CN103111208A - Solid suspension monodisperse emulsion and emulsifying method thereof - Google Patents
Solid suspension monodisperse emulsion and emulsifying method thereof Download PDFInfo
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Abstract
The invention provides a solid suspension monodisperse emulsion and an emulsifying method thereof. The emulsifying method comprises the following steps: 1) preparation of solid suspension: dispersing solid particles with the particle size of 0.05-20 mu m in a solvent A which is compatible with the solid particles, thereby preparing a solid suspension of which the solid particle mass concentration is 1-50 wt%; 2) preparation of continuous phase: dissolving an emulsifier in a solvent B which is incompatible with the solid particles in the step 1); 3) emulsification: at the temperature of 30-80 DEG C, driving the solid suspension to pass through a microporous membrane with the pore size of 1-50 mu m and flow into the continuous phase in the step 2) under the action of 0.01-1 MPa atmospheric pressure to obtain a primary emulsion; and at the temperature of 30-80 DEG C, driving the primary emulsion to pass through the microporous membrane with the pore size of 1-50 mu m under the action of 0.01-1 MPa atmospheric pressure, and repeating the operation several times. The prepared emulsion has the advantages of uniform solid particle content in emulsion droplets and high stability.
Description
Technical field
The present invention relates to a kind of emulsification method that contains the emulsification system of solid particle, be specifically related to a kind of solid suspension and prepare the method for single distribution emulsion through emulsification, contain solid particle in its dispersed phase drop of the emulsion that makes (emulsion droplet).
Background technology
Emulsion is essential and bringing into play greatly effect in daily life, and it can be namely complete product, can derive again the higher rear end product of cost performance.Product such as milk breast, cosmetics, agricultural chemicals, paint, oral liquid etc. are with the form storage of emulsion state mostly and use; The product that the rear end derives is more the goods of capsule, microballoon, and the preparation of nearly all chemical synthesis capsule and microballoon is all first to prepare good emulsion.Emulsion can realize that the stable of heterogeneous material coexists, emulsion droplet one individual system.But a kind of emulsion can realize that again each is to equal property, the more important thing is that the emulsion droplet particle size easily controls, as long as demulsifying phenomenon does not occur emulsion, prepared emulsion droplet just possesses most performance that capsule is arranged, as reducing volatility, the material that makes similar essence is non-volatile before not using to be fallen; Improve the stability (the large easy oxidation of multi-catalyst sees that easily light decomposes, and is subject to temperature or moisture effects) of material; Cover the bad smell of medicine or harmful substance etc.The character of emulsion has the size droplet diameter of very big-difference, particularly decentralized photo and its size droplet diameter to distribute because of the difference of emulsification method.And drop grain diameter and the distribution of formation decentralized photo are the key factors that has a strong impact on stability of emulsion or final products character.And its complexity of emulsification system of introducing solid particle is higher, this emulsification system how emulsification to prepare good stability, the size droplet diameter single single distribution emulsion that distributes be the technical problem that the art needs to be resolved hurrily always.
Along with research and the deepening continuously of production application, emulsifying technology is developed to multiple emulsion from traditional single liquid liquid phase emulsification, and extends to the composite emulsifying of solid liquid phase, as the emulsification in early stage of capsule in electrophoresis showed etc., has effect preferably.But the emulsification of present stage mainly relies on the emulsification of mechanical force, and traditional agitating mode commonly used makes solid suspension oil phase (or water) be dispersed to water (or oil phase), forms unsettled emulsion; Particularly when containing solid particle in emulsification system, its stability of the emulsion that makes is extremely undesirable.Adopt traditional prepared emulsion of agitating mode to have multiple deficiency, distribute wide as the emulsion droplet particle diameter, the stability extreme difference, and under the effect of mechanical force, solids skewness in suspension, easily enrichment and reunion cause the output of the products such as high value capsule of last formation of microemulsion extremely low, and properties of product is very unstable.
Publication number is the Chinese patent application of CN101421027A, a kind of emulsification method is disclosed, its be by with two or more each other abundant inconsistent liquid pass continuously or gradually the plural mesh element that is located at certain intervals in the runner with emulsifying agent, be used for providing the emulsion of the drop with required average particle size particle size and required particle size distribution.This emulsification method needs a kind of exclusive equipment to realize its emulsion process.The emulsification method that this patent provides does not illustrate its emulsifying effectiveness in containing the emulsification system of solid particle yet.
Because the conventional emulsification method has many defectives, people have developed some new emulsification methods gradually in recent years, and the film emulsion process is one of them.The film emulsion process is with the pressurization of decentralized photo liquid, makes it by multiple aperture plasma membrane, forms fine droplets and enters in uniform dielectric (continuous phase), is modulated into the method for emulsion.The people such as big waves have studied employing film emulsion process and have prepared the nominal particle size monodisperse emulsion, by accurate controlling diaphragm emulsification condition, having prepared average grain diameter is 3.24 μ m, decentralization is 0.56 O/W type monodisperse emulsion (document: big waves, Wang Baoguo, the film emulsion process prepares the nominal particle size monodisperse emulsion, Tsing-Hua University's journal natural science edition, 2006,46(3)).But the emulsification system in the document does not relate to the situation that contains solid particle yet, and for the emulsification system that contains solid particle, its emulsifying effectiveness also can't be predicted.
Summary of the invention
For making up the deficiencies in the prior art, the invention provides a kind of emulsification method of solid suspension list distribution emulsion, adopt this emulsification method can make the solid suspension list distribution emulsion of particle diameter narrow distribution, the solid content homogeneous of emulsion droplet in obtained emulsion, the good emulsion stability of preparation has greatly promoted emulsifying power and speed simultaneously.
Technical scheme provided by the present invention is as follows:
A kind of emulsification method of solid suspension list distribution emulsion comprises the steps:
1) preparation solid suspension: be that the hydrophily of 0.05 ~ 20 μ m or oil loving solid particle are scattered in solvent orange 2 A with the solid particle sympathy with particle diameter, make the solid suspension that mass of solid particles concentration is 1 ~ 50wt%; Described solid particle can be modification or unmodified, and the hydrophily of modification or lipophile solid particle preferably adopt chemical graft process or macromolecule modification by coating, can make solid particle have more stable protective layer, and particle disperses more even; The particle diameter of solid particle more preferably 0.1 ~ 0.7 μ m adopts further preferred particle diameter, can greatly reduce the reunion of particle, and particle is more easily disperseed, and also is difficult for blocking microporous membrane pores simultaneously; The kind of solid particle has no particular limits, such as thinking the inorganic matters such as hydrophily or oil loving magnesia, carbon black, titanium dioxide, cupric oxide, cupric oxide, copper-chrome black, iron oxide black, iron oxide red, can be also that the surface is by the polystyrene polymer microsphere of hydrophilic or lipophilicity substance coating, polyethylene microballoon, polypropylene microballoon etc.
2) preparation continuous phase: with emulsifiers dissolve in the solvent B of the non-sympathy of the described solid particle of step 1) in, make continuous phase; The mass concentration of emulsifying agent in continuous phase is preferably 0.5 ~ 3wt%, more preferably 1 ~ 2wt%;
3) emulsification: under 30 ~ 80 ℃ of conditions, with solid suspension under the air pressure of 0.01 ~ 1MPa promotes the microporous barrier by 1 ~ 50 μ m aperture and flow into step 2) continuous phase in, obtain elementary emulsion; Under 30 ~ 80 ℃ of conditions, elementary emulsion is promoted lower microporous barrier by 1 ~ 50 μ m aperture at the air pressure of 0.01 ~ 1MPa, so repeat emulsion to be preferably acquisition solid suspension list distribution emulsion 1-7 time by the microporous barrier several times.Air pressure described in step 3) is 0.1 ~ 0.3MPa more preferably all, adopts preferred air pressure conditions, can reduce as much as possible the generation of bubble in emulsion process, makes simultaneously the emulsion droplet of formation be difficult for being broken through by gas.
Further, when described solid particle was the solid hydrophilic particle, described solvent orange 2 A was water; When described solid particle was the lipophile solid particle, described solvent orange 2 A was the combination of a kind of in the alkane of C4 ~ C8 or aromatic hydrocarbon or at least two kinds, was preferably one or more the combination in toluene, normal heptane, n-hexane, benzinum.
Further, when described solid particle is the solid hydrophilic particle, the combination of a kind of or at least two kinds of solvents in the alkane that described solvent B is C4 ~ C8 or aromatic hydrocarbon is preferably one or more the combination in toluene, normal heptane, n-hexane, benzinum; When described solid particle was the lipophile solid particle, described solvent B was water.
the emulsification method of described solid suspension list distribution emulsion, when described solid particle is the lipophile solid particle, the optional NPE of described emulsifying agent, two tributyl phenol APEOs, the APES polyethenoxy ether, phenethyl phenol polyoxyethylene polyoxypropylene ether, Ben-zylphenol Polyoxyethyl Ether, gelatin, Arabic gum, polyvinyl alcohol, polyethers, PEG200, PEG400, PEG600, PEG1000, compound sugar, neopelex, polyoxyethylene oleic acid ester, polyoxyethylene stearic acid ester, the rosin acid polyoxyethylene ester, castor oil ethylene oxide adduct and derivative thereof, polyol fatty acid ester and ethylene oxide adduct thereof, Tween 80, N-cetyl-N-ethylmorpholine base SES, pure NaLS, the combination of one or more in polyoxyl 40 stearate, when solid particle is the solid hydrophilic particle, described emulsifying agent is one or more the combination in single stearic acid glycerine lipoprotein, two ethyl stearte base ethoxy methylsulfuric acid ammonium methyl, three ethyl stearte base ethoxy methylsulfuric acid ammonium methyls, Span20, Span40, Span60, Span80, Tween85, alkyl tert amine salt, more preferably the composite emulsifier that forms of gelatin and Arabic gum.
Further, the volume ratio of described solid suspension and continuous phase is 1:5 ~ 1:20.
Further, the material of described microporous barrier is preferably chemical inert material, and the microporous barrier of the material such as the chemical inertness such as polytetrafluoroethylene (PTFE), alundum (Al2O3) all can.
Preferably, the emulsification method of described solid suspension list distribution emulsion, step 3) under 30 ~ 80 ℃ of conditions, in atmosphere of inert gases with solid suspension under the air pressure of 0.01 ~ 1MPa promotes the microporous barrier by 1 ~ 50 μ m aperture and flow into step 2) continuous phase in, obtain elementary emulsion; Under 30 ~ 80 ℃ of conditions, in atmosphere of inert gases, elementary emulsion is promoted lower microporous barrier by 1 ~ 50 μ m aperture at the air pressure of 0.01 ~ 1MPa, so repeat emulsion by the microporous barrier several times, as 1-7 time, acquisition solid suspension list distribution emulsion.Adopt this atmosphere of inert gases, can avoid in emulsion process as far as possible, the material generation side reaction in emulsification system further ensures the stability of each component of emulsification system.
Described inert gas can be a kind of gas in nitrogen, argon gas or the mist of two kinds of gases.
The solid suspension list distribution emulsion that the present invention also provides a kind of emulsification method as indicated above to make.This emulsion is the solid suspension list distribution emulsion of decentralized photo emulsion droplet particle diameter narrow distribution, and good stability.
Single distribution emulsion described in literary composition refers to emulsion particle evenly and the emulsion of particle diameter narrow distribution.Solid particle described in literary composition is divided into hydrophily or lipophile solid particle according to water to the difference of solid particle wetability, and solid particles surface can be the solid hydrophilic particle by water-wet, otherwise is the lipophile solid particle.Sympathy described in literary composition refers to consistent with the hydrophilic and oleophilic character of solid particle, otherwise is non-sympathy.
Technical scheme provided by the present invention has following beneficial effect:
The invention provides a kind of emulsification method of novel solid suspension list distribution emulsion, adopt unique emulsification system and emulsification condition, binding film emulsion process and certain air pressure promoted film, can prepare the single distribution emulsion that contains solid particle that has good stability, not only can effectively control the particle diameter of decentralized photo emulsion droplet, and can make the solid content homogeneity of each emulsion droplet in emulsion good; The emulsification method that provides is simple to operate, and emulsifying effectiveness is good, can obtain stable emulsion, and can prepare stable complicated multi-phase emulsion.By the optimization in pressure condition and microporous barrier aperture, effectively control the emulsion droplet particle diameter of prepared emulsion, make the particle diameter distribution single stable of emulsion droplet, the gained emulsion is placed and is had no significant change more than 15 days, in a long time without demulsifying phenomenon.Adopt emulsification method of the present invention to carry out emulsification, can make solid suspension form the single spherical emulsion droplet of particle diameter distribution after emulsification, and the solid particle in emulsion droplet can evenly distribute, avoided the appearance of enrichment and agglomeration, prepared emulsion can be used for the emulsification in early stage (as the emulsification in early stage of microcapsules in electrophoretic display technology) of microencapsulated product, also can be widely used in the fields such as agricultural, pharmacy, printing, paint, chemical industry, food, the while also provides solution for the stable storage of solids.
Description of drawings
Fig. 1 is embodiment 1-7 emulsifier unit used when step 3 emulsification.
Description of reference numerals: 1, hermetically sealed can; 2, microporous barrier; 3, valve; 4, emulsifying tank; 5, air pressure valve; 6, feed pipe.
Fig. 2 is the microphoto of the emulsion that makes of embodiment 2.
Fig. 3 is the microphoto of the emulsion that makes of Comparative Examples.
The specific embodiment
The invention provides a kind of solid suspension list distribution emulsion and emulsification method thereof, this emulsification method is that modification or unmodified solid particle (particle diameter 0.05-20 μ m) are dispersed in a kind of liquid phase of and solid particle sympathy, after fully disperseing, form solid suspension; Then with solid suspension under certain air pressure promotes, by having the microporous membrane of special pore size distribution, and then flow in the liquid phase of the another kind that is dissolved with emulsifying agent and the non-sympathy of solid particle, form elementary emulsion; Repeatedly with after elementary emulsion process microporous membrane several, can obtain the stable single distribution emulsion that contains solid particle.
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1
This example is distributed in the embodiment of the solid suspension list distribution emulsion of 8 ~ 15 μ m for the preparation particle diameter
1) preparation solid suspension: get appropriate oiliness magnesia (MgO) powder (particle diameter 50 ~ 300nm) is dispersed in toluene, ultrasonic 30min, making the MgO mass content is the finely dispersed solid suspension of 18.76wt%.
2) preparation continuous phase: get appropriate emulsifying agent PVA(polyvinyl alcohol, alcoholysis degree 88%, number-average molecular weight 55000) be added in the 500mL beaker, and add appropriate distilled water, stir 30min in 30 ℃ of lower magnetic forces, be warming up to 60 ℃ of stirring 1h after making the PVA complete swelling, making the emulsifying agent mass content is the PVA solution of 3wt% again.
3) emulsification: under 40 ℃, be 1:5's according to the volume ratio of solid suspension and PVA solution
AmountSolid suspension is injected in stainless hermetically sealed can (sees accompanying drawing 1, hermetically sealed can 1 tank base is connected with the pipeline with valve 6, the pipeline exit is connected with microporous barrier 2), inject the nitrogen of air pressure 0.2MPa in hermetically sealed can, open the valve 3 of hermetically sealed can lower end, suspension quick microporous barrier by 10 μ m apertures under the promotion of air pressure, flow in PVA solution, namely get elementary emulsion, elementary emulsion is re-injected in hermetically sealed can, repeated the operation of microporous barrier, and so repeated 2 ~ 3 times, in emulsion process, air pressure is kept 0.2MPa always.Finally make the O/W emulsion.
It is 97% that prepared emulsion, its particle diameter mainly are distributed in 8 ~ 15 μ m(volume contents), average grain diameter 12.3 μ m; Get the heating of 20g emulsion and remove moisture and toluene, and calcine and remove PVA, the content that records MgO in the decentralized photo emulsion droplet is 18.45wt%, and in emulsion, solid particulate distributions is very even, and in emulsion droplet, the solids content uniformity is good.Again test emulsion particle diameter and particle diameter after 15d and distribute, record particle diameter and mainly be distributed in 8 ~ 15.5 μ m, average grain diameter is 12.5 μ m, without significant change, good emulsion stability is described with the initial stage test result.
Embodiment 2(prepares the solid suspension list distribution emulsion that particle diameter is distributed in 20 ~ 25 μ m):
1) preparation solid suspension: with appropriate water-based titanium dioxide (TiO
2) powder (particle diameter 0.1 ~ 3 μ m) is dispersed in deionized water, ultrasonic 30min makes TiO
2Mass content is the finely dispersed solid suspension of 9.1wt%.
2) continuous phase preparation: get appropriate emulsifying agent glycerin monostearate (molecular formula: C
21H
42O
4) be added in appropriate benzinum, 30 ℃ of lower magnetic forces stir 1h, and making the emulsifying agent mass content is the glycerin monostearate solution of 2wt%.
3) emulsification: under 30 ℃, according to the volume ratio of solid suspension and the single stearic acid glycerine lipoprotein solution amount that is 1:8, solid suspension is injected in stainless hermetically sealed can and (sees accompanying drawing 1, tank base is connected with the pipeline with valve, the pipeline exit is connected with microporous barrier), inject the nitrogen of air pressure 0.3MPa in hermetically sealed can, open the valve of hermetically sealed can lower end, suspension quick microporous barrier by 15 μ m apertures under the promotion of air pressure, flow in glycerin monostearate solution, namely get elementary emulsion, elementary emulsion is re-injected in hermetically sealed can, repeated the operation of microporous barrier, so repeat 2 times, in experimentation, air pressure is kept 0.3MPa always.Finally make the W/O emulsion.
It is 93% that prepared emulsion, its particle diameter are distributed in 20 ~ 25 μ m(volume contents), average grain diameter 23 μ m; Get under 300 ℃ of 20g emulsions and dry by the fire 3h, record TiO in the decentralized photo emulsion droplet
2Content be 9.2wt%, in each emulsion droplet, the solids content uniformity is good, the microphoto of emulsion is referring to accompanying drawing 2.Again test emulsion particle diameter and distribution after 15 days, particle diameter mainly is distributed as 20 ~ 25 μ m, and average grain diameter is 23 μ m, and is unchanged with the initial stage test, illustrates that stability of emulsion is very good.
Embodiment 3(prepares the solid suspension list distribution emulsion that particle diameter is distributed in 38 ~ 45 μ m):
1) preparation solid suspension: with oiliness magnesia (MgO) powder (tri-iron tetroxide (Fe of particle diameter 50 ~ 100nm) and surface modification of mass ratio 1:1
3O
4, the surface is lipophile through organic coating or graft modification, particle diameter 50 ~ 100nm) is dispersed in normal heptane, and ultrasonic 2h, the mass content that makes solid particle is the finely dispersed solid suspension of 22.7wt%.
2) continuous phase preparation: gelatin and the Arabic gum of mass ratio 1:1 are added in the 200mL beaker, add appropriate distilled water, 40 ℃ of lower mechanical agitation 1h, making the emulsifying agent mass content is the gelatin-gum arabic solution of 3wt%.
3) emulsification: under 40 ℃, according to the volume ratio of solid suspension and the gelatin gumwater amount that is 1:15, solid suspension is injected in stainless hermetically sealed can and (sees accompanying drawing 1, tank base is connected with the pipeline with valve, the pipeline exit is connected with microporous barrier), inject the nitrogen of 0.1MPa air pressure in hermetically sealed can, open the valve of hermetically sealed can lower end, solid suspension quick microporous barrier by 35 μ m apertures under the promotion of air pressure, flow in gelatin-gum arabic solution, namely get elementary emulsion, elementary emulsion is re-injected in hermetically sealed can, repeated the operation of microporous barrier, so repeat 3 times, in experimentation, air pressure is kept 0.1MPa always.Finally make O/W type emulsion.
It is 90% that prepared emulsion, its particle diameter are distributed in 38 ~ 45 μ m(volume contents), average grain diameter 42.3 μ m; Get after the 20g emulsion carries out drying, the one-step calcination of going forward side by side is to constant weight, records that in the decentralized photo emulsion droplet, solid content is 22wt%, and in each emulsion droplet, the solid content homogeneity is good.Again test emulsion particle diameter and distribution after 15d, particle diameter mainly is distributed in 37 ~ 47 μ m, and average grain diameter is 44 μ m, without significant change, good emulsion stability is described with the initial stage test.
Embodiment 4(prepares the solid suspension list distribution emulsion that particle diameter is distributed in 8 ~ 15 μ m):
1) preparation solid suspension: get appropriate modification carbon black particle (particle diameter 100 ~ 700nm) is dispersed in n-hexane, ultrasonic 30min, making mass of solid particles content is the finely dispersed solid suspension of 6.74wt%.
2) continuous phase preparation: get appropriate emulsifying agent neopelex (C
18H
29NaO
3S) be placed in the 500mL beaker, add appropriate distilled water, 40 ℃ of lower magnetic forces stir 30min, and making the emulsifying agent mass content is the neopelex solution (water) of 3wt%.
3) emulsification: under 40 ℃, according to the volume ratio of solid suspension and the PVA solution amount that is 1:20, solid suspension is injected in stainless hermetically sealed can and (sees accompanying drawing 1, tank base is connected with the pipeline with valve, the pipeline exit is connected with microporous barrier), inject the nitrogen of 0.2MPa air pressure in hermetically sealed can, open the lower end valve of hermetically sealed can, solid suspension quick microporous barrier by 10 μ m apertures under the promotion of air pressure, flow in neopelex solution (water), namely get elementary emulsion, elementary emulsion is re-injected in hermetically sealed can, so repeated the operation 2 times of microporous barrier, finally making the preparation of O/W type emulsion completes.
It is 97% that prepared emulsion, its particle diameter mainly are distributed in 8 ~ 15 μ m(volume contents), average grain diameter 12.3 μ m; Get the heating of 20g emulsion and remove moisture and n-hexane, and calcine and remove PVA, the content that records carbon black particle in emulsion droplet is 6.7%, and in emulsion, solid particulate distributions is even, and in each emulsion droplet, the solids content uniformity is good.Again test emulsion particle diameter and particle diameter after 15d and distribute, record particle diameter and mainly be distributed in 8 ~ 15.5 μ m, average grain diameter is 12.5 μ m, without significant change, good emulsion stability is described with the initial stage test result.
Embodiment 5(prepares the solid suspension list distribution emulsion that particle diameter is distributed in 51 ~ 57 μ m):
1) preparation solid suspension: with appropriate water-based titanium dioxide (TiO
2) powder (particle diameter 8 ~ 20 μ m) is dispersed in the 200mL deionized water, ultrasonic 30min, the content of making TiO2 is the finely dispersed solid suspension of 1wt%.
2) continuous phase preparation: get appropriate emulsifying agent glycerin monostearate (molecular formula: C
21H
42O
4) be added in benzinum, 30 ℃ of lower magnetic forces stir 1h, and making the emulsifying agent mass content is the glycerin monostearate solution of 0.5wt%.
3) emulsification: under 60 ℃, according to the volume ratio of solid suspension and the single stearic acid glycerine lipoprotein solution amount that is 1:10, solid suspension is injected in stainless hermetically sealed can and (sees accompanying drawing 1, tank base is connected with the pipeline with valve, the pipeline exit is connected with microporous barrier), inject the nitrogen of air pressure 0.01MPa in hermetically sealed can, open the valve of hermetically sealed can lower end, suspension quick microporous barrier by 50 μ m apertures under the promotion of air pressure, flow in glycerin monostearate solution, namely get elementary emulsion, elementary emulsion is re-injected in hermetically sealed can, repeated the operation of microporous barrier, so repeat 3 times, in experimentation, air pressure is kept 0.01MPa always.Finally make the W/O emulsion.
It is 95% that prepared emulsion, its particle diameter are distributed in 51 ~ 57 μ m(volume contents), average grain diameter 54 μ m; Get under 300 ℃ of 20g emulsions and dry by the fire 3h, record TiO in emulsion droplet
2Content be 1.15wt%, in each emulsion droplet, the solids content uniformity is good.Again test emulsion particle diameter and distribution after 15 days, particle diameter mainly is distributed as 52 ~ 57 μ m, and average grain diameter is 54.5 μ m, and is unchanged with the initial stage test, illustrates that stability of emulsion is very good.
Embodiment 6(prepares the solid suspension list distribution emulsion that particle diameter is distributed in 33 ~ 38 μ m):
1) preparation solid suspension: with appropriate water-based titanium dioxide (TiO
2) powder (particle diameter 5 ~ 15 μ m) is dispersed in the 200mL deionized water, ultrasonic 30min, the content of making TiO2 is the finely dispersed solid suspension of 50wt%.
2) continuous phase preparation: get appropriate emulsifying agent glycerin monostearate (molecular formula: C
21H
42O
4) be added in benzinum, 30 ℃ of lower magnetic forces stir 1h, and making the emulsifying agent mass content is the glycerin monostearate solution of 1wt%.
3) emulsification: under 80 ℃, according to the volume ratio of solid suspension and the single stearic acid glycerine lipoprotein solution amount that is 1:11, solid suspension is injected in stainless hermetically sealed can and (sees accompanying drawing 1, tank base is connected with the pipeline with valve, the pipeline exit is connected with microporous barrier), inject the nitrogen of air pressure 1MPa in hermetically sealed can, open the valve of hermetically sealed can lower end, suspension quick microporous barrier by 30 μ m apertures under the promotion of air pressure, flow in glycerin monostearate solution, namely get elementary emulsion, elementary emulsion is re-injected in hermetically sealed can, repeated the operation of microporous barrier, so repeat 3 times, in experimentation, air pressure is kept 1MPa always.Finally make the W/O emulsion.
It is 96% that prepared emulsion, its particle diameter are distributed in 33 ~ 38 μ m(volume contents), average grain diameter 35 μ m; Get under 300 ℃ of 20g emulsions and dry by the fire 3h, record TiO in emulsion droplet
2Content be 50wt%, in each emulsion droplet, solids content is consistent.Again test emulsion particle diameter and distribution after 15 days, particle diameter mainly is distributed as 32 ~ 37 μ m, and average grain diameter is 34.5 μ m, and is unchanged with the initial stage test, illustrates that stability of emulsion is very good.
Embodiment 7(prepares the solid suspension list distribution emulsion that particle diameter is distributed in 7 ~ 10 μ m):
This example is substantially the same manner as Example 1, and its difference is that the air pressure of step 3) is different, and the aperture of microporous barrier is different, and the preparation particle diameter is distributed in the solid suspension list distribution emulsion of 7 ~ 10 μ m.
1) preparation solid suspension: with appropriate oiliness magnesia (MgO) powder (particle diameter 50 ~ 300nm) is dispersed in toluene, ultrasonic 30min, making the MgO mass content is the finely dispersed solid suspension of 18.76wt%.
2) preparation continuous phase: get appropriate emulsifying agent PVA(polyvinyl alcohol, alcoholysis degree 88%, number-average molecular weight 55000) be added in the 500mL beaker, and add appropriate distilled water, stir 30min in 30 ℃ of lower magnetic forces, be warming up to 60 ℃ of stirring 1h after making the PVA complete swelling, making the emulsifying agent mass content is the PVA solution of 3wt% again.
3) emulsification: under 40 ℃, according to the volume ratio of solid suspension and the PVA solution amount that is 1:5, solid suspension is injected in stainless hermetically sealed can and (sees accompanying drawing 1, hermetically sealed can 1 tank base is connected with the pipeline with valve 6, the pipeline exit is connected with microporous barrier 2), inject the nitrogen of air pressure 0.3MPa in hermetically sealed can, open the valve 3 of hermetically sealed can lower end, suspension quick microporous barrier by 10 μ m apertures under the promotion of air pressure, flow in PVA solution, namely get elementary emulsion, elementary emulsion is re-injected in hermetically sealed can, repeated the operation of microporous barrier, so repeat 2 ~ 3 times, in emulsion process, air pressure is kept 0.3MPa always.Finally make the O/W emulsion.
It is 96% that prepared emulsion, its particle diameter mainly are distributed in 7 ~ 10 μ m(volume contents), average grain diameter 8.2 μ m; Get the heating of 20g emulsion and remove moisture and toluene, and calcine and remove PVA, the content that records MgO in emulsion droplet is 18.31wt%, and in emulsion, solid particulate distributions is very even, and in emulsion droplet, the solids content uniformity is good.Again test emulsion particle diameter and particle diameter after 15d and distribute, record particle diameter and mainly be distributed in 7.4 ~ 11 μ m, average grain diameter is 8.5 μ m, without significant change, good emulsion stability is described with the initial stage test result.This example is compared with embodiment 1, by changing emulsification condition, can effectively control the emulsion droplet particle diameter, and can make the emulsion that contains solid particle of particle diameter narrow distribution.
Comparative Examples (employing mechanical mixing method):
1) preparation solid suspension: with 20g water-based titanium dioxide (TiO
2) powder (particle diameter 0.1 ~ 3 μ m) is dispersed in the 200mL deionized water, ultrasonic 30min namely gets finely dispersed solid suspension (TiO
2Content be 9.1wt%).
2) continuous phase preparation: get emulsifying agent glycerin monostearate (molecular formula: C
21H
42O
4) 2g is added in the 98g benzinum, 30 ℃ of lower magnetic forces stir 1h, namely get glycerin monostearate solution.
3) emulsification: under 30 ℃, be that the amount of 1:8 is injected stirred tank, 600r/min with solid suspension with when consecutive identical according to the volume ratio of solid suspension and single stearic acid glycerine lipoprotein solution, after stirring 2h, after observing particle diameter, rotating speed is down to 300r/min, stir 1h, both got emulsion.Prepared emulsion, its particle diameter are distributed in 0.5 ~ 105 μ m, average grain diameter 35 μ m, and emulsion is seriously unstable, is sedimentation in 30min; Solid content in each emulsion droplet is different.The microphoto of emulsion is referring to accompanying drawing 3.Compared by Fig. 2 and Fig. 3, can clearly see an emulsion emulsion droplet particle diameter distribution homogeneous that adopts emulsification method of the present invention to make, emulsion is more stable.
By embodiment 1 ~ 7, the emulsification method of solid suspension list distribution emulsion provided by the invention according to the difference of desired emulsion particle diameter and particle diameter distribution, can accurately effectively be controlled the particle diameter of emulsion droplet, reaches and the basic emulsifying effectiveness that coincide of expection; Compare with traditional emulsification method, can prepare single distribution emulsion that stability better contains solid particle, in emulsion, the solid content homogeneity of each emulsion droplet is good; Prepared emulsion particle diameter distribution single stable, and the gained emulsion places and to have no significant change more than 15 days, in a long time without demulsifying phenomenon.
Embodiment mentioned above is only the example that emulsification method of the present invention is described.The material that emulsifying agent in embodiment 1-7 is not limited only to exemplify.difference according to the hydrophilic and oleophilic character of solid particle, when being the solid hydrophilic particle, emulsifying agent used is oil soluble emulsifying agent, can be selected from single stearic acid glycerine lipoprotein, one or more the combination in two ethyl stearte base ethoxy methylsulfuric acid ammonium methyl, three ethyl stearte base ethoxy methylsulfuric acid ammonium methyls, Span20, Span40, Span60, Span80, Tween85, alkyl tert amine salt etc., when being the lipophile solid particle, emulsifying agent used is water soluble emulsifier, can be selected from NPE, two tributyl phenol APEOs, the APES polyethenoxy ether, phenethyl phenol polyoxyethylene polyoxypropylene ether, Ben-zylphenol Polyoxyethyl Ether, gelatin, Arabic gum, polyvinyl alcohol, polyethers, PEG200, PEG400, PEG600, PEG1000, compound sugar, neopelex, polyoxyethylene oleic acid ester, polyoxyethylene stearic acid ester, the rosin acid polyoxyethylene ester, castor oil ethylene oxide adduct and derivative thereof, polyol fatty acid ester and ethylene oxide adduct thereof, Tween 80, N-cetyl-N-ethylmorpholine base SES, pure NaLS, the combination of one or more in polyoxyl 40 stearate etc.
The above, it is only preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, therefore all contents that does not break away from technical solution of the present invention,, all still belong in the scope of technical solution of the present invention any simple modification made for any of the above embodiments, equivalent variations and modification according to technical spirit of the present invention.
Claims (9)
1. the emulsification method of a solid suspension list distribution emulsion, is characterized in that, comprises the steps:
1) preparation solid suspension: the particle diameter solid particle that is 0.05 ~ 20 μ m is scattered in solvent orange 2 A with the solid particle sympathy, makes the solid suspension that mass of solid particles concentration is 1 ~ 50wt%;
2) preparation continuous phase: with emulsifiers dissolve in the solvent B of the non-sympathy of the described solid particle of step 1) in, make continuous phase;
3) emulsification: under 30 ~ 80 ℃ of conditions, with solid suspension under the air pressure of 0.01 ~ 1MPa promotes the microporous barrier by 1 ~ 50 μ m aperture and flow into step 2) continuous phase in, obtain elementary emulsion; Under 30 ~ 80 ℃ of conditions, elementary emulsion is promoted lower microporous barrier by 1 ~ 50 μ m aperture at the air pressure of 0.01 ~ 1MPa, repeat operation several times, acquisition solid suspension list distribution emulsion.
2. the emulsification method of solid suspension list distribution emulsion according to claim 1, is characterized in that, when described solid particle was the solid hydrophilic particle, described solvent orange 2 A was water; When described solid particle was the lipophile solid particle, described solvent orange 2 A was the combination of a kind of in the alkane of C4 ~ C8 or aromatic hydrocarbon or at least two kinds.
3. the emulsification method of solid suspension list distribution emulsion according to claim 1 and 2, is characterized in that, when described solid particle is the solid hydrophilic particle, and the combination of a kind of or at least two kinds of solvents in the alkane that described solvent B is C4 ~ C8 or aromatic hydrocarbon; When described solid particle was the lipophile solid particle, described solvent B was water.
4. the emulsification method of solid suspension list distribution emulsion according to claim 1, it is characterized in that, when solid particle is the lipophile solid particle, described emulsifying agent is NPE, two tributyl phenol APEOs, the APES polyethenoxy ether, phenethyl phenol polyoxyethylene polyoxypropylene ether, Ben-zylphenol Polyoxyethyl Ether, gelatin, Arabic gum, polyvinyl alcohol, polyethers, PEG200, PEG400, PEG600, PEG1000, compound sugar, neopelex, polyoxyethylene oleic acid ester, polyoxyethylene stearic acid ester, the rosin acid polyoxyethylene ester, castor oil ethylene oxide adduct and derivative thereof, polyol fatty acid ester and ethylene oxide adduct thereof, Tween 80, N-cetyl-N-ethylmorpholine base SES, pure NaLS, the combination of one or more in polyoxyl 40 stearate, when solid particle was the solid hydrophilic particle, described emulsifying agent was one or more combination of single stearic acid glycerine lipoprotein, two ethyl stearte base ethoxy methylsulfuric acid ammonium methyl, three ethyl stearte base ethoxy methylsulfuric acid ammonium methyls, Span20, Span40, Span60, Span80, Tween85, alkyl tert amine salt.
5. the emulsification method of solid suspension list distribution emulsion according to claim 1, is characterized in that, the volume ratio of described solid suspension and continuous phase is 1:5 ~ 1:20.
6. the emulsification method of solid suspension list distribution emulsion according to claim 1, is characterized in that, the material of described microporous barrier is chemical inert material.
7. the emulsification method of solid suspension list distribution emulsion according to claim 1, it is characterized in that, step 3) is under 30 ~ 80 ℃ of conditions, in atmosphere of inert gases with solid suspension under the air pressure of 0.01 ~ 1MPa promotes the microporous barrier by 1 ~ 50 μ m aperture and flow into step 2) continuous phase in, obtain elementary emulsion; Under 30 ~ 80 ℃ of conditions, in atmosphere of inert gases, elementary emulsion is promoted lower microporous barrier by 1 ~ 50 μ m aperture at the air pressure of 0.01 ~ 1MPa, repeat operation several times, acquisition solid suspension list distribution emulsion.
8. the emulsification method of solid suspension list distribution emulsion according to claim 7, is characterized in that, described inert gas is a kind of gas in nitrogen, argon gas or the mist of two kinds of gases.
9. a solid suspension list distribution emulsion, is characterized in that, described solid suspension list distribution emulsion adopts and makes as the described emulsification method of claim 1-8 any one.
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