CN115403730B - Food white oil emulsifier and preparation method thereof - Google Patents
Food white oil emulsifier and preparation method thereof Download PDFInfo
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
The invention relates to a food white oil emulsifier and a preparation method thereof, belonging to the technical field of emulsifiers. The emulsifier is an oil-in-water type single-component emulsifier, excessive hexamethylene diisocyanate reacts with diglycerol to prepare a matrix with branched high-activity isocyanate groups, a small amount of di-n-octylamine is grafted on a double-branched saturated alkane chain to improve the compatibility with white oil, the emulsifier is modified by low-viscosity epoxy resin, epoxy groups are introduced to endow the emulsifier with certain crosslinking property, sulfamic acid reacts with partial epoxy groups, and sulfonic acid groups are grafted on the emulsifier to further improve the hydrophilicity of the emulsifier, and meanwhile, the state of the emulsifier is regulated; through tests, the white oil emulsion prepared by the emulsifier has fine particle size, the average particle size is 420-505nm, the storage stability at 50 ℃ reaches 15-22d, and the stability reaches 50-60min under the centrifugation at 4000rpm, and the emulsion state is obviously better than the existing general emulsifier.
Description
Technical Field
The invention belongs to the technical field of emulsifying agents, and particularly relates to a food white oil emulsifying agent and a preparation method thereof.
Background
The white oil is colorless transparent oily liquid, has no smell, is a mixture of liquid hydrocarbons, and is prepared from high-boiling fraction of petroleum fractionation by dewaxing, carbonizing, neutralizing, refining with activated clay, etc.
The white food oil is transparent colorless non-fluorescent mineral oil with high extraction precision, removes a large number of impurities harmful to human bodies such as aromatic hydrocarbon, nitrogen, sulfur and the like in the properties of the mineral oil, and is widely applied to industries such as food, medicine and the like.
The food white oil has good yellowing resistance, oxidation resistance and good viscosity-temperature performance, has extremely low impurity content, can effectively reduce the yellowing of a coating when applied to the coating, and mostly takes the food white oil as a diluent in the existing water-based decorative coating. The existing white oil emulsifier is formed by compounding a plurality of surfactants and auxiliary agents, part of compounding ingredients have great influence on the performance of the paint, particularly yellowing resistance, and in addition, the emulsifying effect of the compounding emulsifier on the white oil is not high, particularly the mechanical stability of emulsion is not high; therefore, the application aims to develop a single-component emulsifier, and fully exert the advantages of the food white oil.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a food white oil emulsifier and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a food white oil emulsifier specifically comprises the following steps:
step S1: uniformly mixing hexamethylene diisocyanate and tetrahydrofuran, adding dibutyl tin dilaurate, setting the stirring speed to be 240-360rpm, heating to 50-55 ℃, slowly adding diglycerol, then adding benzoyl chloride, heating to 70-75 ℃ for reflux reaction for 20-30min, and removing tetrahydrofuran after the reaction is finished by rotary evaporation to obtain an isocyanate-terminated substrate;
further, the amount of diglycerol, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran was used in a ratio of 0.1mol:0.42-0.45mol:0.1-0.15mL:20-30mg:150-180mL of diglycerol is reacted with excessive hexamethylene diisocyanate under the catalysis of dibutyltin dilaurate, and the prepared isocyanate-terminated matrix molecule contains a branched isocyanate group;
further, diglycerol and tetrahydrofuran are dehydrated before use.
Step S2: uniformly mixing an isocyanate end-capped matrix and toluene, heating to 88-95 ℃, setting the stirring speed to 420-600rpm, adding triethylamine and di-n-octylamine, carrying out heat preservation and stirring reaction for 50-60min, and removing toluene by reduced pressure rotary evaporation after the reaction to obtain an oleophylic modified intermediate;
further, the isocyanate-terminated substrate, di-n-octylamine, triethylamine and toluene were used in an amount ratio of 70g:80-90mmol:0.2-0.3mL:100-120mL, a small amount of di-n-octylamine reacts with isocyanate groups on isocyanate-terminated matrix molecules, and the prepared lipophilic modified intermediate molecules contain double-branched saturated alkane chains, so that the lipophilic modified intermediate molecules have good compatibility with white oil.
Step S3: uniformly mixing an oleophylic modified intermediate, epoxy resin and ethyl acetate, maintaining the temperature at 10-15 ℃, adding dodecatertiary amine, stirring at 300rpm for reaction for 20-25min, and removing ethyl acetate after the reaction is finished by reduced pressure rotary evaporation to obtain an epoxidation matrix;
preferably, the epoxy resin is selected from the group consisting of epoxy resin E-51.
Further, the use amount ratio of the lipophilic modified intermediate, the epoxy resin, the dodecylamine and the ethyl acetate was 90g:130-150g:0.8-1.3mL:160-200mL of epoxy resin reacts with residual isocyanate groups on molecules of the lipophilic modified intermediate under the catalysis of laurylamine, and the lipophilic modified intermediate is subjected to epoxidation modification.
Step S4: stirring and dissolving sulfamic acid and water, dripping the dissolved sulfamic acid and water into an epoxidation matrix, stirring at 1000rpm until the viscosity is regulated to 150 mPa.s, and obtaining the white oil emulsifier.
The invention has the beneficial effects that:
the invention prepares an oil-in-water type single-component emulsifier, which is prepared by reacting excessive hexamethylene diisocyanate with diglycerol to prepare a matrix with branched high-activity isocyanate groups, reacting a small amount of di-n-octylamine with partial isocyanate under a specific process, grafting a double-branched saturated alkane chain on the matrix, which has good compatibility with white oil, then reacting low-viscosity epoxy resin with residual isocyanate groups, introducing epoxy groups, endowing the emulsifier with certain crosslinking property, enabling the emulsifier to interact with a coating, avoiding the emulsifier from influencing the film forming property of the coating, and finally reacting sulfamic acid with partial epoxy groups, grafting sulfonic acid groups to further promote the hydrophilicity of the emulsifier, and simultaneously adjusting the state of the emulsifier. The test shows that the emulsifier prepared by the invention is applied to the emulsification of white oil, the prepared emulsion has fine particle size, the average particle size is 420-505nm, the storage stability at 50 ℃ reaches 15-22d, and the stability reaches 50-60min under the centrifugation at 4000rpm, and the emulsification state is obviously better than the existing general emulsifier.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the food white oil emulsifier comprises the following specific implementation processes:
s1, synthetic matrix
In the step, diglycerol is used as a raw material, tetrahydrofuran is used as a solvent, moisture is easy to absorb, and dehydration treatment is carried out before use in order to avoid the influence of moisture on a synthesized product, and the specific method comprises the following steps: diglycerol is decompressed to 100Pa, decompressed and removed at 100 ℃ for 30min, tetrahydrofuran is circularly adsorbed and dehydrated for 1h by adopting a silica gel drying tube, and the same dehydration method is adopted in the following examples;
adding hexamethylene diisocyanate and tetrahydrofuran into a flask, stirring and mixing for 10min at 120rpm, dispersing hexamethylene diisocyanate in tetrahydrofuran, adding dibutyltin dilaurate, setting the stirring speed to be 360rpm, heating to 55 ℃, adding diglycerol into the flask at a constant speed within 10min, adding a small amount of benzoyl chloride after complete addition, lifting the stirring speed to be 600rpm, heating to 75 ℃, carrying out reflux reaction for 20min, removing tetrahydrofuran by rotary evaporation, and obtaining an isocyanate end-capped substrate;
in the above reaction, the amount of diglycerol, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran was used in a ratio of 0.1mol:0.45mol:0.15mL:30mg:180mL, quantified as 0.1mol diglycerol.
s2, lipophilic modification
Adding an isocyanate-terminated matrix and toluene into a flask, stirring and mixing for 5min at 300rpm, keeping stirring and heating to 95 ℃, lifting and stirring at 600rpm, adding triethylamine and di-n-octylamine into the flask after mixing, keeping the temperature and stirring for reacting for 50min, reducing the pressure to 100Pa after reacting, removing toluene by rotary evaporation, and obtaining a rotary evaporation product to obtain an oleophilic modified intermediate;
in the above reaction, the ratio of the isocyanate-terminated substrate, di-n-octylamine, triethylamine and toluene was 70g:90mmol:0.3mL:120mL, quantified as 70g isocyanate-terminated matrix.
s3, epoxidation treatment
Adding an oleophylic modified intermediate, epoxy resin and ethyl acetate into a flask, stirring and mixing at 600rpm for 10min, placing the flask into a water bath, controlling the temperature of a reaction system to be 15 ℃ through circulating ice water, adding dodecylamine, setting the stirring speed to be 300rpm, stirring and reacting for 20min, reducing the pressure to be below 30Pa after the reaction, controlling the temperature to be not higher than 35 ℃, and removing ethyl acetate to obtain an epoxidation matrix;
in the above reaction, the amount ratio of the lipophilic modified intermediate, the epoxy resin, the dodecylamine and the ethyl acetate was 90g:150g:1.3mL:200mL, quantified as 90g of lipophilic modified intermediate, wherein the epoxy resin is selected from epoxy E-51, supplied by Complex advanced Material (Shanghai) Inc., the same starting materials are used in the following examples.
s4, hydrophilic modification
Dissolving sulfamic acid in water, dropwise adding the sulfamic acid into an epoxidation matrix at a speed of 5mL/min, setting the stirring speed to be 1000rpm, and detecting the viscosity of a reaction system on line until the viscosity is reduced to 150 mPa.s to obtain the white oil emulsifier.
Example 2
The preparation method of the food white oil emulsifier comprises the following specific implementation processes:
s1, synthetic matrix
Adding hexamethylene diisocyanate and tetrahydrofuran into a flask, stirring and mixing for 10min at 120rpm, dispersing hexamethylene diisocyanate in tetrahydrofuran, adding dibutyltin dilaurate, setting the stirring speed to 240rpm, heating to 50 ℃, adding diglycerol into the flask at a constant speed within 10min, adding a small amount of benzoyl chloride after complete addition, lifting the stirring speed to 600rpm, heating to 70 ℃ for reflux reaction for 30min, removing tetrahydrofuran after the reaction is finished, and taking a rotary evaporation product to obtain an isocyanate end-capped substrate;
in the above reaction, the amount of diglycerol, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran was used in a ratio of 0.1mol:0.42mol:0.1mL:20mg:150mL, quantified as 0.1mol diglycerol.
s2, lipophilic modification
Adding an isocyanate-terminated matrix and toluene into a flask, stirring and mixing for 5min at 300rpm, keeping stirring and heating to 88 ℃, lifting and stirring at 420rpm, adding triethylamine and di-n-octylamine into the flask after mixing, keeping the temperature and stirring for reacting for 60min, reducing the pressure to 100Pa after reacting, removing toluene by rotary evaporation, and obtaining a rotary evaporation product to obtain an oleophilic modified intermediate;
in the above reaction, the ratio of the isocyanate-terminated substrate, di-n-octylamine, triethylamine and toluene was 70g:80mmol:0.2mL:100mL, quantified as 70g isocyanate-terminated matrix.
s3, epoxidation treatment
Adding an oleophylic modified intermediate, epoxy resin and ethyl acetate into a flask, stirring and mixing at 600rpm for 10min, placing the flask into a water bath, controlling the temperature of a reaction system to be 10 ℃ through circulating ice water, adding dodecylamine, setting the stirring rate to be 300rpm, stirring and reacting for 25min, reducing the pressure to be below 30Pa after the reaction, controlling the temperature to be not higher than 35 ℃, and removing ethyl acetate to obtain an epoxidation matrix;
in the above reaction, the amount ratio of the lipophilic modified intermediate, the epoxy resin, the dodecylamine and the ethyl acetate was 90g:130g:0.8mL:160mL, quantified as 90g of lipophilic modified intermediate.
s4, hydrophilic modification
Dissolving sulfamic acid in water, dropwise adding the sulfamic acid into an epoxidation matrix at a speed of 5mL/min, setting the stirring speed to be 1000rpm, and detecting the viscosity of a reaction system on line until the viscosity is reduced to 150 mPa.s to obtain the white oil emulsifier.
Example 3
The preparation method of the food white oil emulsifier comprises the following specific implementation processes:
s1, synthetic matrix
Adding hexamethylene diisocyanate and tetrahydrofuran into a flask, stirring and mixing for 10min at 120rpm, dispersing hexamethylene diisocyanate in tetrahydrofuran, adding dibutyltin dilaurate, setting the stirring speed to be 360rpm, heating to 50 ℃, adding diglycerol into the flask at a constant speed within 10min, adding a small amount of benzoyl chloride after complete addition, lifting the stirring speed to be 600rpm, heating to 72 ℃ for reflux reaction for 28min, and removing tetrahydrofuran after the reaction is finished by rotary evaporation, and taking a rotary evaporation product to obtain an isocyanate end-capped substrate;
in the above reaction, the amount of diglycerol, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran was used in a ratio of 0.1mol:0.45mol:0.15mL:25mg:160mL, 0.1mol diglycerol.
s2, lipophilic modification
Adding an isocyanate-terminated matrix and toluene into a flask, stirring and mixing for 5min at 300rpm, keeping stirring and heating to 90 ℃, lifting and stirring at 480rpm, adding triethylamine and di-n-octylamine into the flask after mixing, keeping the temperature and stirring for reacting for 55min, reducing the pressure to 100Pa after reacting, removing toluene by rotary evaporation, and obtaining a rotary evaporation product to obtain an oleophilic modified intermediate;
in the above reaction, the ratio of the isocyanate-terminated substrate, di-n-octylamine, triethylamine and toluene was 70g:85mmol:0.25mL:100mL, quantified as 70g isocyanate-terminated matrix.
s3, epoxidation treatment
Adding an oleophylic modified intermediate, epoxy resin and ethyl acetate into a flask, stirring and mixing at 600rpm for 10min, placing the flask into a water bath, controlling the temperature of a reaction system to be 12 ℃ through circulating ice water, adding dodecylamine, setting the stirring speed to be 300rpm, stirring and reacting for 22min, reducing the pressure to be below 30Pa after the reaction, controlling the temperature to be not higher than 35 ℃, and removing ethyl acetate to obtain an epoxidation matrix;
in the above reaction, the amount ratio of the lipophilic modified intermediate, the epoxy resin, the dodecylamine and the ethyl acetate was 90g:140g:1.1mL:180mL, quantified as 90g of lipophilic modified intermediate.
s4, hydrophilic modification
Dissolving sulfamic acid in water, dropwise adding the sulfamic acid into an epoxidation matrix at a speed of 5mL/min, setting the stirring speed to be 1000rpm, and detecting the viscosity of a reaction system on line until the viscosity is reduced to 150 mPa.s to obtain the white oil emulsifier.
Example 4
The preparation method of the food white oil emulsifier comprises the following specific implementation processes:
s1, synthetic matrix
Adding hexamethylene diisocyanate and tetrahydrofuran into a flask, stirring and mixing for 10min at 120rpm, dispersing hexamethylene diisocyanate in tetrahydrofuran, adding dibutyltin dilaurate, setting the stirring speed to be 300rpm, heating to 52 ℃, adding diglycerol into the flask at a constant speed within 10min, adding a small amount of benzoyl chloride after complete addition, lifting the stirring speed to be 600rpm, heating to 75 ℃, carrying out reflux reaction for 25min, removing tetrahydrofuran by rotary evaporation, and obtaining an isocyanate end-capped substrate;
in the above reaction, the amount of diglycerol, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran was used in a ratio of 0.1mol:0.42mol:0.13mL:30mg:180mL, quantified as 0.1mol diglycerol.
s2, lipophilic modification
Adding an isocyanate-terminated matrix and toluene into a flask, stirring and mixing for 5min at 300rpm, keeping stirring and heating to 92 ℃, lifting and stirring at 600rpm, adding triethylamine and di-n-octylamine into the flask after mixing, keeping the temperature and stirring for reacting for 55min, reducing the pressure to 100Pa after reacting, removing toluene by rotary evaporation, and obtaining a rotary evaporation product to obtain an oleophilic modified intermediate;
in the above reaction, the ratio of the isocyanate-terminated substrate, di-n-octylamine, triethylamine and toluene was 70g:90mmol:0.2mL:120mL, quantified as 70g isocyanate-terminated matrix.
s3, epoxidation treatment
Adding an oleophylic modified intermediate, epoxy resin and ethyl acetate into a flask, stirring and mixing at 600rpm for 10min, placing the flask into a water bath, controlling the temperature of a reaction system to be 10 ℃ through circulating ice water, adding dodecylamine, setting the stirring rate to be 300rpm, stirring and reacting for 25min, reducing the pressure to be below 30Pa after the reaction, controlling the temperature to be not higher than 35 ℃, and removing ethyl acetate to obtain an epoxidation matrix;
in the above reaction, the amount ratio of the lipophilic modified intermediate, the epoxy resin, the dodecylamine and the ethyl acetate was 90g:140g:1.2mL:180mL, quantified as 90g of lipophilic modified intermediate.
s4, hydrophilic modification
Dissolving sulfamic acid in water, dropwise adding the sulfamic acid into an epoxidation matrix at a speed of 5mL/min, setting the stirring speed to be 1000rpm, and detecting the viscosity of a reaction system on line until the viscosity is reduced to 150 mPa.s to obtain the white oil emulsifier.
Comparative example 1
The commercial white oil emulsifier of this comparative example is provided by Nantong Chen wetting chemical Co.
The white oil emulsifiers prepared in examples 1-4 and provided in comparative examples were subjected to the following performance tests:
taking 100mL of food white oil test samples provided by auspicious fine oil products limited company in Dongguan, respectively adding more than 10g of emulsifier provided by Dongguan, adding deionized water to a volume of 500mL, and placing the mixture in a high-speed emulsifier to shear at 2800rpm for 10min to obtain emulsion;
emulsion particle size testing: measuring particle size distribution in the emulsion by adopting ZS90 type nanometer laser granularity, wherein the test temperature is 25+/-1 ℃;
storage stability: referring to GB/T6765.3-1986 standard, placing the emulsion sample into a glass bottle, standing at a constant temperature of 50 ℃, observing the emulsion state under a fluorescent lamp, and recording layering time;
mechanical stability: placing the emulsion sample into a glass bottle, placing into a TG16-WS centrifuge, centrifuging at 4000rpm, taking out and standing for 10min, observing the emulsion state under a fluorescent lamp, taking the centrifuging time as a gradient until obvious layering occurs, and recording as layering time;
the specific test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the emulsifier prepared by the invention is applied to the emulsification of white oil, the prepared emulsion has fine particle size, the average particle size is 420-505nm, the storage stability at 50 ℃ reaches 15-22d, and the stability reaches 50-60min under the centrifugation at 4000rpm, and the emulsification state is obviously better than that of the existing general emulsifier.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The preparation method of the food white oil emulsifier is characterized by comprising the following steps:
step S1: mixing hexamethylene diisocyanate and tetrahydrofuran, adding dibutyl tin dilaurate, stirring and heating to 50-55 ℃, slowly adding diglycerol, then adding benzoyl chloride, lifting and stirring at 600rpm, heating to 70-75 ℃, carrying out reflux reaction for 20-30min, and removing tetrahydrofuran after the reaction is finished by rotary evaporation to obtain an isocyanate-terminated substrate;
step S2: mixing an isocyanate end-capped matrix with toluene, heating to 88-95 ℃, setting the stirring speed to 420-600rpm, adding triethylamine and di-n-octylamine, carrying out heat preservation and stirring reaction for 50-60min, and removing toluene by reduced pressure rotary evaporation after the reaction to obtain an oleophylic modified intermediate;
step S3: uniformly mixing an oleophylic modified intermediate, epoxy resin and ethyl acetate, maintaining the temperature at 10-15 ℃, adding dodecylamine, stirring at 300rpm for reaction for 20-25min, and removing ethyl acetate by reduced pressure rotary evaporation after the reaction is finished to obtain an epoxidation matrix;
step S4: stirring and dissolving sulfamic acid and water, dripping the dissolved sulfamic acid and water into an epoxidation matrix, stirring at 1000rpm until the viscosity is regulated to 150 mPa.s, and obtaining the white oil emulsifier.
2. The method for preparing the food white oil emulsifier according to claim 1, wherein the dosage ratio of diglycerol, hexamethylene diisocyanate, dibutyl tin dilaurate, benzoyl chloride and tetrahydrofuran is 0.1mol:0.42-0.45mol:0.1-0.15mL:20-30mg:150-180mL.
3. The method for preparing a white oil emulsifier for foods according to claim 2, wherein the diglycerol and the tetrahydrofuran are dehydrated before use.
4. The method for preparing the white oil emulsifier for foods according to claim 2, wherein the dosage ratio of the isocyanate-terminated substrate, di-n-octylamine, triethylamine and toluene is 70g:80-90mmol:0.2-0.3mL:100-120mL.
5. The method for preparing a white oil emulsifier for food according to claim 4, wherein the ratio of the amount of the lipophilic modified intermediate, the epoxy resin, the dodecylamine and the ethyl acetate is 90g:130-150g:0.8-1.3mL:160-200mL.
6. The method of preparing a white oil emulsifier for food according to claim 5, wherein the epoxy resin is selected from the group consisting of epoxy resin E-51.
7. A food white oil emulsifier, characterized in that it is produced by the method according to any one of claims 1-6.
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Citations (9)
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| CN108178976A (en) * | 2017-11-30 | 2018-06-19 | 广州亮豹涂料科技有限公司 | Anion-type water-thinned epoxy resin latex and preparation method and application |
| US10167395B1 (en) * | 2017-11-30 | 2019-01-01 | Zhejiang University Of Technology | Anti-fouling and anti-corrosion agent for marine steel structure surface and preparation method thereof |
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| CN111378095A (en) * | 2018-12-29 | 2020-07-07 | 万华化学集团股份有限公司 | Emulsifier preparation method, emulsifier, epoxy resin aqueous dispersion and preparation method |
| CN112300360A (en) * | 2020-11-03 | 2021-02-02 | 湘潭大学 | Preparation of amphiphilic dendritic copolymer |
| CN112409558A (en) * | 2020-11-06 | 2021-02-26 | 常州大学 | Epoxy emulsifier with high-branching degree hydrophilic chain and preparation method thereof |
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