阅读说明：本技术 一种三组分催化引发体系催化剂及其应用 (Three-component catalytic initiation system catalyst and application thereof ) 是由 陈满英 路风辉 李健 刘杏宜 刘文贤 陈洁 于 2021-09-24 设计创作，主要内容包括：本发明公开了一种三组分催化引发体系催化剂,包括主催化剂、引发剂、共引发剂和溶剂,所述主催化剂、引发剂、共引发剂的摩尔比为1：0.002～500：0.02～100。还公开了所述三组分催化引发体系催化剂在制备三聚甘油-硬脂酸-月桂酸混合酯中的应用。本发明中的三组分催化引发体系催化剂环保,不含有害成分,用量少,转化率高,反应可控性好；在制备三聚甘油-硬脂酸-月桂酸混合酯中的应用时,三组分催化引发体系催化剂可以使反应过程聚合度可控,反应转化率高。(The invention discloses a three-component catalytic initiation system catalyst, which comprises a main catalyst, an initiator, a co-initiator and a solvent, wherein the molar ratio of the main catalyst to the initiator to the co-initiator is 1: 0.002 to 500: 0.02 to 100. Also discloses application of the three-component catalytic initiation system catalyst in preparation of triglycerol-stearic acid-lauric acid mixed ester. The three-component catalytic initiation system catalyst is environment-friendly, contains no harmful components, and has the advantages of low consumption, high conversion rate and good reaction controllability; when the catalyst is applied to preparation of the triglycerol-stearic acid-lauric acid mixed ester, the polymerization degree in the reaction process can be controlled by the three-component catalytic initiation system catalyst, and the reaction conversion rate is high.)

1. A three-component catalytic initiation system catalyst is characterized in that: the catalyst comprises a main catalyst, an initiator, a co-initiator and a solvent, wherein the molar ratio of the main catalyst to the initiator to the co-initiator is 1: 0.002 to 500: 0.02-100, wherein the main catalyst is a metal organic compound, the initiator is alkyl alcohol, and the co-initiator is a nitrogen-containing ligand, a sulfur-containing ligand or a phosphine-containing ligand.

2. The three-component catalytic initiation system catalyst of claim 1, characterized by: the concentration of the main catalyst is 0.001-0.01 mol/L.

3. The three-component catalytic initiation system catalyst of claim 1, characterized by: the metal organic compound is triisobutyl aluminum, stannous octoate or diethyl zinc; the alkyl alcohol is benzyl alcohol or dodecyl alcohol.

4. The three-component catalytic initiation system catalyst of claim 1, characterized by: the nitrogen-containing ligand is pyridine and biological pyridine derivatives; the pyridine and biological pyridine derivatives are nicotinic acid, nicotinamide, isonicotinyl hydrazine, nicotine, strychnine and vitamin B6; the sulfur-containing ligand is thiophene and thiophene derivatives; the thiophene and the thiophene derivatives are alpha-acetylthiophene, alpha-chlorothiophene, alpha-iodothiophene, alpha-chloromethylthiophene, alpha-ethylenethiophene, thiophene-alpha-formaldehyde, thiophene-alpha-acetic acid, thiophene-alpha-ethanol, thiophene-alpha-acetonitrile, thiophene-alpha-ethylamine and alpha-nitrothiophene; the phosphine-containing ligand is an alkyl phosphine ligand, an aryl phosphine ligand, a diphosphine ligand, a heterocyclic phosphine ligand, a multidentate phosphine ligand, a phosphite ligand or a chiral phosphine ligand.

5. The three-component catalytic initiation system catalyst of claim 1, characterized by: the solvent is ethanol, acetone, chloroform, carbon tetrachloride, ethyl acetate or propyl acetate.

6. Use of a three-component catalytic initiation system catalyst according to any of claims 1 to 5 for the preparation of a triglycerol-stearic acid-lauric acid mixed ester.

7. Use according to claim 6, characterized in that: when the triglycerol-stearic acid-lauric acid mixed ester is applied, triglycerol, stearic acid and lauric acid are selected and used as a three-component catalytic initiation system catalyst, the solvent is removed by vacuumizing at room temperature, nitrogen is filled, the temperature is controlled to be 200-260 ℃ to carry out heterogeneous reaction, the homogeneous phase is transparent, the reaction is stopped, the reaction is cooled to room temperature, the material is taken out, the vacuum pumping and the cooling are carried out, and then the adsorption refining treatment is carried out, so that the triglycerol-stearic acid-lauric acid mixed ester is obtained.

8. Use according to claim 7, characterized in that: the mol ratio of the triglycerol to the stearic acid to the lauric acid is 1: 0.5-2.5: 0.5 to 2.5.

9. Use according to claim 7, characterized in that: the mass part ratio of the total mass of the triglycerol, the stearic acid and the lauric acid to the mass part ratio of the three-component catalytic initiation system catalyst is 1000-2400: 1 to 5.

10. Use according to claim 7, characterized in that: when the solvent is removed by vacuum pumping, the vacuum pumping is carried out for 20 to 24 hours at the temperature of 65 to 85 ℃.

Technical Field

The invention belongs to the technical field of food emulsifiers, and particularly relates to a three-component catalytic initiation system catalyst and application thereof.

Background

The glycerol (1,2, 3-trihydroxy propanol) molecule has three functional groups, and under proper conditions, the glycerol molecules can generate polymerization reaction with each other to generate polyglycerol. TriglycerolThe mixed acid ester is a high-efficiency food emulsifier. In recent years, with the improvement of living standard of people, the food industry of China is greatly developed. The food triglycerol mixed acid ester can not meet the requirement in some aspects, and the excellent emulsifying property of the polymeric glyceride is the supplement and improvement of the monoglyceride product, particularly the situation that other emulsifying agents cannot be compared with those of cold drinks and ice creams. In particular triglycerol monolaurate, also known as polyglycerol monolaurate, of formula C₂₁H₄₂O₈Is a chemical intermediate; and triglycerol monostearate, molecular formula: c₂₇H₅₄O₈Molecular weight: 506.72.

the synthesis of glyceride needs to use a catalyst, and the traditional catalyst usually takes strong acid and strong base as the catalyst at present, and grease and polyglycerol alcohol as raw materials to react under the high temperature condition. The chemical method has the advantages of simple operation, low production cost and high esterification rate, but can easily generate adverse byproducts under the action of high temperature, strong acid and strong alkali, is not easy to subsequently separate and purify, and has high reaction randomness. In recent years, a green synthesis method for preparing polyglycerol ester by lipase catalysis has been developed at home and abroad. Compared with a chemical method, the esterase method has mild reaction conditions, few byproducts and easy separation of materials, is favorable for improving the product quality, but has high enzyme price and is not favorable for industrial popularization, and because the reaction temperature is lower, the viscosity of a reaction system is difficult to reduce, and the esterification rate needs to be improved. Some catalyst systems have the problems of high catalyst consumption, wide molecular weight distribution and the like, low conversion rate, difficulty in controlling polymerization degree, incapability of meeting the standard requirement of food-grade emulsifiers and the like, for example, tin tetrachloride pentahydrate and phosphotungstic acid are used as catalysts, a single-component or double-component catalyst generally initiates high-temperature bulk copolymerization, the side reactions such as ester exchange and the like have high degree and poor reaction controllability; the reaction speed of the phosphotungstic acid and the zirconium-containing compound is too high, and a large amount of heat can be released in a short period of time.

Disclosure of Invention

The invention aims to provide a three-component catalytic initiation system catalyst which is environment-friendly, low in dosage, high in conversion rate and good in reaction controllability.

The invention also aims to provide the application of the catalyst in the preparation of the triglycerol-stearic acid-lauric acid mixed ester.

The first object of the present invention can be achieved by the following technical solutions: a three-component catalytic initiation system catalyst comprises a main catalyst, an initiator, a co-initiator and a solvent, wherein the molar ratio of the main catalyst to the initiator to the co-initiator is 1: 0.002 to 500: 0.02 to 100.

Preferably, the molar ratio of the main catalyst to the initiator to the co-initiator is 1: 0.5 to 200: 0.2 to 10.

Preferably, the concentration of the main catalyst is 0.001-0.01 mol/L.

Preferably, the main catalyst is a metal organic compound.

Preferably, the metal organic compound is triisobutylaluminum, stannous octoate or diethyl zinc.

Preferably, the initiator is an alkyl alcohol.

Preferably, the alkyl alcohol is benzyl alcohol or dodecyl alcohol.

Preferably, the coinitiator is a nitrogen-containing ligand, a sulfur-containing ligand or a phosphine-containing ligand.

Preferably, the nitrogen-containing ligand is pyridine and biological pyridine derivatives.

Preferably, the pyridine and biological pyridine derivatives include, but are not limited to, nicotinic acid, nicotinamide, isonicotinyl hydrazine, nicotine, strychnine, vitamin B6, and the like.

Preferably, the sulfur-containing ligand is thiophene and thiophene derivatives.

Preferably, the thiophene and thiophene derivatives include, but are not limited to, α -acetylthiophene, α -chlorothiophene, α -iodothiophene, α -chloromethylthiophene, α -ethylenethiophene, thiophene- α -formaldehyde, thiophene- α -acetic acid, thiophene- α -ethanol, thiophene- α -acetonitrile, thiophene- α -ethylamine, α -nitrothiophene, and the like.

Preferably, the phosphine-containing ligand is an alkyl phosphine ligand, an aryl phosphine ligand, a diphosphine ligand, a heterocyclic phosphine ligand, a multidentate phosphine ligand, a phosphite ligand, a chiral phosphine ligand, or the like.

Preferably, the alkyl phosphine ligand is tributyl phosphine, tetrabutyl phosphonium chloride, tributyl tetradecyl phosphine, trioctyl phosphine oxide.

Preferably, the arylphosphine ligand is preferably: triphenylphosphine, tri-p-hydroxyphenylphosphine, tris (4-methoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (p-octyloxyphenyl) phosphine, and the like.

Preferably, the solvent is ethanol, acetone, chloroform, carbon tetrachloride, ethyl acetate or propyl acetate.

More preferably, the solvent is ethyl acetate.

The solvent is used in the amount required to prepare the main catalyst, the initiator and the co-initiator with required concentration and amount.

The second object of the present invention can be achieved by the following technical solutions: the three-component catalytic initiation system catalyst is applied to the preparation of triglycerol-stearic acid-lauric acid mixed ester.

Preferably, during application, the triglycerol, the stearic acid and the lauric acid and the three-component catalytic initiation system catalyst are selected, the solvent is removed by vacuumizing at room temperature, nitrogen is filled, the temperature is controlled to be 200-260 ℃ for heterogeneous reaction, the homogeneous phase is transparent, the reaction is stopped, the reaction is cooled to the room temperature, the material is taken out, and the triglycerol-stearic acid-lauric acid mixed ester is obtained by performing adsorption refining treatment after vacuumizing and cooling.

Preferably, the mol ratio of the triglycerol to the stearic acid to the lauric acid is 1: 0.5-2.5: 0.5 to 2.5.

Preferably, the ratio of the total mass of the triglycerol, the stearic acid and the lauric acid to the mass parts of the three-component catalytic initiation system catalyst is 1000-2400: 1 to 5.

When the solvent is removed by vacuum pumping, the vacuum pumping is carried out for 20 to 24 hours at the temperature of 65 to 85 ℃.

The adsorption refining treatment comprises the step of carrying out adsorption refining treatment on the final product by adopting a granular magnesium silicate adsorbent.

According to the embodiment, a three-component catalytic initiation system catalyst is reasonably selected, unreacted fatty acid is removed by high-temperature vacuumizing, then a final product is subjected to adsorption refining treatment by utilizing adsorbents such as granular magnesium silicate, and the like, so that a triglycerol-stearic acid-lauric acid ester mixed ester product is obtained according to a detection standard, and the product quality safety meets the requirements of food additives.

The acid value (calculated by KOH) of the prepared triglycerol-stearic acid-lauric acid ester mixed ester product is less than or equal to 5.0mg/g, and the iodine value (measured by the method for measuring the iodine value in GB 1986) is less than or equal to 3.0g/100 g; the saponification value is 120-135 mgKOH/g (specified in GB8044, 2.3 rules); arsenic/as arsenic (measured by dry ashing method samples and arsenic spot method in GB 8450) is less than 0.0003%; heavy metals (in terms of Pb) (determined by treating the sample with dry ashing according to GB 8451) < 0.001%; free glycerin is less than or equal to 7.0 percent; free acid (calculated by stearic acid) is less than or equal to 2.5 percent; the burning residue is less than or equal to 0.5 percent (GB/T5009.12); ash content of the ash sulfate is less than or equal to 1.0 percent.

Compared with the prior art, the invention has the following advantages:

(1) the three-component catalytic initiation system catalyst is environment-friendly, and has the advantages of small using amount, high conversion rate and good reaction controllability;

(2) when the catalyst is applied to preparation of the triglycerol-stearic acid-lauric acid mixed ester, the polymerization degree in the reaction process can be controlled by the three-component catalytic initiation system catalyst, and the reaction conversion rate is high;

(3) when the preparation method is applied to the preparation of the triglycerol-stearic acid-lauric acid mixed ester, the acid value, iodine value, saponification value, arsenic, heavy metal, free glycerol, free acid, burning residue and ash content in the prepared triglycerol-stearic acid-lauric acid ester product meet the product quality and the actual application requirements.

Detailed Description

The following starting materials are all commercially available products unless otherwise specified.

Example 1

The three-component catalytic initiation system catalyst provided in this embodiment includes a main catalyst, an initiator, a co-initiator, and a solvent, and the molar ratio of the main catalyst, the initiator, and the co-initiator in this embodiment is 1: 0.5: 5.

the concentration of the main catalyst is 0.005 mol/L.

The main catalyst is a metal organic compound.

The metal organic compound is diethyl zinc.

The initiator is alkyl alcohol.

The alkyl alcohol is dodecyl alcohol.

The coinitiator is a nitrogen-containing ligand.

The nitrogen-containing ligand is pyridine and biological pyridine derivatives.

The pyridine and the biological pyridine derivative are nicotinic acid.

The solvent is ethyl acetate.

The solvent is used in the amount required to prepare the main catalyst, the initiator and the co-initiator with required concentration and amount.

The main catalyst, the initiator and the co-initiator are dissolved and configured in an ethyl acetate solvent to prepare the three-component catalytic initiation system catalyst.

The three-component catalytic initiation system catalyst is used for preparing the triglycerol-stearic acid-lauric acid mixed ester, and comprises the following steps: selecting triglycerin, stearic acid, lauric acid and the three-component catalytic initiation system catalyst, vacuumizing to remove the solvent at room temperature, filling nitrogen, heating to control the temperature to be 200 ℃ to perform heterogeneous reaction until the homogeneous phase is transparent, stopping the reaction, cooling to room temperature, taking out the material, vacuumizing, cooling, and performing adsorption refining treatment to obtain the triglycerin-stearic acid-laurate.

Wherein:

the mol ratio of the triglycerol to the stearic acid to the lauric acid is 1: 1: 1.

the mass ratio of the total mass of the triglycerol, the stearic acid and the lauric acid to the mass part of the three-component catalytic initiation system catalyst is 2000: 1.

when the solvent was removed by vacuum, the reaction mixture was evacuated at 65 ℃ for 23 hours.

The adsorption refining treatment comprises the step of carrying out adsorption refining treatment on the final product by adopting a granular magnesium silicate adsorbent.

According to the embodiment, a three-component catalytic initiation system catalyst is reasonably selected, unreacted fatty acid is removed by high-temperature vacuumizing, then a final product is subjected to adsorption refining treatment by utilizing adsorbents such as granular magnesium silicate, and the like, so that a triglycerol-stearic acid-lauric acid ester mixed ester product is obtained according to a detection standard, and the product quality safety meets the requirements of food additives.

The acid value (calculated by KOH) of the obtained triglycerol-stearic acid-lauric acid ester mixed ester is 4.2 mg/g; iodine value (according to the method for measuring the iodine value in GB 1986) is 2.1g/100 g; saponification value 128mgKOH/g (as defined in GB8044, article 2.3); arsenic/as arsenic (determined by treating samples by dry ashing and arsenic spots in GB 8450) was not detected; heavy metals (in terms of Pb) (determined by treating the sample with dry ash according to GB 8451) were not detected; free glycerol/% -4.0%; 1.5 percent of free acid (calculated by stearic acid); burning residue is 0.4% (GB/T5009.12); ash content, sulfated ash content, 0.35%.

Example 2

The three-component catalytic initiation system catalyst provided by the embodiment comprises a main catalyst, an initiator, a co-initiator and a solvent, wherein the molar ratio of the main catalyst to the initiator to the co-initiator is 1: 100: 1.

preferably, the concentration of the main catalyst is 0.008 mol/L.

The main catalyst is a metal organic compound.

The metal organic compound is triisobutylaluminum.

The initiator is alkyl alcohol.

The alkyl alcohol is benzyl alcohol.

The coinitiator is a sulfur-containing ligand.

The sulfur-containing ligand is thiophene and thiophene derivatives.

The thiophene and thiophene derivatives are alpha-acetylthiophene.

The solvent is ethanol.

The solvent is used in the amount required to prepare the main catalyst, the initiator and the co-initiator with required concentration and amount.

The main catalyst, the initiator and the co-initiator are dissolved and configured in an ethanol solvent to prepare the three-component catalytic initiation system catalyst.

The three-component catalytic initiation system catalyst is used for preparing the triglycerol-stearic acid-lauric acid mixed ester, and comprises the following steps: selecting triglycerol, stearic acid, lauric acid and the three-component catalytic initiation system catalyst, vacuumizing to remove the solvent at room temperature, introducing nitrogen, controlling the temperature to be 230 ℃ to perform heterogeneous reaction until the homogeneous phase is transparent, stopping the reaction, cooling to room temperature, taking out the material, vacuumizing, cooling, and performing adsorption refining treatment to obtain the triglycerol-stearic acid-lauric acid mixed ester.

The mol ratio of the triglycerol to the stearic acid to the lauric acid is 1: 0.5: 2.5.

the total mass of the triglycerol, the stearic acid and the lauric acid and the mass part ratio of the three-component catalytic initiation system catalyst are 1000: 5.

when the solvent is removed by vacuum-pumping, the vacuum-pumping is carried out for 20 hours at 75 ℃.

The adsorption refining treatment comprises the step of carrying out adsorption refining treatment on the final product by adopting a granular magnesium silicate adsorbent.

According to the embodiment, a three-component catalytic initiation system catalyst is reasonably selected, unreacted fatty acid is removed by high-temperature vacuumizing, then a final product is subjected to adsorption refining treatment by utilizing adsorbents such as granular magnesium silicate, and the like, so that a triglycerol-stearic acid-lauric acid ester mixed ester product is obtained according to a detection standard, and the product quality safety meets the requirements of food additives.

The acid value (calculated by KOH) of the obtained triglycerol-stearic acid-lauric acid ester mixed ester is 4.8mg/g, and the iodine value (measured by the method for measuring the iodine value in GB 1986) is 2.5g/100 g; the saponification value is determined according to the rule of 2.3 in GB8044, 125 mgKOH/g; arsenic/not detected by arsenic meter (measured by dry ashing method for treating samples and arsenic spot method in GB 8450); heavy metals (in terms of Pb) (determined by treating the sample with dry ash according to GB 8451) were not detected; free glycerol is 3.3%; free acid (calculated as stearic acid) 1.4%; burning residue is 0.4% (GB/T5009.12); ash sulphated ash content is 0.21%.

Example 3

The three-component catalytic initiation system catalyst provided by the embodiment comprises a main catalyst, an initiator, a co-initiator and a solvent, wherein the molar ratio of the main catalyst to the initiator to the co-initiator is 1: 300: 80.

the concentration of the main catalyst is 0.003 mol/L.

The main catalyst is a metal organic compound.

The metal organic compound is stannous octoate.

The initiator is alkyl alcohol.

The alkyl alcohol is dodecyl alcohol.

The coinitiator is a phosphine-containing ligand.

The phosphine-containing ligand is an alkyl phosphine ligand.

The alkyl phosphine ligand is preferably tributylphosphine.

The solvent is ethyl acetate.

The solvent is used in the amount required to prepare the main catalyst, the initiator and the co-initiator with required concentration and amount.

The main catalyst, the initiator and the co-initiator are dissolved and configured in an ethyl acetate solvent to prepare the three-component catalytic initiation system catalyst.

The three-component catalytic initiation system catalyst is used for preparing the triglycerol-stearic acid-lauric acid mixed ester, and comprises the following steps: selecting triglycerol, stearic acid, lauric acid and the three-component catalytic initiation system catalyst, vacuumizing to remove the solvent at room temperature, introducing nitrogen, controlling the temperature to be 250 ℃ to perform heterogeneous reaction until the homogeneous phase is transparent, stopping the reaction, cooling to room temperature, taking out the material, vacuumizing, cooling, and performing adsorption refining treatment to obtain the triglycerol-stearic acid-lauric acid mixed ester.

The mol ratio of the triglycerol to the stearic acid to the lauric acid is 1: 2: 1.

the mass part ratio of the total mass of the triglycerol, the stearic acid and the lauric acid to the mass part ratio of the three-component catalytic initiation system catalyst is 1500: 3.

when the solvent is removed by vacuum pumping, the vacuum pumping is carried out for 24 hours at the temperature of 85 ℃.

The adsorption refining treatment comprises the step of carrying out adsorption refining treatment on the final product by adopting a granular magnesium silicate adsorbent.

According to the embodiment, a three-component catalytic initiation system catalyst is reasonably selected, unreacted fatty acid is removed by high-temperature vacuumizing, then a final product is subjected to adsorption refining treatment by utilizing adsorbents such as granular magnesium silicate, and the like, so that a triglycerol-stearic acid-lauric acid ester mixed ester product is obtained according to a detection standard, and the product quality safety meets the requirements of food additives.

The acid value (calculated by KOH) of the obtained triglycerol-stearic acid-lauric acid ester mixed ester is 2.5mg/g, and the iodine value (determined by the method for determining the iodine value in GB 1986) is 2.0g/100 g; the saponification value is determined according to the rule of 2.3 in GB8044, 130 mgKOH/g; arsenic/not detected by arsenic meter (measured by dry ashing method for treating samples and arsenic spot method in GB 8450); heavy metals (in terms of Pb) (determined by treating the sample with dry ash according to GB 8451) were not detected; free glycerol 2.4%; free acid (calculated as stearic acid) 0.4%; burning residue is 0.21% (GB/T5009.12); ash sulphated ash content is 0.34%.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.