulsion
CN107337689A (en) A kind of synthetic method of alkyl phosphate monoester
CN100506834C (en) Method for preparing alkanoyl tannic acid ester
CN101735287B (en) Method for preparing 2, 3, 4, 6-tetraacylglucopyranose
CN86106683A (en) method for synthesizing sucrose fatty acid ester
CN101070282A (en) Process for room-temperature ion liquid-catalytic preparation of ethyl linoleate
CN105503594A (en) Method for preparing acetyl tributyl citrate by nano scale intercalation hydrotalcite catalyst
CN105384630B (en) Hexylene glycol ester of citric acid three and preparation method thereof
CN108084064B (en) Novel preparation method of D- (-) -tartaric acid
CN106944112A (en) One kind is used for high acid value waste oil fat pre-esterification solid acid catalyst
CN102895912A (en) Gemini surfactant and preparation method thereof
CN113603621B (en) Preparation method of mercaptopropionate series compounds

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee
CP02 Change in the address of a patent holder

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

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20151021

Address after: Daitou town of Liyang City Ferry Street 213311 Jiangsu city of Changzhou province 8-2 No. 7

Patentee after: Liyang Chang Technology Transfer Center Co., Ltd.

Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1

Patentee before: Jiangsu Polytechnic University