CN112778135A - Preparation method of polyglycerol ricinoleate - Google Patents
Preparation method of polyglycerol ricinoleate Download PDFInfo
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- CN112778135A CN112778135A CN202110048336.5A CN202110048336A CN112778135A CN 112778135 A CN112778135 A CN 112778135A CN 202110048336 A CN202110048336 A CN 202110048336A CN 112778135 A CN112778135 A CN 112778135A
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- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention discloses a preparation method of polyglycerol ricinoleate, which comprises the following steps: glycerol is subjected to an alkali-catalyzed dehydrocondensation reaction to produce polyglycerol, and polyglycerol and ricinoleic acid are subjected to an esterification reaction to produce polyglycerol ricinoleate. The step of subjecting glycerol to an alkali-catalyzed dehydrocondensation reaction to produce polyglycerol comprises a first dehydrocondensation reaction with a first basic catalyst and a second dehydrocondensation reaction with a second basic catalyst and the step of subjecting polyglycerol to an esterification reaction with ricinoleic acid to produce polyglycerol ricinoleate comprises a first esterification reaction with a third basic catalyst and a second esterification reaction catalyzed by an enzyme. By the method, the occurrence of side reactions and the generation of byproducts are reduced, the yield of the target product is improved, the process flow is obviously simplified, and the process cost is reduced.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of polyglycerol ricinoleate.
Background
Polyglycerol Fatty Acid Ester (PGFE for short) is a novel, efficient and excellent-performance nonionic surfactant and is prepared by esterifying Polyglycerol and Fatty Acid. The traditional surfactant not only has bad influence on the environment when in use, but also produces rather depending on petrochemical products, the synthetic raw materials of PGFE are easy to obtain, and glycerin and animal and plant lipids are renewable energy sources, most importantly, the surfactant is non-toxic and harmless, can be biodegraded, and has good application prospect.
The polyglycerin fatty acid ester is an ester of polyglycerin and a fatty acid, and its structure differs depending on the degree of polymerization of glycerin, the kind of fatty acid, and the degree of esterification. The polyglycerol fatty acid ester is a polyhydroxy ester nonionic surfactant, the hydrophilicity of the polyglycerol fatty acid ester is enhanced along with the increase of the polymerization degree of glycerol, and the lipophilicity of the polyglycerol fatty acid ester is changed along with the difference of fatty acid alkyl. By changing the polymerization degree, the kind of fatty acid and the esterification degree of the glycerin, a series of nonionic surfactants with the hydrophile-lipophile balance value between 1 and 16 and suitable for various special purposes can be obtained.
The polyglycerol ester has strong emulsifying, dispersing, permeating and dissolving forces and strong salt, acid and heat resistance, thereby being widely applied to different fields. In the food industry, the polyglycerol ester is confirmed to be a non-toxic and harmless high-safety food additive by food and agriculture organization, world health organization, European Union and some countries of the United states, and can be used for emulsifying dairy products, inhibiting food surface crystallization, adjusting food viscosity and resisting bacteria according to the structural characteristics of the polyglycerol ester. In the daily chemical industry, the polyglycerol ester is used as a detergent, the dirt removing capability is relatively low, but the polyglycerol ester has no toxic or side effect, so the polyglycerol ester is used for washing fruits and vegetables, and the residue after washing is safe for human bodies. The polyglycerol ester has mild performance, does not irritate the skin, is particularly suitable for being added into cosmetics, has good skin touch and strong moisturizing type, and the formed microemulsion can maintain the system stability of the product and is easy to wash. The polyglycerol ester has no toxic or side effect on a human body and good emulsifying capacity, so the polyglycerol ester is used in the aspect of medicine, is compounded with the medicine as an auxiliary agent, improves the medicine absorption rate and enhances the medicine effect. Because of good acid resistance and heat resistance, the polyglycerol ester can be added into resins such as polyoxyethylene or polyolefin as an auxiliary agent to improve the material performance. Along with the rise of greenhouse planting technology, because the inside and outside temperature difference of big-arch shelter leads to the canopy membrane to adsorb the water droplet for the luminousness reduces, and the fog removing agent is urgently needed, and polyglycerol ester then has good defogging effect, adds to the canopy membrane, can produce the antifog membrane of high luminousness.
The current common method for producing polyglycerols is to polymerize glycerin by heating it to high temperatures using NaOH as a catalyst, and the polyglycerols obtained are mixtures of linear, branched and cyclic polyglycerols. Cyclic polyglycerols have lower HLB values than linear polyglycerols, and therefore, cyclic polyglycerols actually act as demulsifying agents rather than emulsifying agents. Moreover, the cyclic polyglycerin and the cyclic polyglycerin extrude polyglycerin (free polyglycerin) in the high monoester product solution to make the reaction system two-phase, so that it becomes very difficult to industrially produce a polyglycerin ester product having a high monoester content.
Polyglycerol ricinoleate is an emulsifier, generally obtained from two raw materials: castor oil and glycerol. Polyglycerol ricinoleate has good thermal stability and no bad smell, and can be used as lipophilic emulsifier, W/O emulsifier. In edible products, polyglycerol ricinoleate also has wide application, can prevent oil and fat from separating and seeping out, and improve the shape retention of candies, and can inhibit the crystallization of the oil and fat in chocolate, prevent the chocolate from frosting, and improve the brittleness and shape retention of the chocolate when being used for chocolate production. Polyglycerol ricinoleates commonly used in the industry at present include polyglycerol-10 polyricinoleate and polyglycerol-3 polyricinoleate. The production of polyglycerol polyricinoleate generally requires the following three steps: polymerizing castor oil into long chains; polymerizing glycerol to form polyglycerol; and finally, carrying out esterification reaction on the two polymers, wherein the final product is polyglycerol polyricinoleate.
Chinese patent publication CN102559390A discloses a method for preparing medium-chain polyglycerol fatty acid ester, which comprises using camphor tree seed kernel oil as raw material, hydrolyzing degummed and dehydrated camphor tree seed kernel oil, saponifying and acidifying; putting the separated medium-carbon chain fatty acid and polyglycerol with different polymerization degrees into an esterification reactor, and adding a proper amount of solid alkali KOH/Al203Introducing nitrogen to protect the catalyst, heating and stirring to perform esterification reaction; the obtained medium-carbon chain polyglycerol fatty acid ester enters a deacidification reactor for reaction to obtain medium-carbon chain polyglycerol fatty acid ester with the yield of 95 percent; and (3) placing the deacidified medium-chain fatty acid polyglycerol ester into a dehydration decolorizer to obtain the medium-chain fatty acid polyglycerol ester with the yield of 98%. The invention uses solid alkali KOH/Al203Is used as an esterification catalyst to synthesize medium-chain polyglycerol fatty acid ester.
Chinese patent publication CN106365988A discloses a preparation method of polyglycerol ester, which specifically comprises the following steps: 1) pumping accurately weighed glycerol into a reaction kettle, starting a heating device and a stirring device, and controlling the temperature of the materials to be 65-95 ℃; slowly adding the catalyst A into the reaction kettle, introducing nitrogen, controlling the vacuum degree in the reaction kettle to be 0.01-0.03 MPa, gradually heating to raise the temperature of materials in the reaction kettle to 200-280 ℃, controlling the vacuum degree to be 0.02-0.09 MPa, and keeping the temperature and stirring for 90-180 minutes; stopping heating after heat preservation is finished, opening a cooling water valve, adjusting the vacuum degree to 0.03Mpa, reducing the temperature of the material to 100-120 ℃ under the protection of nitrogen, emptying to eliminate negative pressure, and sampling and detecting; 2) pumping myristic acid into a reaction kettle, starting a stirring device, and adding a catalyst B into the reaction kettle; starting vacuum, controlling the vacuum degree to be 0.02-0.05 MPa, heating to 130-160 ℃, preserving heat and stirring for 20-50 minutes; continuously heating to 175-195 ℃, controlling the vacuum degree at 0.06-0.09 MPa, and stirring for 110-210 minutes under the condition of heat preservation; 3) adding n-hexane into a reaction kettle, fully stirring, standing for 6-8 hours for layering, wherein the upper layer is a mixture of polyglyceryl myristate and n-hexane, removing the upper layer liquid, heating the mixture of polyglyceryl ester and n-hexane to 65-85 ℃, and keeping the temperature for 50-70 minutes to remove the n-hexane; adding diatomite into the reaction kettle, stirring for 20-50 minutes under the protection of nitrogen and under the vacuum degree of 0.03Mpa, filtering by a filter press, and spraying powder to obtain the product.
The reaction by-products in the prior art are more, the color of the product is turbid, the product is dark yellow or brown, and a relatively pure light yellow product can be obtained by a relatively complicated purification step. The distribution range of the polymerization degree and the distribution range of the esterification rate of the polyglycerin oil in the prior art are large and difficult to control, so that the reproduction rate of the synthetic reaction is low, the prepared product is a mixture of various substances, and the hydrophilic-lipophilic balance value is unstable, namely the product quality is difficult to achieve consistency. In addition, the process steps are complex, and the steps of purifying and separating intermediate products, adding inert gas, vacuumizing and the like are involved for many times, so that the process is complex, the cost is obviously increased in industrial manufacturing, and large-scale stable mass production is difficult. Therefore, there is a need for improvements in the prior art.
Furthermore, on the one hand, due to the differences in understanding to the person skilled in the art; on the other hand, since the inventor of the present invention has studied a lot of documents and patents when making the present invention, but the space is not limited to the details and contents listed in the detailed description, however, the present invention is by no means characterized in these prior art, but the present invention has been provided with all the features of the prior art, and the applicant reserves the right to increase the related prior art in the background art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of polyglycerol ricinoleate, which comprises the following steps: glycerol is subjected to an alkali-catalyzed dehydrocondensation reaction to produce polyglycerol, and polyglycerol and ricinoleic acid are subjected to an esterification reaction to produce polyglycerol ricinoleate. The step of subjecting glycerol to a base-catalyzed dehydrocondensation reaction to produce polyglycerol comprises a first stage dehydrocondensation reaction using a first basic catalyst and a second stage dehydrocondensation reaction using a second basic catalyst. The esterification reaction of polyglycerol with ricinoleic acid to produce polyglycerol ricinoleate comprises a first stage esterification reaction using a third basic catalyst and a second stage esterification reaction using an enzyme.
According to a preferred embodiment, the catalytic activity of the first basic catalyst is greater than the catalytic activity of the second basic catalyst with respect to the catalytic activity for the dehydration condensation reaction of glycerin.
According to a preferred embodiment, the first basic catalyst is potassium carbonate and the second basic catalyst is potassium hydroxide.
According to a preferred embodiment, the third basic catalyst is the same as the second basic catalyst.
According to a preferred embodiment, the first stage of the dehydrocondensation reaction produces polyglycerin having an average degree of polymerization of 2 to 3, and the second stage of the dehydrocondensation reaction produces polyglycerin having an average degree of polymerization of 5 to 7.
According to a preferred embodiment, the second esterification reaction catalyzed by an enzyme uses a lipase.
According to a preferred embodiment, the esterification rate of the first stage esterification reaction is 50% to 70%, and the esterification rate of the second stage esterification reaction is more than 90%.
According to a preferred embodiment, the first reaction temperature of the first stage dehydration condensation reaction is lower than the second reaction temperature of the second stage dehydration condensation reaction.
According to a preferred embodiment, the second reaction temperature of the second stage dehydration condensation reaction is higher by more than 10 ℃ than the temperature difference between the third reaction temperatures of the first stage esterification reaction.
The invention discloses a preparation device of polyglycerol ricinoleate on the other hand, which comprises: a first reaction kettle loaded with a first basic catalyst and used for carrying out a first-stage dehydration condensation reaction on the glycerol under the catalysis of the first basic catalyst; a second reaction kettle loaded with a second basic catalyst and used for carrying out a second-stage dehydration condensation reaction on the product of the first-stage dehydration condensation reaction under the catalysis of the second basic catalyst; a third reaction kettle loaded with a third alkaline catalyst and used for carrying out a first-stage esterification reaction on the product of the second-stage dehydration condensation reaction and ricinoleic acid under the catalysis of the third alkaline catalyst; and a fourth reaction kettle loaded with enzyme for catalyzing the product of the first-stage esterification reaction to perform a second-stage esterification reaction with ricinoleic acid.
The beneficial technical effects of the invention at least comprise one or more of the following:
the reaction of glycerin dehydration condensation to generate polyglycerol is carried out in two steps by respectively adopting alkaline catalysts with different activities. The diglycerol or triglycerol with the conversion rate higher than 90% can be obtained in a short time by utilizing the higher catalytic activity of the first basic catalyst in the first-stage dehydration condensation reaction, the reaction temperature and the reaction time are relatively short, and the side reaction, the by-products and the impurities are obviously reduced. The diglycerol or triglycerol is further dehydrated and condensed at a higher reaction temperature under the action of a second basic catalyst with relatively low catalytic activity to generate a linear hexaglycerol as a main product.
In the invention, the second basic catalyst and the third basic catalyst are the same, and the second-stage dehydration condensation reaction and the first-stage esterification reaction are carried out in the same device in sequence, thereby obviously simplifying the process flow.
The method adopts the lipase as the catalyst to continue the second-stage esterification reaction, does not need to raise the temperature, but catalyzes the esterification reaction directionally, obviously improves the esterification rate, reduces the generation of side reactions and byproducts, improves the yield of target products and obviously reduces the process cost.
Detailed Description
The invention discloses a preparation method of polyglycerol ricinoleate, which comprises the following steps: the process comprises subjecting glycerol to base-catalyzed dehydration condensation reaction to produce polyglycerol, and subjecting polyglycerol and ricinoleic acid to esterification reaction to produce polyglycerol ricinoleate. The step of subjecting glycerol to a base-catalyzed dehydrocondensation reaction to produce polyglycerol comprises a first stage dehydrocondensation reaction using a first basic catalyst and a second stage dehydrocondensation reaction using a second basic catalyst. The esterification of polyglycerol with ricinoleic acid to produce polyglycerol ricinoleate involves a first stage esterification reaction using a third basic catalyst and a second stage esterification reaction using an enzyme.
The dehydration condensation reaction of glycerin is carried out under high-temperature and strong-base conditions, and side reactions such as the formation of acrolein and colored polymers thereof are liable to occur. The crude polyglycerol is generally yellow to dark brown depending on the level of by-product impurities. Generally, the higher the reaction temperature, the higher the activity of the basic catalyst, the longer the reaction time, the higher the degree of polymerization, and the darker the color of the produced polyglycerol. The prior art discloses technical schemes for preparing polyglycerol by using various basic catalysts, but all have problems of different degrees. For example, if a high-activity catalyst is adopted, the reaction degree, such as polymerization degree and branched polymer byproducts, is difficult to control, the product has high impurity content and deep color, the subsequent purification work is difficult, and the yield of purified and separated polyglycerol is low. The low-activity catalyst is adopted, so that the reaction time is long, the reaction efficiency is low, the time cost and the energy consumption for maintaining high temperature for a long time are high, and the economic benefit and the environmental benefit are poor.
The reaction of glycerin dehydration condensation to generate polyglycerol is carried out in two steps by respectively adopting alkaline catalysts with different activities. Preferably, the first basic catalyst has a catalytic activity greater than that of the second basic catalyst in terms of catalytic activity for the dehydration condensation reaction of glycerin. And preferably, the first reaction temperature of the first stage dehydration condensation reaction is lower than the second reaction temperature of the second stage dehydration condensation reaction. The first reaction time of the first stage dehydration condensation reaction is less than the second reaction time of the second stage dehydration condensation reaction. That is, the first-stage dehydration condensation reaction of glycerin occurs at a relatively low reaction temperature and over a relatively short first reaction time under the action of the first basic catalyst having a relatively high activity, to produce polyglycerin having a first average degree of polymerization. The polyglycerol having the first average degree of polymerization is reacted at a relatively high reaction temperature for a relatively long second reaction time under the action of a second basic catalyst having a relatively weak activity to produce a polyglycerol product having a second average degree of polymerization. In the first-stage dehydration condensation reaction, the catalytic activity of the first basic catalyst is high, and in order to avoid the increase of side reactions and byproducts brought by high temperature and long reaction time, lower reaction temperature and shorter reaction time are used. In this way, after the first dehydration condensation reaction, glycerol mostly forms dimers or trimers, mainly dimers. The average degree of polymerization of polyglycerol was determined by measuring the hydroxyl value, which was calculated by measuring the refractive index of polyglycerol, and the average degree of polymerization of polyglycerol was calculated. After the first dehydrating condensation reaction, the average degree of polymerization of the polyglycerin is 2 to 3, preferably 2.2 to 2.4, and the reaction product is in a light pale yellowish color.
After the first-stage dehydration condensation reaction is completed, the produced polyglycerol with the first average polymerization degree is not subjected to further dehydration condensation under the action of a first basic catalyst with higher catalytic activity, but is subjected to second-stage dehydration condensation under the action of a second basic catalyst with lower catalytic activity directly or after being separated from water and glycerol. The second reaction temperature of the second dehydration condensation reaction is relatively high, and the second reaction time is relatively long. In the second-stage dehydration condensation reaction, polyglycerin having a polymerization degree of 2 or 3 is further subjected to dehydration condensation with each other or with glycerin molecules to produce polyglycerin having an average polymerization degree of 5 to 7, preferably 5.8 to 6.2, and the reaction product is pale yellow.
Through the two-stage dehydration condensation reaction, the diglycerol or triglycerol with the conversion rate higher than 90% can be obtained in a short time by utilizing the higher catalytic activity of the first basic catalyst in the first-stage dehydration condensation reaction, the reaction temperature and the reaction time are relatively short, and the side reaction, the by-products and the impurities are obviously reduced. The diglycerol or triglycerol is further dehydrated and condensed at a higher reaction temperature under the action of a second basic catalyst with relatively low catalytic activity to generate the hexaglycerol with the linear hexaglycerol as a main product, preferably the yield of more than 75%, more preferably more than 80%, more preferably more than 85%, and more preferably more than 90%. The reaction product has less impurities and light color, the separation and purification difficulty is obviously reduced, and the yield of the target product is obviously improved.
Preferably, the first basic catalyst is potassium carbonate, lithium carbonate or sodium carbonate and the second basic catalyst is potassium hydroxide, sodium hydroxide or calcium hydroxide. Preferably, the first reaction time is 80 to 120 minutes and the second reaction time is 150 to 240 minutes. Preferably, the first reaction temperature is 180 to 220 ℃ and the second reaction temperature is 240 to 270 ℃. According to a specific embodiment, the first basic catalyst is potassium carbonate and the second basic catalyst is potassium hydroxide. According to another specific embodiment, the first basic catalyst is sodium carbonate and the second basic catalyst is sodium hydroxide. Experiments show that the first basic catalyst and the second basic catalyst are respectively matched by using carbonate and hydroxide of the same alkali metal, compared with the matching mode of carbonate and hydroxide of different alkali metals, the total reaction time of the first-stage dehydration condensation reaction and the second-stage dehydration condensation reaction is relatively short, the color of the product is lighter, the repeatability of multiple reactions is better, the polymerization degree distribution interval of the polyglycerol product is narrower, and the performance of the product is more stable.
Preferably, heat is directly provided for the second stage dehydration condensation reaction by an external heat source, and reactants of the second stage dehydration condensation reaction are used as a heat source for the first stage dehydration condensation reaction. In this way, the temperature of the first stage dehydration condensation reaction can be kept lower than that of the second stage dehydration condensation reaction, and the energy utilization rate of an external heat source can be improved.
Preferably, the third basic catalyst is the same as the second basic catalyst. The dehydration condensation reaction of glycerol and the esterification reaction of polyglycerol and ricinoleic acid or polyricinoleic acid are both alkali-catalyzed reactions. The temperature of the esterification reaction is lower than the temperature of further dehydration condensation of the hexaglycerol. Therefore, after the second-stage dehydration condensation reaction is finished, the reaction temperature is reduced by adding ricinoleic acid or polyricinoleic acid, the dehydration condensation reaction can be stopped, and reactants mainly adopt esterification reaction. In this way, the second stage dehydration condensation reaction and the first stage esterification reaction can be carried out in the same reaction vessel using the same basic catalyst. Normal-temperature unrepre-heated ricinoleic acid or polyricinoleic acid can be directly added, on one hand, reactants of esterification reaction are added, and on the other hand, the reaction temperature is reduced. In the invention, ricinoleic acid or polyricinoleic acid is directly added into the reactant and the reaction vessel of the second-stage dehydration condensation reaction, so that the reaction temperature can be directly reduced, the dehydration condensation reaction is terminated, and the esterification reaction is started. By the mode, the process flow is obviously reduced or simplified, and the utilization efficiency of energy is further improved. Preferably, in the first stage esterification reaction, the molar ratio of ricinoleic acid or polyricinoleic acid to polyglycerol product is from 2.5 to 4: 1. in a specific embodiment, the second basic catalyst and the third basic catalyst are both potassium hydroxide, in which case the temperature of the first esterification reaction is 180 to 250 ℃, preferably 180 to 200 ℃, and the reaction time of the first esterification reaction is 100 to 150 minutes. In another specific embodiment, the second basic catalyst and the third basic catalyst are both sodium hydroxide, in which case the temperature of the first esterification reaction is 200 to 270 ℃, preferably 200 to 240 ℃, and the reaction time of the first esterification reaction is 120 to 180 minutes. Preferably, the esterification rate of the first stage esterification reaction is 40% to 50%. In the present invention, the esterification ratio refers to the total proportion of esterified hydroxyl groups in the polyglycerin. Preferably, after the first stage esterification reaction, an average of 2 to 3 hydroxyl groups in the molecule of the hexaglycerol are esterified. In the present invention, the esterification rate is determined by a titration method of the separated and purified product known in the prior art, or by a refractometer detection and calculation method in the prior art, which is not described in detail herein.
Preferably, lipase is used for the second esterification reaction catalyzed by enzyme. After the first esterification reaction, in order to further increase the esterification rate, a method of increasing the reaction time, or increasing the reaction temperature, or increasing the amount of the ricinoleic acid or polyricinoleic acid reactant, or both, is generally used. However, this method increases the reaction costs, both with regard to energy consumption, time and raw material consumption. On the other hand, the three measures can greatly improve the occurrence probability of side reactions, such as condensation, esterification or etherification reaction among ricinoleic acid. The invention adopts lipase as catalyst to continue the second-stage esterification reaction, and the esterification reaction is catalyzed directionally without increasing temperature. Preferably, the reaction temperature is 20 to 40 ℃ and the reaction time is 3 to 5 hours. The esterification rate of the second stage esterification reaction is more than 70 percent, namely, more than 4 to 5 hydroxyl groups in the molecule of the hexaglycerol are esterified on average.
Preferably, the temperature difference between the second reaction temperature of the second stage dehydration condensation reaction and the third reaction temperature of the first stage esterification reaction is 10 ℃ or more, preferably 20 ℃ or more, more preferably 30 ℃ or more. Preferably, the third reaction temperature of the first stage esterification reaction is 25 ℃ lower than the second reaction temperature of the second stage dehydration condensation reaction. By the method, the second-stage dehydration condensation reaction can be definitely stopped, side reactions in the esterification reaction are reduced, the yield of the target product is improved, and the difficulty of subsequent separation and purification is reduced.
The invention discloses a preparation device of polyglycerol ricinoleate on the other hand, which comprises: a first reaction kettle loaded with a first basic catalyst and used for carrying out a first-stage dehydration condensation reaction on the glycerol under the catalysis of the first basic catalyst; a second reaction kettle loaded with a second basic catalyst and used for carrying out a second-stage dehydration condensation reaction on a product of the first-stage dehydration condensation reaction under the catalysis of the second basic catalyst; a third reaction kettle loaded with a third alkaline catalyst and used for carrying out a first-stage esterification reaction on a product of the second-stage dehydration condensation reaction and ricinoleic acid under the catalysis of the third alkaline catalyst; and a fourth reaction kettle loaded with enzyme for catalyzing the product of the first-stage esterification reaction and the ricinoleic acid to perform the second-stage esterification reaction.
Preferably, an external heat source is used for directly providing heat for the second-stage reaction kettle, and the second reaction kettle is used as a heat source of the first reaction kettle. In this way, the temperature of the first stage dehydration condensation reaction can be kept lower than that of the second stage dehydration condensation reaction, and the energy utilization rate of an external heat source can be improved.
Preferably, the second reaction vessel and the third reaction vessel are embodied as the same apparatus. Preferably, the basic catalysts in the invention are all solid basic catalysts, and preferably, the fixed basic catalysts are dispersed in alumina to improve the catalytic activity. After the reaction of the solid catalyst is finished, the solid catalyst can be directly separated from the product in a filtering mode without neutralization. Preferably, the hydroxyl groups of ricinoleic acid are protected by etherification of the hydroxyl groups, for example to form tert-butyl or benzyl ethers, to avoid side reactions involving the hydroxyl groups of ricinoleic acid. Preferably, the first dehydration condensation reaction, the second dehydration condensation reaction, the first esterification reaction and the second esterification reaction are all carried out under the atmosphere of nitrogen and at low pressure.
Example 1
Adding glycerol under the nitrogen atmosphere condition with the vacuum degree of 0.05-0.1 MPa, heating to 60-80 ℃, adding 0.1-0.5 wt% of solid potassium carbonate/alumina catalyst, continuously heating to 180-200 ℃, carrying out heat preservation reaction for 100 minutes to prepare a mixture with diglycerol and triglycerol as main products, and measuring the refractive index after separation to calculate the hydroxyl value so as to calculate the average polymerization degree of 2.36; separating the mixed polyglycerol from the solid potassium carbonate/alumina catalyst, adding the solid potassium hydroxide/alumina catalyst, continuing to heat to 240-250 ℃, keeping the temperature for reaction for 200 minutes to prepare a reaction product taking the hexaglycerol as a main product, and measuring the refractive index after separation to calculate the hydroxyl value, so that the average polymerization degree is 6.27, and the reaction product is light yellow; adding the mixture to the reaction product in a molar ratio of about 3: 1, reducing the temperature to 180-200 ℃, and reacting for 120-150 minutes under the vacuum degree of 0.08-0.1 MPa to obtain polyglycerol ricinoleate with the total average esterification rate of about 48%. And (3) adding the separated reaction product into a bubbling reactor, reducing the reaction temperature to 35 ℃, and continuously adding the reaction product into the bubbling reactor by using fatty acid as a catalyst in a molar ratio of about 2: 1 to 3: 1, keeping the temperature for reaction for 4 hours to prepare polyglycerol ricinoleate with the average esterification rate of about 75 percent. The reaction product is light yellow in color.
Example 2
Adding glycerol under the condition of nitrogen atmosphere with the vacuum degree of 0.05-0.1 MPa, heating to 60-80 ℃, adding 0.1-0.5 wt% of solid sodium carbonate/alumina catalyst, continuously heating to 220-240 ℃, carrying out heat preservation reaction for 120 minutes to prepare a mixture with diglycerol and triglycerol as main products, and measuring the refractive index after separation to calculate the hydroxyl value so as to calculate the average polymerization degree of 2.25; separating the mixed polyglycerol from the solid sodium carbonate/alumina catalyst, adding the solid sodium hydroxide/alumina catalyst, continuing to heat to 260-270 ℃, preserving the temperature for reaction for 240 minutes to prepare a reaction product taking the hexaglycerol as a main product, and measuring the refractive index after separation to calculate the hydroxyl value, so that the average polymerization degree is 6.18, and the reaction product is light yellow; adding the mixture to the reaction product in a molar ratio of about 3: 1, reducing the temperature to 200 ℃, and reacting for 120-150 minutes under the vacuum degree of 0.08-0.1 MPa to obtain polyglycerol ricinoleate with the total average esterification rate of about 45%. And (3) adding the separated reaction product into a bubbling reactor, reducing the reaction temperature to 35 ℃, and continuously adding the reaction product into the bubbling reactor by using fatty acid as a catalyst, wherein the molar ratio of the reaction product to the reaction product is about 2: 1 to 3: 1, keeping the temperature for reaction for 5 hours to prepare polyglycerol ricinoleate with the average esterification rate of about 72 percent. The reaction product is light yellow in color.
Example 3
Adding glycerol under the nitrogen atmosphere condition with the vacuum degree of 0.05-0.1 MPa, heating to 60-80 ℃, adding 0.1-0.5 wt% of solid potassium carbonate/alumina catalyst, continuously heating to 180-200 ℃, carrying out heat preservation reaction for 100 minutes to prepare a mixture with diglycerol and triglycerol as main products, and measuring the refractive index after separation to calculate the hydroxyl value so as to calculate the average polymerization degree of 2.35; separating the mixed polyglycerol from the solid potassium carbonate/alumina catalyst, adding the solid sodium hydroxide/alumina catalyst, continuously heating to 250-270 ℃, keeping the temperature for reaction for 220 minutes to prepare a reaction product taking the hexaglycerol as a main product, and measuring the refractive index after separation to calculate the hydroxyl value, so that the average polymerization degree is 6.36, and the reaction product is yellow; adding the mixture to the reaction product in a molar ratio of about 3: 1, reducing the temperature to 200 ℃, and reacting for 120-150 minutes under the vacuum degree of 0.08-0.1 MPa to obtain polyglycerol ricinoleate with the total average esterification rate of about 42%. And (3) adding the separated reaction product into a bubbling reactor, reducing the reaction temperature to 35 ℃, and continuously adding the reaction product into the bubbling reactor by using fatty acid as a catalyst, wherein the molar ratio of the reaction product to the reaction product is about 2: 1 to 3: 1, keeping the temperature for reaction for 5 hours to prepare polyglycerol ricinoleate with the average esterification rate of about 70 percent. The reaction product was yellow in color.
It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It is to be understood by persons skilled in the art that the present description is illustrative and not restrictive of the claims. The scope of the invention is defined by the claims and their equivalents.
Claims (10)
1. A method for preparing polyglycerol ricinoleate comprises the following steps:
subjecting glycerol to a base-catalyzed dehydrocondensation reaction to form polyglycerol, an
The polyglycerol and the ricinoleic acid are subjected to esterification reaction to generate polyglycerol ricinoleate,
it is characterized in that the preparation method is characterized in that,
the step of subjecting glycerin to a base-catalyzed dehydration condensation reaction to produce polyglycerin includes a first-stage dehydration condensation reaction using a first basic catalyst and a second-stage dehydration condensation reaction using a second basic catalyst,
the esterification reaction of polyglycerol with ricinoleic acid to produce polyglycerol ricinoleate comprises a first stage esterification reaction using a third basic catalyst and a second stage esterification reaction using enzyme catalysis.
2. The method according to claim 1, wherein the catalytic activity of the first basic catalyst is higher than that of the second basic catalyst with respect to the catalytic activity for the dehydration condensation reaction of glycerin.
3. The method of producing polyglycerol ricinoleate according to claim 2, wherein the first basic catalyst is potassium carbonate and the second basic catalyst is potassium hydroxide.
4. The method according to claim 3, wherein the third basic catalyst is the same as the second basic catalyst.
5. The method according to claim 4, wherein the first-stage dehydration condensation reaction produces polyglycerin having an average degree of polymerization of 2 to 3, and the second-stage dehydration condensation reaction produces polyglycerin having an average degree of polymerization of 5 to 7.
6. The method according to claim 5, wherein the second esterification reaction catalyzed by an enzyme is performed using a lipase.
7. The method according to claim 6, wherein the first esterification reaction has an esterification rate of 40% to 50% and the second esterification reaction has an esterification rate of more than 70%.
8. The method according to claim 7, wherein a first reaction temperature of the first dehydration condensation reaction is lower than a second reaction temperature of the second dehydration condensation reaction.
9. The method according to claim 8, wherein the second reaction temperature of the second dehydration condensation reaction is 10 ℃ or higher than the third reaction temperature of the first esterification reaction.
10. A preparation facilities of polyglycerol ricinoleate, its characterized in that includes:
a first reaction kettle which is loaded with a first basic catalyst and is used for carrying out a first-stage dehydration condensation reaction on glycerol under the catalysis of the first basic catalyst;
a second reaction kettle loaded with a second basic catalyst and used for carrying out a second-stage dehydration condensation reaction on the product of the first-stage dehydration condensation reaction under the catalysis of the second basic catalyst;
a third reaction kettle loaded with a third alkaline catalyst and used for carrying out a first-stage esterification reaction on the product of the second-stage dehydration condensation reaction and ricinoleic acid under the catalysis of the third alkaline catalyst; and
and the fourth reaction kettle is loaded with enzyme for catalyzing the product of the first-stage esterification reaction and ricinoleic acid to perform second-stage esterification reaction.
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|---|---|---|---|---|
| DE4442988C1 (en) * | 1994-12-02 | 1996-02-08 | Henkel Kgaa | Prepn. of complex ester useful as emulsifier for pharmaceutical etc. |
| US20080233059A1 (en) * | 2005-08-30 | 2008-09-25 | Tenore Richard R | Process for the Direct Manufacture of Polyglycerol Polyricinoleate |
| CN109628232A (en) * | 2019-01-09 | 2019-04-16 | 广州美晨科技实业有限公司 | A kind of preparation method of polyglyceryl fatty acid ester |
| CN109734563A (en) * | 2019-01-16 | 2019-05-10 | 浙江昊唐实业有限公司 | A kind of preparation method of Natrulon H-10 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4442988C1 (en) * | 1994-12-02 | 1996-02-08 | Henkel Kgaa | Prepn. of complex ester useful as emulsifier for pharmaceutical etc. |
| US20080233059A1 (en) * | 2005-08-30 | 2008-09-25 | Tenore Richard R | Process for the Direct Manufacture of Polyglycerol Polyricinoleate |
| CN109628232A (en) * | 2019-01-09 | 2019-04-16 | 广州美晨科技实业有限公司 | A kind of preparation method of polyglyceryl fatty acid ester |
| CN109734563A (en) * | 2019-01-16 | 2019-05-10 | 浙江昊唐实业有限公司 | A kind of preparation method of Natrulon H-10 |
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