CN113185720B - Modified cellulose stable oil-in-oil Pickering emulsion and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of anhydrous emulsions, and discloses a modified cellulose particle stable oil-in-oil type Pickering emulsion and a preparation method thereof, wherein the preparation method comprises the following steps: adding modified cellulose particles into the continuous phase solvent I, and uniformly dispersing to obtain modified cellulose particle dispersion liquid with the mass fraction of (0.5-4.0) wt.%; adding a dispersed phase solvent II incompatible with the continuous phase solvent I into the modified cellulose particle dispersion liquid to form an incompatible two-phase solvent mixture, and stirring to obtain an oil-in-oil Pickering emulsion with stable modified cellulose particles; wherein the mass ratio of the continuous phase solvent I to the disperse phase solvent II is 1-20: 1. the modified cellulose is used as the oil-in-oil emulsion stabilizer, has the advantages of mild and simple preparation method, adjustable surface wettability, adjustable emulsion type and the like, and avoids the limitations and the defects of complex preparation process, lack of controllability of surface wettability and the like of the block polymer and the two-dimensional nanosheet oil-in-oil stabilizer.
Description
Technical Field
The invention belongs to the technical field of oil-in-oil type Pickering emulsion, and particularly relates to modified cellulose stable oil-in-oil type Pickering emulsion and a preparation method thereof.
Background
Emulsions are generally dispersed systems composed of two incompatible liquids, and these two-phase systems have unique advantages in terms of mass and heat transfer, and are widely used in polymer preparation, cosmetics, coatings, and other fields. However, at present, most emulsions are oil-water systems, i.e. water-in-oil emulsions or oil-in-water emulsions. Therefore, the conventional emulsion system can only be applied to water-insensitive monomers and catalyst systems, namely, a large amount of general plastics and engineering plastics such as polyolefin (a coordination metal catalyst is decomposed in water), polyamide (the polymerization temperature is higher than the boiling point of water by 100 ℃), polyurethane (isocyanate generates side reaction in water) and the like can not be obtained by oil-water emulsion polymerization.
The anhydrous emulsion (oil-in-oil emulsion) system provides an ideal choice for solving the problems, namely, the polar solvent is used for replacing the water phase to prepare the emulsion, so that the limitations of water-sensitive monomers, catalysts and reaction temperature in the oil-water emulsion can be completely avoided, the advantages of low viscosity, excellent heat exchange, high polymerization rate, high molecular weight and the like of the traditional emulsion polymerization are retained, and the application prospect is very wide. Notably, the anhydrous conditions of oil-in-oil emulsions provide great convenience to the polymerization reaction, as well as great challenges to emulsion stability. The surface tension difference of the water phase and the oil phase in the traditional oil-water emulsion is larger (generally more than 50 mN/m), and the selection of the surfactant is more. The continuous phase and the disperse phase of the oil-in-oil emulsion are both solvent systems, the surface tension difference is very small (generally less than 5 mN/m), the oil-in-oil emulsion has no hydration effect, electric charges which are not uniformly distributed do not exist in the system, an electric double layer stabilizing effect is lacked at the interface of the emulsion, and the interface stability only depends on the steric hindrance of a stabilizer. Therefore, the surface characteristics and molecular weight of the stabilizer must be precisely controlled to achieve interfacial stabilization of oil-in-oil emulsions.
At present, the surfactants used to stabilize anhydrous emulsions fall into only two broad classes: structurally specific block polymers and surface functionalized nanoplates, wherein the block Polymer preparation process is complex and not conducive to precise control of interfacial wettability (Journal of the American Chemical Society,2016,138 (14): 4714-4717, journal of Colloid and Interface science,2020, 580. In summary, the prior oil-in-oil emulsion stabilizer has few kinds and lacks regulation and control performance, so that the preparation process of the oil-in-oil emulsion is complex and is not easy to popularize on a large scale.
Disclosure of Invention
The invention aims to provide a modified cellulose particle stable oil-in-oil type Pickering emulsion and a preparation method thereof, and solves the problems that the preparation process of the oil-in-oil emulsion is complex and the large-scale popularization is difficult due to the lack of an oil-in-oil emulsion stabilizer and the lack of regulation and control performance at the present stage.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of modified cellulose particle stable oil-in-oil Pickering emulsion comprises the following steps:
(1) Adding modified cellulose particles into the continuous phase solvent I, and uniformly dispersing to obtain modified cellulose particle dispersion liquid with the mass fraction of (0.5-4.0) wt.%;
(2) Adding a dispersed phase solvent II incompatible with the continuous phase solvent I into the modified cellulose particle dispersion liquid to form an incompatible two-phase solvent mixture, and stirring to obtain an oil-in-oil Pickering emulsion with stable modified cellulose particles;
wherein the mass ratio of the continuous phase solvent I to the disperse phase solvent II is 1-20: 1.
further, in the step (1), the continuous phase solvent I is a polar solvent, and the disperse phase solvent II is a non-polar solvent;
or the continuous phase solvent I is a non-polar solvent, and the disperse phase solvent II is a polar solvent.
Further, the nonpolar solvent is one or more of n-hexane, n-heptane, n-dodecane, n-tetradecane, n-hexadecane and n-octadecane.
Further, the polar solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide and acetonitrile.
Further, in the step (2), the stirring speed is 300-3000 rpm, and the stirring time is 3-10 min.
Further, in the step (1), the modified cellulose particles are alkylamine-modified cellulose particles, and are prepared by the following steps:
(1.1) adding the cellulose particles to methylene chloride, and stirring to obtain a cellulose particle dispersion;
(1.2) adding N, N' -carbonyl diimidazole into the cellulose particle dispersion liquid, and stirring and reacting for 2-12 h at 40 ℃ to obtain fiber particle dispersion liquid with activated surface hydroxyl groups; wherein the mass ratio of the cellulose particles to the N, N' -carbonyldiimidazole is 1 (1-10);
(1.3) adding alkylamine into the fiber particle dispersion liquid with the activated surface hydroxyl, continuously reacting for 12 hours at the temperature of 40 ℃, and filtering, cleaning and drying to obtain modified cellulose particles; wherein the mass ratio of the surface hydroxyl activated fiber particles to the alkylamine is 1 (1-10).
Further, in the step (1.1), the cellulose particles have a particle diameter of 1 μm to 50 μm and are of the type of α -cellulose.
Further, in the step (1.1), the mass fraction of the cellulose particles in the cellulose particle dispersion is from 1.0wt.% to 10.0wt.%.
Further, in the step (1.2), the alkylamine is one or more of n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine and n-octadecylamine.
The invention also discloses the modified cellulose particle stable oil-in-oil Pickering emulsion prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a modified cellulose particle stable oil-in-oil type Pickering emulsion, which takes modified cellulose as an oil-in-oil emulsion stabilizer, wherein the modified cellulose has the advantages of mild and simple preparation method, adjustable surface wettability, adjustable emulsion type and the like, can realize the preparation of the oil-in-oil emulsion of a polar solvent and a non-polar solvent, can realize the stability of the oil-in-oil emulsions of different types, and provides an ideal reaction system for the fields of water sensitive monomers, packaging reaction and the like. Compared with two stabilizers (block polymer and functional nano-sheet) of the oil-in-oil emulsion at present, the method has simple steps and convenient operation, the functional product has excellent stabilizing effect on the oil-in-oil emulsion, the preparation process of the invention is greatly simplified, harsh conditions such as deoxygenation, dehydration and the like are not needed, the preparation process is obviously shortened, and chain segment molecular weight design and nano-sheet stripping links are not needed.
The invention further discloses a preparation method of the modified cellulose particles, which comprises the steps of firstly using the cellulose particles as a base material, using N, N '-carbonyldiimidazole and long-chain alkylamine as reaction raw materials, activating hydroxyl on cellulose through the N, N' -carbonyldiimidazole, and further performing exchange reaction on the activated cellulose through the alkylamine and the activated cellulose to obtain the cellulose particles with different carbon chains connected with the urethane bonds. The alkylamine is used for modifying the cellulose, so that the preparation condition is mild, the process is simple and efficient, the raw material is a biomass material, the reserve is large, the price is low, and the dependence on fossil raw materials is reduced.
Drawings
FIG. 1 is a FTIR chart of virgin cellulose particles, n-hexylamine, n-decylamine, n-tetradecylamine, n-octadecylamine modified cellulose particles;
FIG. 2 is a digital photograph of the emulsions prepared in examples 1 to 6;
FIG. 3 is a digital photograph of the emulsions prepared in examples 1-6 after half a year;
FIG. 4 is a microscopic image of the N, N' -dimethylformamide dodecane emulsion prepared in example 1;
FIG. 5 is a microscopic image of an emulsion of N, N' -dimethylacetamide in dodecane prepared in example 2;
FIG. 6 is a microscope photograph of an N, N '-dimethylacetamide emulsion containing N, N' -dodecane prepared in example 3.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The invention discloses a preparation method of n-decylamine modified cellulose particles, which comprises the following steps:
(1) 0.5g of cellulose particles having a particle diameter of 25 μm was added to 49.5g of methylene chloride and stirred at room temperature to obtain a cellulose particle dispersion;
(2) Adding 0.5g of N, N' -Carbonyldiimidazole (CDI) to the cellulose particle dispersion to activate hydroxyl groups on the surface of cellulose, and reacting the mixture at 40 ℃ for 2 hours with stirring to obtain a surface hydroxyl group-activated fiber particle dispersion;
(3) Subsequently, 0.6g of n-decylamine was added to the surface hydroxyl group-activated fiber particle dispersion, and the reaction was continued at 40 ℃ for 12 hours, followed by filtration, washing to remove unreacted substances, and further drying to obtain n-decylamine-modified cellulose particles.
The application of the n-decylamine modified cellulose particles in the oil-in-oil emulsion is as follows:
weighing 0.1g of N-decylamine modified cellulose particles, adding the N-decylamine modified cellulose particles into 20.0g of continuous phase solvent N, N' -dimethylformamide, and stirring to obtain a modified cellulose dispersion liquid; weighing 2.0g of dodecane serving as a disperse phase solvent, adding the dodecane serving as the disperse phase solvent into the modified cellulose dispersion liquid to form an incompatible two-phase solvent mixture, and stirring at 300rpm for 3.0min to obtain a white oil-in-oil Pickering emulsion containing the dodecane in N, N' -dimethylformamide.
As shown in fig. 2 and 4, the oil-in-oil type Pickering emulsion of dodecane in N, N' -dimethylformamide has regular droplets and uniform size, and shows good stability.
As shown in FIG. 3, the prepared emulsion remained stable for half a year at room temperature without significant phase separation.
Example 2
The invention discloses a preparation method of n-octadecylamine modified cellulose particles, which comprises the following steps of:
(1) 0.5g of cellulose particles having a particle diameter of 25 μm was added to 9.5g of methylene chloride and stirred at room temperature to obtain a cellulose particle dispersion;
(2) Adding 1.5g of N, N' -Carbonyldiimidazole (CDI) into the cellulose particle dispersion liquid to activate the surface hydroxyl groups of the cellulose, and stirring and reacting at 40 ℃ for 2 hours to obtain the surface hydroxyl group activated fiber particle dispersion liquid;
(3) Subsequently, 1.8g of n-octadecylamine was added to the dispersion of surface hydroxyl-activated fiber particles, and the reaction was continued at 40 ℃ for 12 hours, followed by filtration, washing to remove unreacted substances, and further drying to obtain n-octadecylamine-modified cellulose particles.
The application of n-octadecylamine modified cellulose particles in oil-in-oil emulsion is as follows:
weighing 0.4g of n-octadecylamine modified cellulose particles, adding the n-octadecylamine modified cellulose particles into 40g of dodecane serving as a continuous phase solvent, and stirring to obtain a modified cellulose dispersion liquid; weighing 20.0g of disperse phase solvent N, N ' -dimethylacetamide, adding the disperse phase solvent N, N ' -dimethylacetamide into the cellulose dispersion to form an incompatible two-phase solvent mixture, and stirring at 3000rpm for 1.0min to obtain white N-dodecane N, N ' -dimethylacetamide oil-in-oil Pickering emulsion.
As shown in fig. 2 and 5, N-dodecane-in-N, N' -dimethylacetamide Pickering emulsion has regular droplets and uniform size, and shows good stability.
As shown in FIG. 3, the prepared emulsion remained stable after half a year of storage at room temperature, and no significant phase separation was observed.
Example 3
The invention discloses a preparation method of n-hexadecylamine modified cellulose particles, which comprises the following steps:
(1) Adding 0.5g of cellulose particles having a particle diameter of 5 μm to 4.5g of methylene chloride, and stirring at room temperature to obtain a cellulose particle dispersion;
(2) Adding 0.5g of N, N' -Carbonyldiimidazole (CDI) into the cellulose particle dispersion liquid to activate the surface hydroxyl groups of the cellulose, and stirring and reacting at 40 ℃ for 2 hours to obtain the surface hydroxyl group activated fiber particle dispersion liquid;
(2) Subsequently, 0.5g of n-hexadecylamine was added to the dispersion of surface hydroxyl-activated fiber particles, and the reaction was continued at 40 ℃ for 12 hours, followed by filtration, washing to remove unreacted substances, and further drying to obtain n-hexadecylamine-modified cellulose particles.
The application of the n-hexadecylamine modified cellulose particles in the oil-in-oil emulsion comprises the following steps:
weighing 0.4g of n-hexadecylamine modified cellulose particles, adding the n-hexadecylamine modified cellulose particles into 40g of dodecane serving as a continuous phase solvent, and stirring to obtain a modified cellulose dispersion liquid; weighing 40.0g of disperse phase solvent N, N ' -dimethylacetamide, adding the disperse phase solvent N, N ' -dimethylacetamide into the cellulose dispersion to form an incompatible two-phase solvent mixture, and stirring at 2000rpm for 2.0min to obtain white N-dodecane N, N ' -dimethylacetamide oil-in-oil Pickering emulsion.
As shown in fig. 2 and fig. 6, N' -dimethylacetamide-in-dodecane oil-in-oil Pickering emulsion has regular droplets and uniform size, and exhibits good stability.
As shown in FIG. 3, the prepared emulsion remained stable for half a year at room temperature without significant phase separation.
Example 4
The invention discloses a preparation method of n-tetradecylamine modified cellulose particles, which comprises the following steps:
(1) 0.5g of cellulose particles having a particle diameter of 5 μm was added to 49.5g of methylene chloride and stirred at room temperature to obtain a cellulose particle dispersion;
(2) Adding 5.0g of N, N' -Carbonyldiimidazole (CDI) to the cellulose particle dispersion to activate hydroxyl groups on the surface of cellulose, and reacting the mixture at 40 ℃ for 2 hours with stirring to obtain a fiber particle dispersion with activated hydroxyl groups on the surface;
(3) And then, adding 5.0g of n-tetradecylamine into the fiber particle dispersion liquid with the activated surface hydroxyl, continuously reacting for 12 hours at 40 ℃, filtering, cleaning to remove unreacted substances, and further drying to obtain n-tetradecylamine modified cellulose particles.
The application of the n-tetradecylamine modified cellulose particles in the oil-in-oil emulsion comprises the following steps:
weighing 0.4g of n-tetradecylamine modified cellulose particles, adding the n-tetradecylamine modified cellulose particles into 40g of dodecane serving as a continuous phase solvent, and stirring to obtain a modified cellulose dispersion liquid; weighing 10.0g of disperse phase solvent dimethyl sulfoxide, adding into the above cellulose dispersion to form an incompatible two-phase solvent mixture, and stirring at 2000rpm for 2.0min to obtain white n-dodecane dimethyl sulfoxide-coated oil-in-oil Pickering emulsion.
As shown in fig. 2, the oil-in-oil type Pickering emulsion containing dimethyl sulfoxide in n-dodecane has regular droplets and uniform size, and shows good stability.
As shown in FIG. 3, the prepared emulsion remained stable for half a year at room temperature without significant phase separation.
Example 5
The invention discloses a preparation method of n-hexylamine modified cellulose particles, which comprises the following steps:
(1) Adding 0.5g of cellulose fiber particles with the particle size of 50 mu m into 19.5g of dichloromethane, and stirring at room temperature to obtain cellulose particle dispersion liquid;
(2) Adding 3.0g of N, N' -Carbonyldiimidazole (CDI) to the cellulose particle dispersion to activate hydroxyl groups on the surface of cellulose, and reacting the mixture at 40 ℃ for 2 hours with stirring to obtain a dispersion of surface hydroxyl-activated cellulose particles;
(3) And then adding 3.0g of n-hexylamine into the fiber particle dispersion liquid with the activated surface hydroxyl, continuing to react for 12h at 40 ℃, filtering, cleaning to remove unreacted substances, and further drying to obtain n-hexylamine modified cellulose particles.
The use of n-hexylamine modified cellulose particles in an oil-in-oil emulsion is as follows:
weighing 0.4g of n-hexylamine modified cellulose particles, adding the n-hexylamine modified cellulose particles into 20g of continuous phase solvent acetonitrile, and stirring to obtain a modified cellulose dispersion liquid; weighing 10.0g of disperse phase solvent n-heptane, adding into the above cellulose dispersion to form incompatible two-phase solvent mixture, and stirring at 1000rpm for 2.0min to obtain white oil-in-acetonitrile n-heptane-containing Pickering emulsion.
As shown in fig. 2, the oil-in-oil Pickering emulsion containing n-heptane in acetonitrile has regular droplets and uniform size, and shows good stability.
As shown in FIG. 3, the prepared emulsion remained stable for half a year at room temperature without significant phase separation.
Example 6
The invention discloses a preparation method of n-octylamine modified cellulose particles, which comprises the following steps:
(1) Adding 0.5g of cellulose particles having a particle size of 1 μm to 19.5g of methylene chloride, and stirring at room temperature to obtain a cellulose particle dispersion;
(2) Adding 3.0g of N, N' -Carbonyl Diimidazole (CDI) into the system to activate the surface hydroxyl of the cellulose, and stirring and reacting for 2 hours at 40 ℃ to obtain a fiber particle dispersion liquid with the activated surface hydroxyl;
(3) Subsequently, 3.0g of n-octylamine was added to the dispersion of surface hydroxyl-activated fiber particles, and the reaction was continued at 40 ℃ for 12 hours, followed by filtration, washing to remove unreacted substances, and further drying to obtain n-octylamine-modified cellulose particles.
The application of the n-octylamine modified cellulose particles in the oil-in-oil emulsion comprises the following specific steps:
weighing 0.4g of N-octylamine modified cellulose particles, adding the N-octylamine modified cellulose particles into 20g of continuous phase solvent N, N' -dimethylformamide, and stirring to obtain a modified cellulose dispersion liquid; weighing 10.0g of dispersed phase solvent N-hexadecane, adding into the above cellulose dispersion to form incompatible two-phase solvent mixture, and stirring at 1000rpm for 2.0min to obtain white oil-in-oil type Pickering emulsion containing N, N' -dimethylformamide and N-hexadecane.
As shown in fig. 2, the N, N' -dimethylformamide-N-hexadecane oil-in-oil Pickering emulsion has regular droplets and uniform size, and shows good stability.
As shown in FIG. 3, the prepared emulsion remained stable for half a year at room temperature without significant phase separation.
As shown in figure 1, the wave number of the hexylamine, n-decylamine, n-tetradecylamine and n-octadecylamine functionalized cellulose particles prepared by the invention on an infrared spectrum is 1710-1730cm -1 A carbonyl absorption peak was observed, indicating that the CDI activation-amine exchange method successfully introduced alkylamine on the surface of the cellulose particles via urethane bonds.
Claims (8)
1. A preparation method of modified cellulose particle stable oil-in-oil Pickering emulsion is characterized by comprising the following steps:
(1) Adding modified cellulose particles into the continuous phase solvent I, and uniformly dispersing to obtain modified cellulose particle dispersion liquid with the mass fraction of (0.5-4.0) wt.%;
in the step (1), the modified cellulose particles are alkylamine-modified cellulose particles, and are prepared by the following steps:
(1.1) adding the cellulose particles to methylene chloride, and stirring to obtain a cellulose particle dispersion;
(1.2) adding N, N' -carbonyldiimidazole into the cellulose particle dispersion liquid, and stirring and reacting for 2-12 h at 40 ℃ to obtain the fiber particle dispersion liquid with activated surface hydroxyl groups; wherein the mass ratio of the cellulose particles to the N, N' -carbonyldiimidazole is 1 (1-10);
(1.3) adding alkylamine into the fiber particle dispersion liquid with the surface hydroxyl activated, continuing to react for 12 hours at the temperature of 40 ℃, and filtering, cleaning and drying to obtain modified cellulose particles; wherein the mass ratio of the surface hydroxyl activated fiber particles to the alkylamine is 1 (1-10);
(2) Adding a dispersed phase solvent II incompatible with the continuous phase solvent I into the modified cellulose particle dispersion liquid to form an incompatible two-phase solvent mixture, and stirring to obtain an oil-in-oil Pickering emulsion with stable modified cellulose particles;
wherein the mass ratio of the continuous phase solvent I to the disperse phase solvent II is 1-20:1;
in the step (1), the continuous phase solvent I is a polar solvent, and the dispersed phase solvent II is a non-polar solvent;
or the continuous phase solvent I is a non-polar solvent, and the disperse phase solvent II is a polar solvent.
2. The method for preparing the modified cellulose particle-stabilized oil-in-oil type Pickering emulsion as claimed in claim 1, wherein the non-polar solvent is one or more of n-hexane, n-heptane, n-dodecane, n-tetradecane, n-hexadecane and n-octadecane.
3. The method for preparing the modified cellulose particle-stabilized oil-in-oil Pickering emulsion as claimed in claim 1, wherein the polar solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide and acetonitrile.
4. The method for preparing the modified cellulose particle-stabilized oil-in-oil Pickering emulsion as claimed in claim 1, wherein in the step (2), the stirring speed is 300-3000 rpm, and the stirring time is 3-10 min.
5. The method for preparing a modified cellulose particle-stabilized oil-in-oil type Pickering emulsion as claimed in claim 1, wherein in the step (1.1), the cellulose particles have a particle size of 1 μm to 50 μm and are of the type of α -cellulose.
6. The method for preparing a modified cellulose particle-stabilized oil-in-oil type Pickering emulsion as claimed in claim 1, wherein in the step (1.1), the mass fraction of the cellulose particles in the cellulose particle dispersion is 1.0wt.% to 10.0wt.%.
7. The method for preparing the modified cellulose particle-stabilized oil-in-oil type Pickering emulsion as claimed in claim 1, wherein in the step (1.2), the alkylamine is one or more of n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine and n-octadecylamine.
8. The modified cellulose particle-stabilized oil-in-oil Pickering emulsion obtained by the production method as set forth in any one of claims 1 to 7.
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| CN106750375A (en) * | 2017-01-23 | 2017-05-31 | 陕西科技大学 | The method that Pickering emulsions are prepared using modified nanometer cellulose |
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