阅读说明：本技术 一种石榴酸的制备方法 (A kind of preparation method of punicic acid ) 是由 姚倩 郭晓强 赵琦 杨萍 申元福 李小红 周闯 于 2019-09-03 设计创作，主要内容包括：本发明公开了一种石榴酸的制备方法,具体制备过程是：取石榴籽油混合脂肪酸,加入有机溶剂溶解,在-30～-10℃下冷冻0.5～2h,若全部冻结为固态,则取固态冷冻物,室温下放置,分段收集熔化物,靠后熔出的部分为富含石榴酸的片段,将富含石榴酸的片段除去有机溶剂即得高纯度石榴酸。本发明利用石榴酸与其他脂肪酸熔点的差异达到分离目的,具有生产周期短、收率高、成本低、操作简便等优点。(The invention discloses a kind of preparation methods of punicic acid, specific preparation process is: taking granada seed oil fatty acid mixed, organic solvent dissolution is added, 0.5~2h is freezed at -30~-10 DEG C, if all freezing to take solid-state frozen material for solid-state, it places at room temperature, Fractional Collections melt, the part melted out rearward are the segment rich in punicic acid, and the segment that will be enriched in punicic acid removes organic solvent up to high purity punicic acid.The present invention, which is reached using punicic acid with the difference of other fatty acid fusing points, separates purpose, has many advantages, such as with short production cycle, high income, at low cost, easy to operate.)

1. a kind of preparation method of punicic acid, it is characterised in that: granada seed oil fatty acid mixed is taken, organic solvent dissolution is added, 0.5~2h is freezed at -30~-10 DEG C, if all freezing solid-state scars to be taken, placed at room temperature for solid-state, Fractional Collections Melt, the part melted out rearward are the segment rich in punicic acid, and the segment that will be enriched in punicic acid removes organic solvent up to high Purity punicic acid.

2. the preparation method of punicic acid according to claim 1, it is characterised in that: contain gained high purity punicic acid Amount detection will carry out again primary or two through high purity punicic acid obtained by a Freeze crystallization if content not up to requires Secondary Freeze crystallization, until pomegranate acid content reaches requirement.

3. the preparation method of punicic acid according to claim 1 or 2, it is characterised in that: the part melted out rearward is Refer to that last 30%~60% melts out object.

4. the preparation method of punicic acid according to claim 1, it is characterised in that: if granada seed oil fatty acid mixed is dissolved in After organic solution and chilled processing, only partially freeze then to filter for solid-state, collects the residue on filter up to punicic acid.

5. the preparation method of high purity punicic acid according to claim 1 or 4, it is characterised in that: the granada seed oil is mixed It closes fatty acid and is made after saponification, acidification, extraction and removing organic solvent by granada seed oil.

6. the preparation method of high purity punicic acid according to claim 1 or 4, it is characterised in that: the organic solvent is One of acetone, dehydrated alcohol, methanol, n-hexane, petroleum ether or more than one combination.

7. the preparation method of high purity punicic acid according to claim 1 or 4, it is characterised in that: the organic solvent Additional amount is 8~20 times of granada seed oil fatty acid mixed weight.

Technical field

The present invention relates to the preparation methods of a kind of preparation method of punicic acid, especially high purity punicic acid.

Background technique

Punicic acid is main fatty acid contained in granada seed oil, accounts for 60% or more of fatty acid gross weight.Punicic acid tool There are reducing blood lipid, blood pressure lowering, prevention cardiovascular and cerebrovascular disease, antibacterial and the multiple efficacies such as anti-inflammatory, is that granada seed oil plays pharmacological action Most important component.Punicic acid is isolated and purified out from granada seed oil, helps to improve activity and curative effect, agent is taken in reduction Amount, facilitates preparations shaping.

Punicic acid exists in the form of glyceride and phosphatide in granada seed oil, needs first through saponification by granada seed oil In aliphatic ester be decomposed into fatty acid, the punicic acid of high-purity is further isolated from fatty acid mixed.Common point It is pillar layer separation from technology, mixture passes through the chromatographic column of opposed polarity, through elution and Fractional Collections, can obtain high-purity Target compound, disadvantage be time-consuming, target compound is often adsorbed by chromatographic column, leads to low yield；Cross the organic solvent of column Dosage is big, recycles after need to often recycling.Patent " a method of produce high purity punicic acid " (patent No. ZL 200510012802.5) urea adduct method is used to prepare high purity punicic acid, pass through supercritical carbon dioxide extraction method first Obtain granada seed oil, then by granada seed oil through saponification, acidification and extraction and etc. obtain granada seed oil fatty acid mixed after processing； Urea dissolution is added in fatty acid mixed in methyl alcohol, freezes 10h or more, filters, is precipitated as urea-containing saturated fatty acid And monounsaturated fatty acids, filtrate are punicic acid methanol solution, after removing methanol, pomegranate acid content is up to 92%.Urea clathrate The principle of method are as follows: urea is easily in conjunction with saturated fatty acid and monounsaturated fatty acids, after chilled, is divided into solid-liquid two condition, solid In the main conjugate containing urea and saturated fatty acid and monounsaturated fatty acids, be enriched containing two or two or more in filtrate The polyunsaturated fatty acid of double bond, after removing urea and organic solvent, the content of polyunsaturated fatty acid is significantly improved.This method Disadvantage are as follows: it is practical also containing the urea dissolved on a small quantity in filtrate, need acidified and extraction process that can remove urea (Zhao Duckweed waits urea adduct method to study oil engineering to the enrichment of sunflower oil Linoleic acid, 2015,12,31-34.), operation compared with To be cumbersome, punicic acid loss is larger in extraction process, causes last yield not high.In addition, cooling time is in 10h or more, production Period is long, and efficiency is relatively low.

It yet there are no the report for separating punicic acid from granada seed oil fatty acid mixed using freezing and crystallizing method.

Summary of the invention

The purpose of the present invention is to provide a kind of time-consumings short, at low cost, high income and high purity punicic acid easy to operate Preparation method.

The preparation method of punicic acid provided by the invention is: granada seed oil fatty acid mixed taken, organic solvent dissolution is added, 0.5~2h is freezed at -30~-10 DEG C, if all freezing solid-state scars to be taken, placed at room temperature for solid-state, Fractional Collections Melt, the part melted out rearward are the segment rich in punicic acid, and the segment that will be enriched in punicic acid removes organic solvent up to high Purity punicic acid.

Further, gained high purity punicic acid is subjected to content detection, it, will be through primary cold if content not up to requires Freeze high purity punicic acid obtained by crystallization treatment and carry out primary or secondary Freeze crystallization again, until pomegranate acid content reaches and wants It asks.

Further, the part melted out rearward refers to that last 30%~60% melts out object.

Further, if after granada seed oil fatty acid mixed is dissolved in organic solution and chilled processing, only partially freeze for Solid-state then filters, and collects the residue on filter up to punicic acid.

Further, the organic solvent is one of acetone, dehydrated alcohol, methanol, n-hexane, petroleum ether or one kind Above combination.

Further, the additional amount of the organic solvent is 8~20 times of granada seed oil fatty acid mixed weight.

Further, the granada seed oil fatty acid mixed through saponification, acidification, extraction and is removed organic molten by granada seed oil It is made after agent, comprises the concrete steps that: taking granada seed oil, the KOH- that concentration is 3% to 10% is added in the ratio of 1:10 to 1:20 95% ethanol solution is heated to reflux 1-2h under 70-90 DEG C of water-bath, adds appropriate warm water dissolution saponified, is cooled to room temperature, with acid PH to 2-4 is adjusted, 10-30 min is stirred, keeps fatty acid sufficiently free, then extract fatty acid therein with organic solvent；It has taken Solvent layer, it is neutral for being washed with warm water to washing lotion, anhydrous sodium sulfate drying is added, filtration is removed in evaporation on Rotary Evaporators Go organic solvent to get fatty acid mixed.It is described extract fatty acid organic solvent, be petroleum ether, n-hexane, methylene chloride, One of ethyl acetate, hexamethylene or more than one combination.

Unsaturated fatty acid contained in granada seed oil mainly includes oleic acid, linoleic acid and punicic acid, they are 18 Carbon enoic acid contains one, two and three double bond respectively, and ethylene linkage causes intermolecular binding force to increase, freezing point decline, and organic molten After -10 DEG C or less freezings, through being placed at room temperature for, saturated fatty acid is melted with organic solvent at first because fusing point is higher, is then for agent Oleic acid containing double bond and the linoleic acid containing two double bonds, finally melting is the punicic acid containing three double bonds, passes through segmentation The melt of fatty acid mixed and organic solvent is collected, and removes organic solvent rich in pomegranate acid fragment for what is melted out rearward, i.e., It can get punicic acid.

The present invention, which is reached using punicic acid with the difference of other fatty acid fusing points, separates purpose, only comprising freezing, fusing and Except three steps of solvent, cooling time is in 2h hereinafter, having many advantages, such as with short production cycle, high income, at low cost, easy to operate. Experiments have shown that punicic acid purity can be improved by 78% to 85% or more, through secondary freezing and crystallizing, punicic acid through a freezing and crystallizing Purity can reach 89% or more (used granada seed oil be homemade, pomegranate acid content is 75% or more).

Detailed description of the invention

Fig. 1 is the GC figure for finally melting out segment in embodiment 1 after a freezing and crystallizing.

Fig. 2 is the GC figure for finally melting out segment in embodiment 1 after secondary freezing and crystallizing.

Fig. 3 is the GC figure for finally melting out segment in embodiment 1 after freezing and crystallizing three times.

In figure: 1, capric acid (internal standard)；2, palmitinic acid；3, linoleic acid；4, oleic acid；5, stearic acid；6, punicic acid；7-9, pomegranate Acid isomer.

Specific embodiment

For a better understanding of the present invention, present invention is further described in detail combined with specific embodiments below, but this The protection scope of invention is without being limited thereto.