CN104496813A - Acylglycerol cinnamate antioxidant and synthesis method thereof - Google Patents
Acylglycerol cinnamate antioxidant and synthesis method thereof Download PDFInfo
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- CN104496813A CN104496813A CN201410713112.1A CN201410713112A CN104496813A CN 104496813 A CN104496813 A CN 104496813A CN 201410713112 A CN201410713112 A CN 201410713112A CN 104496813 A CN104496813 A CN 104496813A
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- antioxidant
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- styracin
- cinnamate
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- 0 C*(CC*C(C=Cc1ccccc1)=[U])OC(C=Cc1ccccc1)N Chemical compound C*(CC*C(C=Cc1ccccc1)=[U])OC(C=Cc1ccccc1)N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3481—Organic compounds containing oxygen
- A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
- A23L3/3517—Carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention relates to an acylglycerol cinnamate antioxidant and a synthesis method thereof and belongs to the technical field of production of food additives. The synthesis method of the acylglycerol cinnamate antioxidant comprises the following steps of: carrying out interesterification on ethyl cinnamate and glycerol in the presence of a composite catalyst, heating, reducing pressure, removing ethanol which is a byproduct, and separating a reaction solution centrifugally to obtain a product which is acylglycerol cinnamate antioxidant, wherein the product conversion rate is more than 98%, and the reaction solution does not need to be purified by crystallizing with a solvent. The composite catalyst is prepared by compounding an ionic liquid catalyst with an inorganic catalyst. The acylglycerol cinnamate antioxidant provided by the invention can be applied to the food industry, and the synthesis method of the acylglycerol cinnamate antioxidant has the advantages of high reaction speed and mild reaction conditions. In addition, the reaction time can be shortened greatly, and the catalyst can be recycled easily.
Description
Technical field
the invention provides a kind of antioxidant and synthetic method thereof, particularly a kind of styracin acyl glyceride antioxidant and synthetic method thereof, belong to foodstuff additive production technical field.
Background technology
tellurian biology needs oxygen to survive, but oxygen is again a kind of molecule of high reaction activity simultaneously, organism can be destroyed by producing reactive oxygen species, so establish a set of complex networks system be made up of oxidation resistant meta-bolites and enzyme in organism, come from oxidative damage by the Metabolic Intermediate of Wheat Protein and the coordinated between product and enzyme, antioxidant arises at the historic moment.
antioxidant prevents or delays Food Oxidation, the stability improving food and the material extending storage period.Food antioxidant can be divided into oil-soluble inhibitor and water soluble antioxidant by its dissolving properties.Oil-soluble inhibitor can be dissolved in grease, can play antioxygenation well, prevent its oxidative rancidity and rusting phenomenon to grease with containing fatty foods.Conventional has butyl base phenylmethylether, butylated hydroxytoluene, Nutgalls propyl propionate etc.Water soluble antioxidant can be water-soluble, and be mainly used in Food Oxidation variable color, conventional is Vitamin C acids, different anti-hematic acid and salt, phytic acid, disodium ethylene diamine tetraacetate, amino acids, peptide class, spice and glycitols etc.As antioxidant, must meet the following requirements: to human body fanout free region as far as possible; Bad taste, smell and color can not be had; Lower concentration, namely applicable; If add in grease then for fat-soluble; The resistance of oxidation still can remained valid after processing; Need rapid efficient and cost-effective.Antioxidant is widely used in the fields such as vegetables oil, animal tallow, chewing gum, soup stock, food flavouring, VITAMIN, cereal foods, kernel, essence, sausage, animal-feed, cereal foods packaging, candy, instant potato, fragrance matter, yeast, makeup.
styracin, have another name called β-cinnamic acid, cinnamic acid, from Cortex Cinnamomi or the isolated organic acid of st-yrax, there is good anti-oxidant activity, have very strong scavenging(action) to hydrogen peroxide, superoxide radical, hydroxy radical qiao, cinnamic acid derivative antioxidant can exist with the form of free acid or acid radical anion in the solution.At present, Japan has allowed it to make foodstuff additive, can also be applied in food as antioxidant, and it has good restraining effect as the oxidation of becoming sour of antioxidant to oil-based foods.But the low ester dissolubility of styracin limits its application in food.
at present; most research is all the biological enzyme synthesizing cinnamic acid acyl group structure ester of traditional strong acid catalyst or costliness; little to the research catalyzed and synthesized of " green " ionic liquid, more without ionic liquid and the catalyst compounded report to fat-soluble styracin acyl group structure ester of organic catalyst.
chinese invention " a kind of foodstuff additive and preparation method thereof ", application number 201210077490.6 discloses a kind of styracin D-araboascorbic acid ester and preparation method thereof, react by styracin and thionyl chloride and generate cinnamyl chloride, cinnamyl chloride reacts with D-saccharosonic acid and generates styracin D-saccharosonic acid ester, as food antioxidant.
Summary of the invention
the object of the invention is to provide a kind of styracin acyl glyceride antioxidant and synthetic method thereof, and the method obtains easily separated, coloury product, and can realize reusing of catalyzer.
to achieve these goals, the present invention is achieved through the following technical solutions:
under the effect of composite catalyst; ethyl cinnamate and glyceryl ester carry out transesterify; by heating, pressurization; slough coproduct ethanol; reaction terminates rear low-temperature centrifugation and is separated and obtains target product and can catalyzer as used herein; the object product obtained is the mixture of styracin acyl glyceride, and its structural formula is:
wherein R is the straight or branched alkane of C1-C22, the carbochain on R and double bond number identical or different.
described composite catalyst is the compound of ionic-liquid catalyst and organic catalyst; Ionic liquid is acidic ion liquid, and organic catalyst is tin, palladium, nickel carboxylate.
described composite catalyst is any composite use in ionic-liquid catalyst and organic catalyst.
the existing efficient catalyzed reaction effect of composite catalyst of the present invention has again good product color protected effect; after transesterification reaction terminates; reaction solution is colourless transparent liquid; conversion rate of products is greater than 98.5%; can obtain object product after only needing simple centrifugation, and catalyzer directly can be reused.Save energy, reduces waste discharge.
the composite weight ratio of described ionic-liquid catalyst and organic catalyst is 1-10:1, recommends than being 5:1.Of the present invention catalyst compounded can be the combination collocation of any one or a few acidic ion liquid and any one or a few tin, palladium, nickel carboxylate catalyzer.
the add-on of the composite catalyst in ester-exchange reaction is the 0.05-3% of laurate.Optimal addn is 0.1-1%.Transesterification reaction temperature 60-100 DEG C, recommendation response temperature 70-80 DEG C.
glyceryl ester charging capacity under normal circumstances in transesterification reaction is the 50-150% of laurate weight ratio.
reaction of the present invention is under reduced pressure carried out, and pressure is 500-20Pa, and optimum pressure is 200-50Pa.
transesterification reaction time 2-18 hour, optimum reacting time 6-12 hour.
after transesterification reaction, reaction solution without the need to adopting complicated separation purifying technique, directly at temperature 5-15 DEG C, 4000-10000r/min, centrifugal 2-10min, upper strata namely for the purpose of product, and lower floor's composite catalyst can directly apply in lower secondary response and reuses.Conventional art strong acid catalyst meeting etching apparatus, product color is dark, and product needs molecular distillation to be separated, and process is complicated, and power consumption is large, and pollution is heavy.
the present invention has following advantages:
(1) conversion rate of products is high, the time is short, is colourless transparent liquid, and product separation is simple, consumes energy low, pollutes little;
(2) avoid the radiation of traditional strong acid catalyst to equipment, reduce experimental cost;
(3) compare conventional catalyst reaction, catalyzer is reusable.
Embodiment
be described in further details the present invention below by example, these examples are only used for the present invention is described, do not limit the scope of the invention.
embodiment 1
100 grams of ethyl cinnamate and 50 grams of soybean oil join and are equipped with in the reaction flask of magnetic stirring apparatus, add the good composite catalyst of configured in advance 10 grams (1-sulfonic acid butyl-3-Methylimidazole tosilate and the different monooctyl ester di-n-butyl tin of two maleic acid lists again, composite ratio is 5:1), vacuum pump using circulatory water is to system 98kPa vacuum tightness, Heating temperature is 75 DEG C, reaction 8h.Reaction solution is the centrifugal 6min of 8000r/min at 10 DEG C, is separated and obtains upper strata object product and lower catalyst agent.
under this reaction conditions, obtain product 127.5g, product final yield is 85%.
embodiment 2
90 grams of vinyl cinnamates and 40 grams of soybean oil join and are equipped with in the reaction flask of magnetic stirring apparatus, add the good composite catalyst of configured in advance 8.5 grams (1-sulfonic acid butyl-3-Methylimidazole sulfonate and two maleic acid list isobutyl ester di-n-butyl nickel again, composite ratio is 7:1), vacuum pump using circulatory water is to system 50kPa vacuum tightness, Heating temperature is 85 DEG C, reaction 9.5h.Reaction solution is the centrifugal 3min of 10000r/min at 6 DEG C, is separated and obtains upper strata object product and lower catalyst agent.
under this reaction conditions, obtain product 107.1g, product final yield is 89.25%.
embodiment 3(first time example catalyst recycles)
110 grams of ethyl cinnamate and 40 grams of soybean oil join and are equipped with in the reaction flask of magnetic stirring apparatus, add the good composite catalyst of configured in advance 9 grams (1-propyl sulfonic acid-3-Methylimidazole tosilate and lauric acid dibutyitin maleate again, composite ratio is 5:1), vacuum pump using circulatory water is to system 80kPa vacuum tightness, Heating temperature is 65 DEG C, reaction 12h.Reaction solution is the centrifugal 8min of 5000r/min at 8 DEG C, is separated and obtains upper strata object product and lower catalyst agent.
under this reaction conditions, obtain product 120.4g, product final yield is 86%.
in embodiment 4(embodiment 3, catalyzer recycles again)
105 grams of ethyl cinnamate and 60 grams of soybean oil join and are equipped with in the reaction flask of magnetic stirring apparatus, add the good composite catalyst of configured in advance 10.5 grams (1-propyl sulfonic acid-3-Methylimidazole tosilate and lauric acid dibutyitin maleate again, composite ratio is 7:1), vacuum pump using circulatory water is to system 90kPa vacuum tightness, Heating temperature is 75 DEG C, reaction 14h.Reaction solution is the centrifugal 8min of 5000r/min at 10 DEG C, is separated and obtains upper strata object product and lower catalyst agent.
under this reaction conditions, obtain product 141.1g, product final yield is 85.5%.
Claims (9)
1. a laurate antioxidant, is characterized in that: the structural formula of styracin acyl glyceride antioxidant is:
Wherein R is the straight or branched alkane of C1-C22, the carbochain on R and double bond number identical or different.
2. a synthetic method for styracin acyl glyceride antioxidant, is characterized in that: comprise the steps:
Under the effect of composite catalyst, ethyl cinnamate and glyceryl ester carry out transesterify, by heating, decompression, deviate from coproduct ethanol, obtain object product and catalyzer by centrifugation after reaction terminates, and catalyzer just repeatedly uses without the need to process, described composite catalyst is the compound of ionic-liquid catalyst and organic catalyst; Ionic liquid is acidic ion liquid, and organic catalyst is tin, palladium, nickel carboxylate; Described composite catalyst is any composite use in ionic-liquid catalyst and organic catalyst.
3. the synthetic method of a kind of styracin acyl glyceride antioxidant according to claim 2, is characterized in that: ionic-liquid catalyst and the composite weight ratio of organic catalyst are 1:10-5, and catalyst compounded add-on is the 0.05-3% of ethyl cinnamate.
4. the synthetic method of a kind of styracin acyl glyceride antioxidant according to claim 2, is characterized in that: described ethyl cinnamate, is not limited to ethyl cinnamate, also comprises styracin, methyl cinnamate, vinyl cinnamate.
5. the synthetic method of a kind of styracin acyl glyceride antioxidant according to claim 2, is characterized in that: described glyceryl ester is one or more mixing in a sweet ester, DAG and sweet three esters.
6. the synthetic method of a kind of styracin acyl glyceride antioxidant according to claim 2, is characterized in that: described transesterification reaction: temperature is 60-100 DEG C, absolute pressure is 500-20kPa.
7.
a kind of synthetic method of styracin acyl glyceride antioxidant according to claim 2; it is characterized in that: after transesterification reaction, reaction mixture is at temperature 4-10 DEG C; centrifugal speed 5000-1000r/min, centrifugal 2-10min, obtain target product and catalyzer.
8. the synthetic method of a kind of styracin acyl glyceride antioxidant according to claim 2, is characterized in that: the centrifugal catalyzer obtained is reusable.
9.
according to claim 2, a synthetic method for styracin acyl glyceride antioxidant, is characterized in that: the centrifugal target product that obtains without the need to being separated, and does not affect the quality product of antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410713112.1A CN104496813A (en) | 2014-12-02 | 2014-12-02 | Acylglycerol cinnamate antioxidant and synthesis method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410713112.1A CN104496813A (en) | 2014-12-02 | 2014-12-02 | Acylglycerol cinnamate antioxidant and synthesis method thereof |
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| CN104496813A true CN104496813A (en) | 2015-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410713112.1A Pending CN104496813A (en) | 2014-12-02 | 2014-12-02 | Acylglycerol cinnamate antioxidant and synthesis method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218794A (en) * | 1997-10-16 | 1999-06-09 | 三共株式会社 | Process for preparing cinnamate |
| CN1327379A (en) * | 1999-10-01 | 2001-12-19 | 欧莱雅 | Method for improving UV radiation stability of photosensitive sunscreen filters |
| CN1481351A (en) * | 2000-12-22 | 2004-03-10 | ����µ��ɷ�����˾ | Malodor counteractant compsns |
-
2014
- 2014-12-02 CN CN201410713112.1A patent/CN104496813A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218794A (en) * | 1997-10-16 | 1999-06-09 | 三共株式会社 | Process for preparing cinnamate |
| CN1327379A (en) * | 1999-10-01 | 2001-12-19 | 欧莱雅 | Method for improving UV radiation stability of photosensitive sunscreen filters |
| CN1481351A (en) * | 2000-12-22 | 2004-03-10 | ����µ��ɷ�����˾ | Malodor counteractant compsns |
Non-Patent Citations (1)
| Title |
|---|
| THOMAS H. SCHULTZ, ET AL.: ""Turkey Mullein Volatile Constituents"", 《J. AGRIC. FOOD.CHEM.》 * |
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Application publication date: 20150408 |