CN115403730A - Food white oil emulsifier and preparation method thereof - Google Patents
Food white oil emulsifier and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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
- C09D7/65—Additives macromolecular
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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, excess hexamethylene diisocyanate reacts with diglycerol to prepare a substrate with branched high-activity isocyanate groups, a small amount of di-n-octylamine is grafted with a double-branched saturated alkane chain to improve the compatibility with white oil, low-viscosity epoxy resin is used for modifying the substrate, an epoxy group is introduced to endow the emulsifier with certain cross-linking property, sulfamic acid reacts with a part of epoxy group, a sulfonic group is grafted to further improve the hydrophilicity of the emulsifier, and the state of the emulsifier is adjusted; tests show that the white oil emulsion prepared from the emulsifier has fine particle size, the average particle size is 420-505nm, the storage stability reaches 15-22d at 50 ℃ and the stability reaches 50-60min under the condition of centrifugation at 4000rpm, and the emulsifying state is obviously superior to that of the conventional universal emulsifier.
Description
Technical Field
The invention belongs to the technical field of emulsifiers, and particularly relates to a food white oil emulsifier and a preparation method thereof.
Background
The white oil is colorless transparent oily liquid without odor, is a mixture of liquid hydrocarbons, contains C16-C31 n-isoparaffin as main component, and is prepared from high boiling fraction of petroleum fraction by dewaxing, carbonizing, neutralizing, and refining with activated clay.
The food white oil is transparent colorless non-fluorescent mineral oil with high extraction precision, removes most of impurities harmful to human bodies, such as aromatic hydrocarbon, nitrogen, sulfur and the like in the attribute of the food white 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 viscosity-temperature performance, the impurity content is extremely low, the food white oil can effectively reduce the yellowing of a coating when being applied to the coating, and the food white oil is mostly used as a diluent in the existing water-based decorative coating. The existing white oil emulsifier is compounded by a plurality of surfactants and auxiliaries, part of compounded components have great influence on the performance of the coating, particularly the yellowing resistance, and in addition, the compound emulsifier has low emulsification effect on the white oil, particularly the mechanical stability of the emulsion; therefore, the application aims to develop the single-component emulsifier which fully exerts the advantages of the white oil food.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide a food white oil emulsifier and a preparation method thereof.
The purpose of the invention can be realized 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 dibutyltin dilaurate, setting the stirring speed to 240-360rpm, heating to 50-55 ℃, slowly adding diglycerol, then adding benzoyl chloride, increasing the stirring speed to 600rpm, heating to 70-75 ℃, performing reflux reaction for 20-30min, and removing tetrahydrofuran by rotary evaporation after the reaction is finished to obtain an isocyanate-terminated matrix;
further, diglycerin, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran were used in a ratio of 0.1mol:0.42-0.45mol:0.1-0.15mL:20-30mg:150-180mL, reacting diglycerin with excessive hexamethylene diisocyanate under the catalysis of dibutyltin dilaurate to prepare an isocyanate-terminated matrix molecule containing branched isocyanate groups;
further, diglycerin and tetrahydrofuran were dehydrated before use.
Step S2: uniformly mixing an isocyanate-terminated matrix and toluene, heating to 88-95 ℃, setting the stirring speed at 420-600rpm, adding triethylamine and di-n-octylamine, carrying out heat preservation stirring reaction for 50-60min, and carrying out reduced pressure rotary evaporation to remove toluene after the reaction to obtain an oleophylic modified intermediate;
further, the amount ratio of the isocyanate-terminated base, di-n-octylamine, triethylamine and toluene was 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 oleophylic modified intermediate molecules contain double-branched saturated alkane chains and have good compatibility with white oil.
And step S3: uniformly mixing the oleophylic modified intermediate, epoxy resin and ethyl acetate, maintaining the temperature at 10-15 ℃, adding the dodecyl tertiary amine, stirring and reacting at 300rpm for 20-25min, depressurizing and rotary-steaming after the reaction is finished, and removing the ethyl acetate to obtain an epoxidized matrix;
preferably, the epoxy resin is selected from epoxy E-51.
Further, the dosage ratio of the oleophylic modified intermediate, the epoxy resin, the dodecyl tertiary amine and the ethyl acetate is 90g:130-150g:0.8-1.3mL:160-200mL of the modified intermediate, and the epoxy resin reacts with the residual isocyanate group on the molecule of the modified intermediate under the catalysis of the dodecyl tertiary amine to perform epoxidation modification on the modified intermediate.
And step S4: stirring and dissolving sulfamic acid and water, then dropwise adding the dissolved sulfamic acid and water into an epoxidation matrix, and stirring at 1000rpm until the viscosity is adjusted to 150mPa & s to obtain 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 the reaction of excessive hexamethylene diisocyanate and diglycerol to prepare a substrate with branched high-activity isocyanate groups, a small amount of di-n-octylamine reacts with partial isocyanate under a specific process, a double-branched saturated alkane chain is grafted on the substrate, the double-branched saturated alkane chain has good compatibility with white oil, then low-viscosity epoxy resin is adopted to react with residual isocyanate groups, epoxy groups are introduced to endow the emulsifier with certain cross-linking property, so that the emulsifier can interact with a coating, the film forming property of the coating is prevented from being influenced by the emulsifier, and finally sulfonic groups are grafted by the reaction of sulfamic acid and partial epoxy groups to further improve the hydrophilicity of the emulsifier and adjust the state of the emulsifier. Tests show that the emulsifier prepared by the invention is applied to 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 centrifugation at 4000rpm, and the emulsification state is obviously superior to that of the existing general emulsifier.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In this example, the food white oil emulsifier is prepared by the following specific steps:
s1, synthesis of the substrate
In the step, diglycerol is used as a raw material, tetrahydrofuran is used as a solvent, the diglycerol and the tetrahydrofuran are easy to absorb moisture, and in order to avoid the influence of moisture on a synthetic product, dehydration treatment is carried out before use, and the specific method comprises the following steps: decompressing the diglycerol to 100Pa, decompressing and removing at 100 ℃ for 30min, circularly adsorbing and dehydrating tetrahydrofuran for 1h by adopting a silica gel drying tube, and adopting the same dehydration method in the following examples;
adding hexamethylene diisocyanate and tetrahydrofuran into a flask, stirring and mixing at 120rpm for 10min, dispersing the hexamethylene diisocyanate in the tetrahydrofuran, adding dibutyltin dilaurate, setting the stirring speed to be 360rpm, heating to 55 ℃, adding diglycerin into the flask at a constant speed within 10min, adding a small amount of benzoyl chloride after completely adding, increasing the stirring speed to be 600rpm, heating to 75 ℃, performing reflux reaction for 20min, performing rotary evaporation to remove the tetrahydrofuran after the reaction is finished, and taking a rotary evaporation product to obtain an isocyanate-terminated matrix;
in the above reaction, diglycerin, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran were used in a ratio of 0.1mol:0.45mol:0.15mL:30mg:180mL, and the amount of diglycerol was determined by 0.1 mol.
s2, lipophilic modification
Adding an isocyanate-terminated matrix and toluene into a flask, stirring and mixing at 300rpm for 5min, keeping stirring and heating to 95 ℃, increasing the stirring speed to 600rpm, mixing triethylamine and di-n-octylamine, adding into the flask, keeping the temperature, stirring and reacting for 50min, reducing the pressure to 100Pa after reaction, removing the toluene by rotary evaporation, and taking a rotary evaporation product to obtain an oleophylic modified intermediate;
in the above reaction, the amount ratio of the isocyanate terminated matrix, di-n-octylamine, triethylamine and toluene was 70g:90mmol:0.3mL:120mL, based on 70g of isocyanate-terminated substrate.
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 kettle, controlling the temperature of a reaction system to be 15 ℃ by circulating ice water, adding dodecyl tertiary amine, stirring at a stirring speed of 300rpm for 20min, reducing the pressure to be below 30Pa after the reaction is finished, controlling the temperature to be not higher than 35 ℃, and removing the ethyl acetate to obtain an epoxidized matrix;
in the above reaction, the amount ratio of the oleophilic modified intermediate, epoxy resin, tertiary dodecyl amine and ethyl acetate is 90g:150g:1.3mL:200mL, as quantified as 90g of oleophilic modified intermediate, wherein the epoxy resin is selected from epoxy resin E-51, provided by Complex advanced materials (Shanghai) Co., ltd, the following examples employ the same raw materials.
s4, hydrophilic modification
Dissolving sulfamic acid in water, dropwise adding the dissolved 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 150mPa & s to obtain the white oil emulsifier.
Example 2
In this example, the food white oil emulsifier is prepared by the following specific steps:
s1, synthesis of the substrate
Adding hexamethylene diisocyanate and tetrahydrofuran into a flask, stirring and mixing at 120rpm for 10min, dispersing the hexamethylene diisocyanate in the tetrahydrofuran, adding dibutyltin dilaurate, setting the stirring speed to 240rpm, heating to 50 ℃, adding diglycerin into the flask at a constant speed within 10min, adding a small amount of benzoyl chloride after completely adding, increasing the stirring speed to 600rpm, heating to 70 ℃, performing reflux reaction for 30min, removing the tetrahydrofuran by rotary evaporation after the reaction is finished, taking a rotary evaporation product, and obtaining an isocyanate-terminated matrix;
in the above reaction, diglycerin, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran were used in a ratio of 0.1mol:0.42mol:0.1mL:20mg:150mL, and the amount of diglycerin was 0.1 mol.
s2, lipophilic modification
Adding an isocyanate-terminated matrix and toluene into a flask, stirring and mixing at 300rpm for 5min, keeping stirring and heating to 88 ℃, increasing the stirring speed to 420rpm, mixing triethylamine and di-n-octylamine, adding into the flask, keeping the temperature, stirring and reacting for 60min, reducing the pressure to 100Pa after the reaction, removing the toluene by rotary evaporation, and taking a rotary evaporation product to obtain an oleophylic modified intermediate;
in the above reaction, the amount ratio of the isocyanate-terminated base, di-n-octylamine, triethylamine and toluene was 70g:80mmol:0.2mL:100mL, quantified as 70g of isocyanate-terminated substrate.
s3 epoxidation treatment
Adding the 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 kettle, controlling the temperature of a reaction system to be 10 ℃ by circulating ice water, adding dodecyl tertiary amine, stirring and reacting at a stirring speed of 300rpm for 25min, reducing the pressure to be below 30Pa after the reaction is finished, controlling the temperature to be not higher than 35 ℃, and removing the ethyl acetate to obtain an epoxidized matrix;
in the above reaction, the amount ratio of the oleophilic modified intermediate, epoxy resin, tertiary dodecyl amine and ethyl acetate is 90g:130g:0.8mL:160mL, determined as 90g of lipophilic modified intermediate.
s4, hydrophilic modification
Dissolving sulfamic acid in water, dropwise adding the dissolved 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 150mPa & s to obtain the white oil emulsifier.
Example 3
The food white oil emulsifier prepared by the embodiment is specifically implemented as follows:
s1, synthesis of the substrate
Adding hexamethylene diisocyanate and tetrahydrofuran into a flask, stirring and mixing at 120rpm for 10min, dispersing the hexamethylene diisocyanate into the tetrahydrofuran, adding dibutyltin dilaurate, setting the stirring speed to 360rpm, heating to 50 ℃, adding diglycerin into the flask at a constant speed within 10min, adding a small amount of benzoyl chloride after completely adding, increasing the stirring speed to 600rpm, heating to 72 ℃, performing reflux reaction for 28min, removing the tetrahydrofuran by rotary evaporation after the reaction is finished, and taking a rotary evaporation product to obtain an isocyanate-terminated matrix;
in the above reaction, diglycerin, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran were used in a ratio of 0.1mol:0.45mol:0.15mL:25mg:160mL, and the amount of the reagent was determined as 0.1mol of diglycerol.
s2, lipophilic modification
Adding an isocyanate-terminated matrix and toluene into a flask, stirring and mixing at 300rpm for 5min, keeping stirring and heating to 90 ℃, increasing the stirring speed to 480rpm, mixing triethylamine and di-n-octylamine, adding into the flask, keeping the temperature, stirring and reacting for 55min, reducing the pressure to 100Pa after reaction, removing the toluene by rotary evaporation, and taking a rotary evaporation product to obtain an oleophylic modified intermediate;
in the above reaction, the amount ratio of the isocyanate terminated matrix, di-n-octylamine, triethylamine and toluene was 70g:85mmol:0.25mL:100mL, quantified as 70g of isocyanate-terminated substrate.
s3 epoxidation treatment
Adding the 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 kettle, controlling the temperature of a reaction system to be 12 ℃ by circulating ice water, adding dodecyl tertiary amine, stirring and reacting at a stirring speed of 300rpm for 22min, reducing the pressure to be below 30Pa after the reaction is finished, controlling the temperature to be not higher than 35 ℃, and removing the ethyl acetate to obtain an epoxidized matrix;
in the above reaction, the amount ratio of the oleophilic modified intermediate, epoxy resin, tertiary dodecyl amine and ethyl acetate is 90g:140g:1.1mL:180mL, determined as 90g of lipophilic modified intermediate.
s4, hydrophilic modification
Dissolving sulfamic acid in water, dropwise adding the dissolved 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 150mPa & s to obtain the white oil emulsifier.
Example 4
The food white oil emulsifier prepared by the embodiment is specifically implemented as follows:
s1 Synthesis of the substrate
Adding hexamethylene diisocyanate and tetrahydrofuran into a flask, stirring and mixing at 120rpm for 10min, dispersing the hexamethylene diisocyanate in the tetrahydrofuran, adding dibutyltin dilaurate, setting the stirring speed to 300rpm, heating to 52 ℃, adding diglycerin into the flask at a constant speed within 10min, adding a small amount of benzoyl chloride after completely adding, increasing the stirring speed to 600rpm, heating to 75 ℃, performing reflux reaction for 25min, performing rotary evaporation to remove the tetrahydrofuran after the reaction is finished, and taking a rotary evaporation product to obtain an isocyanate-terminated matrix;
in the above reaction, diglycerin, hexamethylene diisocyanate, dibutyltin dilaurate, benzoyl chloride and tetrahydrofuran were used in a ratio of 0.1mol:0.42mol:0.13mL:30mg:180mL, and the amount of diglycerol was determined by 0.1 mol.
s2, lipophilic modification
Adding an isocyanate-terminated matrix and toluene into a flask, stirring and mixing at 300rpm for 5min, keeping stirring and heating to 92 ℃, increasing the stirring speed to 600rpm, mixing triethylamine and di-n-octylamine, adding into the flask, keeping the temperature, stirring and reacting for 55min, reducing the pressure to 100Pa after reaction, removing the toluene by rotary evaporation, and taking a rotary evaporation product to obtain an oleophylic modified intermediate;
in the above reaction, the amount ratio of the isocyanate-terminated base, di-n-octylamine, triethylamine and toluene was 70g:90mmol:0.2mL:120mL, based on 70g of isocyanate-terminated substrate.
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 kettle, controlling the temperature of a reaction system to be 10 ℃ by circulating ice water, adding dodecyl tertiary amine, stirring at a stirring speed of 300rpm for reaction for 25min, reducing the pressure to be below 30Pa after the reaction is finished, controlling the temperature to be not higher than 35 ℃, and removing the ethyl acetate to obtain an epoxidized matrix;
in the above reaction, the amount ratio of the oleophilic modified intermediate, epoxy resin, tertiary dodecyl amine and ethyl acetate is 90g:140g:1.2mL:180mL, and 90g lipophilic modified intermediate.
s4, hydrophilic modification
Dissolving sulfamic acid in water, dropwise adding the dissolved 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 150mPa & s to obtain the white oil emulsifier.
Comparative example 1
The white oil emulsifier sold in the market of the comparative example is provided by Nantong Chen Runjiang chemical Co.
The following performance tests were performed on the white oil emulsifiers prepared in examples 1-4 and the white oil emulsifier provided in the comparative example:
taking 100mL of food white oil test samples provided by Xiang Fine oil products Co., ltd, dongguan, respectively adding more than 10g of emulsifier, adding deionized water to quantify to 500mL, placing in a high-speed emulsifier, and shearing at 2800rpm for 10min to obtain emulsion;
testing the particle size of the emulsion: adopting ZS90 type nanometer laser particle size to measure the particle size distribution in the emulsion, wherein the testing temperature is 25 +/-1 ℃;
storage stability: according to the GB/T6765.3-1986 standard, the emulsion is sampled and placed in a glass bottle, the glass bottle is kept stand at the constant temperature of 50 ℃, the state of the emulsion is observed under a fluorescent lamp, and the layering time is recorded;
mechanical stability: sampling the emulsion, placing the sample in a glass bottle, placing the glass bottle in a TG16-WS centrifugal machine, centrifuging at 4000rpm, taking out the obtained product after centrifugation, standing for 10min, observing the state of the emulsion under a fluorescent lamp, taking the centrifugation time as 5min as a gradient until obvious layering occurs, and recording the obtained gradient as the layering time;
specific test data are shown in table 1:
TABLE 1
The data in Table 1 show 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 of 4000rpm, and the emulsification state is obviously superior to that of the existing general emulsifier.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of 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 dibutyltin dilaurate, stirring and heating to 50-55 ℃, slowly adding diglycerin, then adding benzoyl chloride, increasing the stirring speed to 600rpm, heating to 70-75 ℃, carrying out reflux reaction for 20-30min, and removing tetrahydrofuran by rotary evaporation after the reaction is finished to obtain an isocyanate terminated matrix;
step S2: mixing an isocyanate-terminated matrix and toluene, heating to 88-95 ℃, setting the stirring speed at 420-600rpm, adding triethylamine and di-n-octylamine, carrying out heat preservation stirring reaction for 50-60min, and carrying out reduced pressure rotary evaporation to remove toluene after the reaction to obtain an oleophylic modified intermediate;
and step S3: uniformly mixing the oleophylic modified intermediate, epoxy resin and ethyl acetate, maintaining the temperature at 10-15 ℃, adding dodecyl tertiary amine, stirring and reacting at 300rpm for 20-25min, and performing reduced pressure rotary evaporation to remove ethyl acetate after the reaction is finished to obtain an epoxidized matrix;
and step S4: stirring and dissolving sulfamic acid and water, then dropwise adding the mixture into an epoxidized matrix, and stirring at 1000rpm until the viscosity is adjusted to 150mPa & s to obtain the white oil emulsifier.
2. The method for preparing the food white oil emulsifier according to claim 1, wherein the diglycerin, the hexamethylene diisocyanate, the dibutyltin dilaurate, the benzoyl chloride and the tetrahydrofuran are used in a ratio of 0.1mol:0.42-0.45mol:0.1-0.15mL:20-30mg:150-180mL.
3. The method of claim 2, wherein the diglycerin and tetrahydrofuran are dehydrated before use.
4. The method for preparing the food white oil emulsifier according to claim 2, wherein the ratio of the isocyanate-terminated matrix, di-n-octylamine, triethylamine and toluene is 70g:80-90mmol:0.2-0.3mL:100-120mL.
5. The method for preparing the food white oil emulsifier according to claim 4, wherein the ratio of the amount of the oleophilic modified intermediate, the epoxy resin, the lauryl tertiary amine and the ethyl acetate is 90g:130-150g:0.8-1.3mL:160-200mL.
6. The method for preparing a food white oil emulsifier according to claim 5, wherein the epoxy resin is selected from epoxy resin E-51.
7. A process for the preparation of a food white oil emulsifier, characterised in that it is prepared by a process as claimed in any one of claims 1 to 6.
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| CN202211251585.5A CN115403730B (en) | 2022-10-13 | 2022-10-13 | Food white oil emulsifier and preparation method thereof |
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| CN202211251585.5A CN115403730B (en) | 2022-10-13 | 2022-10-13 | Food white oil emulsifier and preparation method thereof |
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| CN115403730B CN115403730B (en) | 2023-06-27 |
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