CN115746199A - Inverse emulsion and preparation method and application thereof - Google Patents
Inverse emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an inverse emulsion and a preparation method and application thereof. The preparation method comprises the following steps: dispersing an aqueous solution of a water-soluble monomer into an oil phase in the presence of a water-in-oil emulsifier to form a water-in-oil system, then carrying out a polymerization reaction in the presence of an initiator, and after the reaction is finished, mixing the obtained emulsion with an oil-in-water emulsifier to obtain the inverse emulsion; the raw materials of the water-in-oil emulsifier comprise long-chain fatty acid and diethanol amine. In the invention, the polymer with high number average molecular weight and strength can be prepared by adopting the water-in-oil emulsifier with a special structure, and the inverse emulsion can be used as a thickening agent and an emulsifier, has excellent long-term heat storage stability, has simple preparation process and low cost, and can be used as the thickening agent and the emulsifier in skin care products.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to an inverse emulsion, and a preparation method and application thereof.
Background
Thickeners are of vital importance in cosmetics, whereas thickeners used in the cosmetic field are used to thicken aqueous phases, or cream-gel systems. In cream-gel systems, especially when high levels of oil are added to the system, a certain amount of emulsifier is also added. However, emulsifiers are generally low molecular weight substances which are less resistant to the skin than polymers. Therefore, it is required to develop a polymer having both thickening and emulsifying functions.
US8668915B2 discloses inverse emulsions of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and Acrylamide (AM) under N, N-methylenebisacrylamide crosslinking, which are polymerized by forming water-in-oil inverse emulsions to give emulsions with a thickening and emulsifying function, but the long-term heat storage stability of the emulsion emulsification is to be further improved.
CN107987212A discloses a fast dissolving anionic polyacrylamide inverse emulsion and its preparation method, the preparation method comprises: preparing an oil phase and a water phase; (2) Dropwise adding the water phase into the oil phase to obtain a water-in-oil pre-emulsion; (3) introducing nitrogen into the water-in-oil pre-emulsion to remove oxygen; (4) Adding an initiator into the water-in-oil pre-emulsion to initiate polymerization reaction; (5) Adding a phase inversion agent into the reaction mixture to obtain the fast-dissolving anionic polyacrylamide inverse emulsion. The rapid-dissolving type ionic polyacrylamide reverse phase emulsion has a rapid dissolving speed, the dissolving time in water is less than 1min, and the effect of instant dissolving can be realized. However, the long-term heat storage stability of the emulsion emulsification is to be further improved.
For the thickening auxiliary agent used in the daily chemical field, the heat storage stability of the emulsification is an important index of attention of customers.
Therefore, the development of an inverse emulsion which can be used as a thickener and an emulsifier in a skin care product, has good thickening and emulsifying effects, and has good long-term thermal storage stability is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an inverse emulsion and a preparation method and application thereof. In the preparation method of the inverse emulsion, a water-in-oil emulsifier with a special structure is adopted, so that a high molecular weight and high strength polymerized emulsion can be prepared, and the inverse emulsion can be used as a thickening agent and an emulsifier and has excellent long-term heat storage stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of preparing an inverse emulsion, the method comprising the steps of:
dispersing an aqueous solution of a water-soluble monomer into an oil phase in the presence of a water-in-oil emulsifier to form a water-in-oil system, then carrying out a polymerization reaction in the presence of an initiator, and after the reaction is finished, mixing the obtained emulsion with an oil-in-water emulsifier to obtain the inverse emulsion; the raw materials of the water-in-oil emulsifier comprise long-carbon-chain fatty acid and diethanolamine.
According to the invention, the water-in-oil emulsifier prepared from the long-carbon-chain fatty acid and the diethanol amine can realize uniform emulsification of the inverse emulsion by regulating the structure of the water-in-oil emulsifier, and the prepared polymer particles are spherical, have large molecular weight and high strength, have excellent thickening performance and emulsifying performance, and have good long-term emulsification and heat storage stability.
Preferably, the water-in-oil emulsifier in the inverse emulsion is present in an amount of 2 to 4.5% by mass, and may be, for example, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, etc.
In the invention, the dosage of the water-in-oil emulsifier is too small, and gel is easy to form; too much amount is used, the workability is poor, and the elimination of the monomer is not favorable.
Preferably, the water-in-oil emulsifier has an integrated area ratio of the infrared spectrum of the amide groups to the ester groups of (0.1 to 8): 1, wherein specific values of (0.1 to 8) may be, for example, 0.5, 0.8, 1, 1.2, 1.6, 2, 2.2, 2.6, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, etc., and more preferably (3 to 8): 1.
According to the invention, the infrared spectrum integral area ratio of an amide group to an ester group in the water-in-oil emulsifier is more than 8, the hydrophilicity of the emulsifier is enhanced, the HLB value is increased, the uniformity of the water-in-oil emulsion is reduced, in the polymerization initiation process, a part of monomers migrate to the periphery of emulsion droplets, the strength of a polymer is reduced, the molecular weight of the polymer at the periphery of the emulsion droplets is small, the thickening capability is reduced, the heat storage stability of emulsification is influenced, the polymer is curled and shrunk when being heated, and the oil and fat emulsification effect is poor.
Preferably, the long carbon chain fatty acid comprises a C15 to C20 fatty acid, which may be, for example, a C16, C17, C18, C19 fatty acid, and the like.
Preferably, the long carbon chain fatty acid comprises at least one of oleic acid, linoleic acid or soy oleic acid.
Preferably, the molar ratio of the long-carbon-chain fatty acid to diethanolamine is (1-2): 1, and for example, 1.1.
Preferably, the water-in-oil emulsifier is prepared by a method comprising:
and (3) reacting the long-carbon-chain fatty acid with diethanolamine to obtain the water-in-oil emulsifier.
The pressure of the reaction is preferably 0.1 to 2MPa, and may be, for example, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa or the like, and more preferably 0.5 to 1.5MPa.
The reaction temperature is preferably 200 to 260 ℃, and may be, for example, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃ or the like.
Preferably, the reaction time is 2 to 4 hours, and for example, may be 2.5 hours, 3 hours, 3.5 hours, and the like.
Preferably, the water-soluble monomer includes at least one of a hydrophilic nonionic monomer, an acidic monomer, and/or a salt thereof.
Preferably, the hydrophilic nonionic monomer comprises at least one of acrylamide, N-vinyl pyrrolidone, or methacrylamide.
Preferably, the acidic monomer and/or salt thereof comprises at least one of acrylic acid, an acrylic acid salt, 2-acrylamido-2-methylpropanesulfonic acid salt, methacrylic acid, or a methacrylic acid salt.
Preferably, the water solution of the water-soluble monomer further comprises a cross-linking agent and/or a chelating agent.
Preferably, the crosslinking agent comprises at least one of N, N-methylene bisacrylamide, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, or polyethylene glycol dimethacrylate.
Preferably, the mass ratio of the hydrophilic nonionic monomer, the acidic monomer and/or the salt thereof and the cross-linking agent is (1-20) to (2-50) to (0.01-1), wherein the specific value in (1-20) can be, for example, 2, 4, 6, 8, 10, 12, 14, 16, 18 and the like; specific values in (2 to 50) may be, for example, 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, etc.; specific values in (0.01 to 1) may be, for example, 0.1, 0.2, 0.4, 0.6, 0.8, and the like.
In the present invention, the acidic monomer and/or a salt thereof means an acidic monomer and/or an acidic monomer salt; the mass ratio of the hydrophilic nonionic monomer, the acidic monomer and/or the salt thereof and the crosslinking agent refers to the mass ratio of the total mass of the acidic monomer and/or the salt thereof to the hydrophilic nonionic monomer and the crosslinking agent.
Preferably, the chelating agent comprises disodium ethylenediaminetetraacetate and/or tetrasodium ethylenediaminetetraacetate.
The pH of the aqueous solution of the water-soluble monomer is preferably 4 to 7, and may be, for example, 4.5, 5, 5.5, 6, 6.5, or the like.
Preferably, when the aqueous solution of the water-soluble monomer is dispersed in the oil phase, the temperature of the oil phase is5 to 15 ℃, and may be, for example, 6 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃, or the like.
Preferably, the oil phase comprises isoparaffins and/or cosmetic grade white oil.
Preferably, the oil phase comprises isomeric tridecanes.
Preferably, the initiator comprises an oxidizing agent and a reducing agent.
The amount of the oxidizing agent is preferably 0.01 to 1% by mass, for example, 0.05%, 0.1%, 0.2%, 0.4%, 0.6%, 0.8% or the like, based on the total mass of the water-soluble monomers.
Preferably, the oxidant comprises at least one of sodium persulfate, potassium persulfate, hydrogen peroxide or tert-butyl hydroperoxide.
The reducing agent is preferably used in an amount of 0.01 to 2% by mass, for example, 0.05%, 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, etc., based on the total mass of the water-soluble monomers.
Preferably, the reducing agent comprises at least one of erythorbic acid, sodium metabisulfite, sodium bisulfite, or ferrous sulfate.
Preferably, the polymerization reaction comprises adding an oxidizing agent, removing oxygen, and then dropping a reducing agent to initiate the polymerization reaction.
Preferably, the time for oxygen removal is 20 to 40min, for example, 22min, 26min, 30min, 35min, 38min, etc.
The time for dropping the reducing agent is preferably 1 to 2 hours, and may be, for example, 1.2 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.8 hours, or the like.
Preferably, the method further comprises the step of keeping the temperature after the polymerization reaction is finished.
Preferably, the temperature for the heat preservation is 60 to 80 ℃, for example, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ and the like.
Preferably, the incubation time is 0.5 to 2 hours, for example, 0.6 hour, 0.8 hour, 1 hour, 1.2 hour, 1.4 hour, 1.6 hour, 1.8 hour, etc.
Preferably, the mixing temperature is 30-40 ℃, for example, can be 32 ℃, 34 ℃, 36 ℃, 38 ℃.
Preferably, the oil-in-water emulsifier in the inverse emulsion is 2.5 to 5% by mass, and may be, for example, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, or the like.
Preferably, the oil-in-water emulsifier comprises at least one of fatty alcohol-polyoxyethylene ether and/or salt thereof, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, tween60 or Tween 80.
Preferably, the mixing time is 15-45 min, such as 16min, 18min, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min, 42min, 44min, etc.
In the invention, the mixing comprises the steps of dropwise adding the oil-in-water emulsifier into the emulsion after the polymerization reaction is finished, wherein the dropwise adding time is 15-30 min, after the dropwise adding is finished, continuously stirring for 10-20 min (for example, 12min, 14min, 16min, 18min and the like), filtering, discharging and obtaining the inverse emulsion.
As a preferred technical solution of the present invention, the preparation method comprises:
(1) Dissolving hydrophilic nonionic monomer, acidic monomer and salt thereof, cross-linking agent and chelating agent in water, and adjusting the pH value to 4-7 to obtain water solution of water-soluble monomer;
(2) Mixing and stirring an oil phase and a water-in-oil emulsifier, adding the water-soluble monomer aqueous solution obtained in the step (1) into the oil phase at the temperature of 5-15 ℃, adding an oxidant at one time, removing oxygen for 20-40 min, and then dropwise adding a reducing agent for polymerization reaction, wherein the dropwise adding time is 1-2 h; after the dropwise addition is finished, preserving the heat for 0.5-2 h at the temperature of 60-80 ℃, cooling to 30-40 ℃, adding an oil-in-water emulsifier, filtering and discharging to obtain the inverse emulsion.
In the present invention, the inverse emulsion is prepared by using the hydrophilic monomer throughout the preparation process, and the continuous phase of the emulsion is the oil phase, so that the inverse emulsion polymerization is called. The polymer particles are strongly hydrophilic. Under the premise of pre-adjusting the pH, the polymer chain segment can be rapidly expanded in water due to charge repulsion to form a certain microgel particle, and the water-in-oil emulsifier with a specific structure ensures that the prepared polymer has high strength and excellent performance in the aspect of emulsification heat storage stability.
In a second aspect, the present invention provides an inverse emulsion prepared according to the preparation method of the first aspect.
In a third aspect, the present invention provides a thickener comprising an inverse emulsion as described in the first aspect.
In a fourth aspect, the present invention provides an emulsifier comprising an invert emulsion according to the first aspect.
In a fifth aspect, the present invention provides a use of a thickener according to the third aspect and/or an emulsifier according to the fourth aspect in a skin care product.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the inverse emulsion provided by the invention, the water-in-oil emulsifier with a special structure is adopted, the inverse emulsion with high molecular weight and strength can be prepared, the inverse emulsion can be used as a thickening agent and also can be used as an emulsifier, the stability of the inverse emulsion in long-term heat storage is excellent, the oil is not layered after being emulsified and stored for 30 days at 45 ℃, and the thickening effect and the emulsifying effect are good.
Drawings
FIG. 1 is a scanning electron micrograph of the inverse emulsion provided in example 1;
FIG. 2 is a scanning electron micrograph of the inverse emulsion provided in example 9;
FIG. 3 is an infrared spectrum of the water-in-oil emulsifier obtained in preparation examples 1 and 5.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The materials used in the invention are as follows:
acrylamide (AM): the purity of Jiangsu Changjiu agricultural chemical is more than 99.5 percent;
2-acrylamido-2-methylpropanesulfonic Acid (AMPS): the shouguanhong creates an environment-friendly technology with the purity of more than 98 percent;
2-acrylamido-2-methylpropanesulfonic acid sodium salt aqueous solution (50%) (AMPS-Na): the longevity hong creates an environment-friendly technology with the purity of more than 98 percent;
acrylic Acid (AA): the purity is more than 99 percent, and the cigarette is made of Wanhua chemical;
sodium acrylate (AA-Na): the purity is more than 98 percent, and the cigarette is made of Wanhua chemical;
50% sodium hydroxide aqueous solution (NaOH): tabasheer chemistry;
trimethylolpropane triacrylate (TMPTA): chemical of three wood, the purity is more than 95%;
n, N-Methylenebisacrylamide (MBA): chemical engineering, with purity of more than 98%;
sodium Persulfate (SPS): traditional Chinese medicine with purity of more than 99%;
30% hydrogen peroxide (H) 2 O 2 ): chinese medicine, the purity is more than 98%;
isoparaffin (Isopar M): exxonmobil with purity of more than 99%;
erythorbic acid (IAA): zhengzhou Tuoyang with purity over 99%;
aliphatic polyoxyethylene ether: AEO-7 and AEO-9, basf, purity over 99%;
chelating agent: EDTA-2Na.
Preparation example 1
The water-in-oil emulsifier is prepared from raw materials comprising diethanol amine and oleic acid in a molar ratio of 1.1; the integrated area ratio of the infrared spectrum of the amide groups to the ester groups in the water-in-oil emulsifier is 3.8, and the preparation method of the water-in-oil emulsifier comprises the following steps:
according to the formula amount, putting diethanol amine and oleic acid into a reaction kettle, raising the reaction temperature to 230 ℃, adjusting the pressure of the reaction kettle to 0.5MPa, and reacting for 3 hours to obtain the water-in-oil emulsifier.
The structure of the water-in-oil emulsifier obtained in preparation example 1 was characterized by an infrared spectrometer (model: thermo Scientific iS50 FT-IR), and the result iS shown in FIG. 3, in which 1625cm of a water-in-oil emulsifier containing an amide group and an ester group was obtained -1 The peak is the amide bond absorption peak at 1741cm -1 Is an ester bond absorption peak; and by integrating the infrared area of the amide group and the ester group, the ratio of integration of the two is 3.8.
Preparation example 2
A water-in-oil emulsifier which is different from the preparation example 1 only in that the ratio of the infrared spectrum integrated area of an amide group to an ester group in the water-in-oil emulsifier is 5.6, and the preparation method of the water-in-oil emulsifier is that the pressure of a reaction kettle is 1MPa, and other raw materials, the using amount and the preparation method are the same as those of the preparation example 1.
Preparation example 3
A water-in-oil emulsifier which is different from the preparation example 1 only in that the ratio of the infrared spectrum integrated area of an amide group to an ester group in the water-in-oil emulsifier is 7.8, the preparation method of the water-in-oil emulsifier is that the pressure of a reaction kettle is 1.5MPa, and other raw materials, the using amount and the preparation method are the same as those of the preparation example 1.
Preparation example 4
A water-in-oil emulsifier which is different from preparation example 1 only in that the oleic acid is replaced with an equimolar amount of linoleic acid, and other raw materials, amounts and preparation methods are the same as those of preparation example 1.
Preparation example 5
A water-in-oil emulsifier which is different from the preparation example 1 only in that the ratio of the infrared spectrum integrated area of an amide group to an ester group in the water-in-oil emulsifier is 8.5, the preparation method of the water-in-oil emulsifier is that the pressure of a reaction kettle is 1.8MPa, and other raw materials, the using amount and the preparation method are the same as those of the preparation example 1.
The structure of the water-in-oil emulsifier obtained in preparation example 5 was characterized by an infrared spectrometer (model: thermo Scientific iS50 FT-IR), and the result iS shown in FIG. 3, in which 1625cm of a water-in-oil emulsifier containing an amide group and an ester group was obtained -1 The peak is the amide bond absorption peak at 1741cm -1 Is an ester bond absorption peak; and by integrating the infrared areas of the amide group and the ester group, the ratio of integration of the two was 8.5.
Preparation example 6
A water-in-oil emulsifier which is different from the preparation example 1 only in that the integrated area ratio of the infrared spectrum of an amide group to an ester group in the water-in-oil emulsifier is 11.3, and the preparation method of the water-in-oil emulsifier is that the pressure of a reaction kettle is 2MPa, and other raw materials, the using amount and the preparation method are the same as those in the preparation example 1.
Preparation example 7
A water-in-oil emulsifier is different from the preparation example 1 only in that the pressure of a reaction kettle in the preparation method of the water-in-oil emulsifier is 0.2MPa, and other raw materials, the using amount and the preparation method are the same as those in the preparation example 1.
Preparation example 8
A water-in-oil emulsifier which is different from preparation example 1 only in that the oleic acid is replaced with an equimolar amount of tetracosanoic acid, and other raw materials, amounts and preparation methods are the same as those of preparation example 1.
Preparation example 9
A water-in-oil emulsifier which is different from preparation example 1 only in that the oleic acid is replaced with an equimolar amount of undecanoic acid, and other raw materials, amounts and preparation methods are the same as those of preparation example 1.
Example 1
The embodiment provides a preparation method of an inverse emulsion, which specifically comprises the following steps:
(1) Mixing 125g of AM, 220g of AMPS, 320g of AMPS-Na solution, 0.2g of MBA, 1g of EDTA-2Na and 180g of deionized water, neutralizing with NaOH solution, and adjusting the pH value to 5.5 to obtain a water-soluble monomer aqueous solution;
(2) Mixing 300g of Isopar M and 30g of water-in-oil emulsifier (preparation example 1), dropwise adding the aqueous solution obtained in the step (1) into the oil phase at 5 ℃, adding 1g of 2% SPS aqueous solution once, deoxidizing for 30min, dropwise adding 2g of 2% IAA aqueous solution into the mixture to initiate polymerization, wherein the dropping time of IAA is 1h, keeping the temperature at 70 ℃ for 1h after the dropwise adding is finished, cooling to 30 ℃, slowly adding 40g of AEO-7, adding for 15min, continuing stirring for 15min after the adding is finished, filtering, and discharging to obtain the inverse emulsion (the total mass is 1346.2 g).
The morphology of the inverse emulsion obtained in example 1 was characterized by a scanning electron microscope (type: japanese Electron JSM-7900F), and the results are shown in FIG. 1, which shows that the emulsification effect is better.
Example 2
The embodiment provides a preparation method of an inverse emulsion, which specifically comprises the following steps:
(1) Mixing 180g of AM, 180g of AMPS, 320g of AMPS-Na solution, 0.4g of TMPTA, 0.5g of EDTA-2Na and 180g of deionized water, neutralizing with NaOH solution, and adjusting the pH value to 6 to obtain a water-soluble monomer aqueous solution;
(2) Mixing 300g of Isopar M and 45g of water-in-oil emulsifier (preparation example 2), dropwise adding the aqueous solution obtained in the step (1) into the oil phase at 5 ℃, adding 20g of 2% SPS aqueous solution at one time, deoxidizing for 30min, dropwise adding 35g of 2% IAA aqueous solution into the mixture to initiate polymerization, wherein the dropwise adding time of IAA is 1h, keeping the temperature at 70 ℃ for 1h after the dropwise adding is finished, cooling to 30 ℃, slowly adding 60g of AEO-7, adding for 15min, continuing stirring for 15min after the adding is finished, filtering, discharging, and obtaining the inverse emulsion (the total mass is 1410.9 g).
Example 3
The embodiment provides a preparation method of an inverse emulsion, which specifically comprises the following steps:
(1) Mixing 130g of AM, 180g of AA, 200g of AA-Na solution, 0.2g of MBA, 1g of EDTA-2Na and 150g of deionized water, neutralizing with NaOH solution, and adjusting the pH value to 7 to obtain a water-soluble monomer aqueous solution;
(2) Mixing 250g of Isopar M and 50g of water-in-oil emulsifier (preparation example 3), dropwise adding the aqueous solution obtained in the step (1) into the oil phase at 5 ℃, adding 1g of 2% SPS aqueous solution once, deoxidizing for 30min, dropwise adding 2g of 2% IAA aqueous solution into the mixture to initiate polymerization, wherein the dropping time of IAA is 1h, keeping the temperature at 70 ℃ for 1h after the dropwise adding is finished, cooling to 30 ℃, slowly adding 35g of AEO-7, adding for 15min, continuing stirring for 15min after the adding is finished, filtering, and discharging to obtain the inverse emulsion (the total mass is 1101.2 g).
Example 4
The embodiment provides a preparation method of an inverse emulsion, which specifically comprises the following steps:
(1) Mixing 100g of AM, 260g of AMPS, 220g of AMPS-Na solution, 0.5g of TMPTA, 1g of EDTA-2Na and 160g of deionized water, neutralizing with NaOH solution, and adjusting the pH value to 4 to obtain water-soluble monomer aqueous solution;
(2) Mixing 300g of Isopar M and 35g of water-in-oil emulsifier (preparation example 2), dropwise adding the aqueous solution obtained in the step (1) into the oil phase at 5 ℃, adding 15g of 2% SPS aqueous solution at one time, deoxidizing for 30min, then dropwise adding 25g of 2% IAA aqueous solution into the mixture to initiate polymerization, wherein the IAA is dropwise added for 1h, keeping the temperature at 70 ℃ for 1h after dropwise adding is finished, cooling to 30 ℃, slowly adding 65g of AEO-7, adding for 15min, continuing stirring for 15min after the addition is finished, filtering, discharging, and obtaining the inverse emulsion (the total mass is 1241.5 g).
Example 5
The embodiment provides a preparation method of an inverse emulsion, which specifically comprises the following steps:
(1) Mixing 130g of AM, 220g of AMPS, 300g of AMPS-Na solution, 0.2g of MBA, 1g of EDTA-2Na and 180g of deionized water, neutralizing with NaOH solution, and adjusting the pH value to 5.5 to obtain a water-soluble monomer aqueous solution;
(2) Mixing 300g of Isopar M and 30g of water-in-oil emulsifier (preparation example 1), dropwise adding the aqueous solution obtained in the step (1) into the oil phase at 15 ℃, adding 50g of 2% SPS aqueous solution at one time, deoxidizing for 30min, then dropwise adding 80g of 2% IAA aqueous solution into the mixture to initiate polymerization, wherein the IAA dropwise adding time is 2h, keeping the temperature at 70 ℃ for 1h after the dropwise adding is finished, cooling to 40 ℃, slowly adding 40g of AEO-7, adding for 15min, continuing stirring for 15min after the adding is finished, filtering, discharging, and obtaining the inverse emulsion (the total mass is 1431.2 g).
Example 6
The embodiment provides a preparation method of an inverse emulsion, which specifically comprises the following steps:
(1) Mixing 130g of AM, 220g of AMPS, 300g of AMPS-Na solution, 0.2g of MBA, 1g of EDTA-2Na and 180g of deionized water, neutralizing with NaOH solution, and adjusting the pH value to 5.5 to obtain a water-soluble monomer aqueous solution;
(2) 200g of Isopar M and 40g of water-in-oil emulsifier (preparation example 3) are mixed, the aqueous solution obtained in the step (1) is dripped into the oil phase at the temperature of 5 ℃, 10g of 2% SPS aqueous solution is added at one time, oxygen is removed for 30min, 20g of 2% IAA aqueous solution is dripped into the mixture to initiate polymerization, the dripping time of IAA is 1h, the temperature is kept at 80 ℃ for 0.5h after the dripping is finished, the temperature is reduced to 30 ℃, 40g of AEO-7 is slowly added, the adding time is 30min, the mixture is continuously stirred for 15min after the adding is finished, and the mixture is filtered and discharged to obtain the inverse emulsion (the total mass is 1241.2 g).
Example 7
This example provides a method for preparing an invert emulsion, which is different from example 1 only in that the water-in-oil emulsifier is the water-in-oil emulsifier provided in example 4, and other raw materials, amounts and preparation methods are the same as those of example 1.
Example 8
This example provides a method for preparing an inverse emulsion, which is different from example 1 only in that the water-in-oil emulsifier is the water-in-oil emulsifier provided in preparation example 5, and other raw materials, amounts and preparation methods are the same as those of example 1.
Example 9
This example provides a method for preparing an inverse emulsion, which is different from example 1 only in that the water-in-oil emulsifier is the water-in-oil emulsifier provided in preparation example 6, and other raw materials, amounts and preparation methods are the same as those of example 1.
The morphology of the inverse emulsion obtained in example 9 was characterized by a scanning electron microscope (model: japanese Electron JSM-7900F), and the results are shown in FIG. 2, which shows that the emulsification effect is poor.
Examples 10 to 12
Examples 10 to 12 differ from example 1 only in that the water-in-oil emulsifiers were the water-in-oil emulsifiers provided in examples 7 to 9, respectively, and the other raw materials, amounts, and preparation methods were the same as those of example 1.
Example 13
This example provides a method for preparing an invert emulsion, which is different from example 1 only in that the amount of the water-in-oil emulsifier is reduced such that the water-in-oil emulsifier in the invert emulsion has a mass percentage of 1.5%, and the other raw materials, the amount and the preparation method are the same as those in example 1.
Example 14
This example provides a method for preparing an inverse emulsion, which is different from example 1 only in that the amount of the water-in-oil emulsifier is increased to 5.5% by weight, and other raw materials, amounts and preparation methods are the same as those of example 1.
Comparative example 1
This example provides a method for preparing an inverse emulsion, which is different from example 1 only in that the water-in-oil emulsifier is Witcamide 511, and other raw materials, amounts and preparation methods are the same as example 1.
Comparative example 2
This example provides a method for preparing an inverse emulsion, which is different from example 1 only in that the water-in-oil emulsifier is soya diethanolamide, and other raw materials, amounts and preparation methods are the same as those of example 1.
Comparative example 3
This example provides a method for preparing an inverse emulsion, which is different from example 1 only in that the water-in-oil emulsifier is sorbitan oleate and oleic acid diethanolamide in a mass ratio of 1.
Performance test
(1) Thickening effect: weighing 99g of deionized water in a 200mL straight bottle; stirring with an IKA R1303 stirring paddle at 1000 rpm; shaking up the samples of the inverse emulsion prepared in the examples 1 to 14 and the comparative examples 1 to 3, weighing 1g or 2g, and adding the samples into the deionized water under the condition of stirring; stirring is continued for 30 minutes at 1000 rpm; the resulting liquid was transferred with a spatula into a 100ml transparent plastic bottle and stored at room temperature. The viscosity was measured.
(2) The emulsification effect is as follows: in a 200mL straight body bottle, 15g of liquid paraffin or silicone oil (100 cp) was weighed; in a straight bottle, 84g of deionized water was weighed; stirring with an IKA R1303 stirring paddle at 1000 rpm; shaking up the samples of the inverse emulsions prepared in examples 1 to 14 and comparative examples 1 to 3, weighing 1g, and adding the solution while stirring; stirring was continued for 30 minutes at 1000 rpm; the resulting liquid was transferred to a 100mL transparent plastic bottle with a spatula and stored at room temperature. The viscosity was measured.
(3) Long-term thermal storage stability: placing the emulsified liquid paraffin and emulsified silicone oil sample obtained in the step (2) in a constant-temperature oven at 45 ℃ for one month, testing the viscosity of the sample again, and observing whether oil drops are separated out;
in the present invention, the apparatus for viscosity testing: BROOKFIELD DV2T; accessories: RV-6 rotor; the testing steps are as follows: after initializing the instrument, setting the corresponding rotor, setting the rotating speed to be 5rpm, keeping the viscosity unchanged for 1min, and recording the final reading.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the above table, the method for preparing the inverse emulsion provided by the present invention can prepare the inverse emulsion having high molecular weight and strength by using the water-in-oil emulsifier having a specific structure, and the inverse emulsion can be used as both a thickener and an emulsifier, has excellent long-term thermal storage stability, does not delaminate after being thermally stored at 45 ℃ for 30 days after emulsifying oil, and has good thickening effect and emulsifying effect.
From examples 1 and 8 to 10, it is found that the heat storage stability after emulsification of an oil or fat with the water-in-oil emulsifier is deteriorated since the infrared spectrum integrated area ratio of the amide group to the ester group in the water-in-oil emulsifier is not within a specific range.
As can be seen from the examples 1 and 11 to 12, the number of the long-chain fatty acid carbon in the water-in-oil emulsifier is not in a specific range, the carbon chain is too long, the preparation reaction efficiency of the emulsifier is low, and the molecular weight of the emulsifier is large, so that the migration of the initiator and the monomer conversion are limited; the carbon chain is too short, the hydrophilicity of the emulsifier is enhanced, the formation of a water-in-oil emulsifying system is not facilitated, and the polymerization stability is insufficient.
From the embodiment 1 and the embodiments 13 to 14, it is known that the amount of the water-in-oil emulsifier is not within a specific range, and when the amount is small, the emulsifying effect is poor, so that the polymerization is demulsified and even gelled, and the expected product cannot be obtained; when the dosage is large, the emulsifying effect is good, but the emulsifier wraps the particles too tightly, the initiator migration is limited, the monomer conversion rate in the system is not enough, and the residual unreacted monomer can exceed the standard.
As can be seen from comparison between example 1 and the comparative example, when the water-in-oil emulsifier is replaced by another water-in-oil emulsifier, the emulsification effect is problematic, and the particle morphology after emulsification is severely affected, so that polymerization is problematic, and monomer conversion rate and strength are limited, so that the performance of the final product cannot meet the use requirements.
In conclusion, the preparation method of the inverse emulsion provided by the invention regulates and controls the structure of the water-in-oil emulsifier, adopts the water-in-oil emulsifier with a special structure, so that the inverse emulsion can be used as a thickening agent and an emulsifier, has good thickening and emulsifying effects, does not delaminate after being placed at 45 ℃ for 30 days after oil is emulsified, has good thermal storage stability, and is particularly suitable for the thickening agent and the emulsifier in skin care products.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing an inverse emulsion, comprising the steps of:
dispersing an aqueous solution of a water-soluble monomer into an oil phase in the presence of a water-in-oil emulsifier to form a water-in-oil system, then carrying out a polymerization reaction in the presence of an initiator, and after the reaction is finished, mixing the obtained emulsion with an oil-in-water emulsifier to obtain the inverse emulsion;
the raw materials of the water-in-oil emulsifier comprise long-chain fatty acid and diethanol amine.
2. The method of claim 1, wherein the water-in-oil emulsifier in the inverse emulsion is present in an amount of 2 to 4.5% by weight;
preferably, the infrared spectrum integral area ratio of the amide group to the ester group in the water-in-oil emulsifier is (0.1-8) to 1, and more preferably (3-8) to 1;
preferably, the long carbon chain fatty acids include C15 to C20 fatty acids;
preferably, the long carbon chain fatty acid comprises at least one of oleic acid, linoleic acid, or soy oleic acid;
preferably, the molar ratio of the long-carbon-chain fatty acid to the diethanolamine is (1-2): 1;
preferably, the water-in-oil emulsifier is prepared by a method comprising:
reacting long-chain fatty acid with diethanol amine to obtain the water-in-oil emulsifier;
preferably, the pressure of the reaction is 0.1 to 2MPa, and more preferably 0.5 to 1.5MPa;
preferably, the temperature of the reaction is 200-260 ℃;
preferably, the reaction time is 2 to 4 hours.
3. The production method according to claim 1 or 2, wherein the water-soluble monomer comprises at least one of a hydrophilic nonionic monomer, an acidic monomer, and/or a salt thereof;
preferably, the hydrophilic nonionic monomer comprises at least one of acrylamide, N-vinyl pyrrolidone, or methacrylamide;
preferably, the acidic monomer and/or salt thereof comprises at least one of acrylic acid, an acrylate salt, 2-acrylamido-2-methylpropanesulfonic acid salt, methacrylic acid, or a methacrylate salt;
preferably, the water solution of the water-soluble monomer also comprises a cross-linking agent and/or a chelating agent;
preferably, the crosslinking agent comprises at least one of N, N-methylene bisacrylamide, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, or polyethylene glycol dimethacrylate;
preferably, the mass ratio of the hydrophilic nonionic monomer, the acidic monomer and/or the salt thereof and the cross-linking agent is (1-20): 2-50): 0.01-1;
preferably, the chelating agent comprises disodium ethylenediaminetetraacetate and/or tetrasodium ethylenediaminetetraacetate;
preferably, the pH of the aqueous solution of the water-soluble monomer is 4 to 7.
4. The production method according to any one of claims 1 to 3, wherein the temperature of the oil phase is5 to 15 ℃ when the aqueous solution of the water-soluble monomer is dispersed in the oil phase;
preferably, the oil phase comprises isoparaffins and/or cosmetic grade white oil;
preferably, the oil phase comprises isomeric tridecanes;
preferably, the initiator comprises an oxidizing agent and a reducing agent;
preferably, the amount of the oxidant accounts for 0.01-1% of the total mass of the water-soluble monomer;
preferably, the oxidizing agent comprises at least one of sodium persulfate, potassium persulfate, hydrogen peroxide or tert-butyl hydroperoxide;
preferably, the amount of the reducing agent is 0.01 to 2 percent of the total mass of the water-soluble monomer;
preferably, the reducing agent comprises at least one of erythorbic acid, sodium metabisulfite, sodium bisulfite, or ferrous sulfate;
preferably, the polymerization reaction comprises adding an oxidizing agent, and after deoxidizing, dropwise adding a reducing agent to initiate the polymerization reaction;
preferably, the time for removing oxygen is 20-40 min;
preferably, the time for dripping the reducing agent is 1 to 2 hours.
5. The process according to any one of claims 1 to 4, further comprising a step of keeping the temperature after the polymerization reaction;
preferably, the temperature of the heat preservation is 60-80 ℃;
preferably, the heat preservation time is 0.5-2 h;
preferably, the temperature of the mixing is 30-40 ℃;
preferably, the mass percentage of the oil-in-water emulsifier in the inverse emulsion is 2.5-5%;
preferably, the oil-in-water emulsifier comprises at least one of fatty alcohol-polyoxyethylene ether and/or salt thereof, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, tween60 or Tween 80;
preferably, the mixing time is 15 to 45min.
6. The production method according to any one of claims 1 to 5, characterized by comprising:
(1) Dissolving hydrophilic nonionic monomer, acid monomer and/or salt thereof, cross-linking agent and chelating agent in water, and adjusting the pH value to 4-7 to obtain water solution of water-soluble monomer;
(2) Mixing and stirring an oil phase and a water-in-oil emulsifier, adding the water-soluble monomer aqueous solution obtained in the step (1) into the oil phase at the temperature of 5-15 ℃, adding an oxidant at one time, removing oxygen for 20-40 min, and then dropwise adding a reducing agent for polymerization reaction, wherein the dropwise adding time is 1-2 h; after the dropwise addition is finished, preserving the heat for 0.5-2 h at the temperature of 60-80 ℃, cooling to 30-40 ℃, adding an oil-in-water emulsifier, filtering and discharging to obtain the inverse emulsion; the raw materials of the water-in-oil emulsifier comprise long-chain fatty acid and diethanol amine.
7. An inverse emulsion produced by the production method according to any one of claims 1 to 6.
8. A thickener comprising the inverse emulsion of claim 7.
9. An emulsifier comprising the inverse emulsion of claim 7.
10. Use of a thickener according to claim 8 and/or an emulsifier according to claim 9 in skin care products.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382003A (en) * | 2011-07-28 | 2012-03-21 | 西安石油大学 | Preparation method of long-chain fatty acyl ethanolamine |
| CN109666475A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt low-tension nanosphere profile control agent and preparation method thereof |
| CN114349908A (en) * | 2022-01-21 | 2022-04-15 | 万华化学集团股份有限公司 | Preparation method of inverse emulsion, thickener and emulsifier |
| WO2022207696A1 (en) * | 2021-03-31 | 2022-10-06 | Scott Bader Company Limited | Inverse emulsion thickeners |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382003A (en) * | 2011-07-28 | 2012-03-21 | 西安石油大学 | Preparation method of long-chain fatty acyl ethanolamine |
| CN109666475A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt low-tension nanosphere profile control agent and preparation method thereof |
| WO2022207696A1 (en) * | 2021-03-31 | 2022-10-06 | Scott Bader Company Limited | Inverse emulsion thickeners |
| CN114349908A (en) * | 2022-01-21 | 2022-04-15 | 万华化学集团股份有限公司 | Preparation method of inverse emulsion, thickener and emulsifier |
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