CN104226191A - Normal temperature preparation method of ethyl cellulose porous particles - Google Patents
Normal temperature preparation method of ethyl cellulose porous particles Download PDFInfo
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Abstract
The invention discloses a normal temperature preparation method of ethyl cellulose porous particles. The method comprises the following steps: preparing solvent-containing ethyl cellulose sol; emulsifying water or a surfactant-containing aqueous solution into the ethyl cellulose sol, thereby obtaining high polymer emulsion of which an internal phase is water or aqueous solution; secondarily dispersing the high polymer emulsion into an aqueous solution containing a dispersing agent to form spherical droplets; adding lots of water or aqueous solution into the system so as to gradually transform the spherical droplets into solid particles, separating the solid particles containing water or aqueous solution and drying, thereby obtaining the ethyl cellulose porous particles. The separated aqueous solution is recycled after the solvent is recovered. The method has the characteristics that the process flow is short, the operation is simple and convenient, the power consumption is low, the particle size and pore structure of the prepared porous particles are easily adjusted and the like. Moreover, the method is suitable for batch preparation of ethyl cellulose porous particles.
Description
Technical field
The present invention relates to the preparation method of porous polymer materials, particularly a kind of normal temperature preparation method of ethyl cellulose porous particle.
Background technology
Ethyl cellulose is the derivative that in cellulose molecular chain, ethyoxyl displacement hydroxyl is formed, have that toxicity is little, stable, non-activity, viscosity are large, filming performance is good, simultaneously it has and is permeated by hydrone and not by the feature of dissolving, be widely used in the carrier of the sustained release pharmaceutical formulation of various ways.The surface area of pore type spheric granules is large, and mobility, dissolubility are better, and the improvement of these physical property can control the release of medicine more effectively, improves curative effect.Zhang Yan etc. (supercritical CO_2 antisolvent precipitation prepares Ethylcellulose Microspheres, Chemical Engineering, 2005,33 (3): 63-67) are by the supercritical CO of designed, designed
2microballoon preparation facilities, utilizes ethyl cellulose-acetone mixed solution to prepare smooth surface and the good Ethylcellulose Microspheres of sphericity.Microballoon size can be regulated and controled in a big way.
But the device structure complexity that this kind of method is used, processing step is more, under high pressure completes preparation, and manufacturing cost is very high, is unsuitable for mass production.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of porous polymer materials, particularly a kind of normal temperature preparation method of ethyl cellulose porous particle of low cost.
The technical solution realizing the object of the invention is: a kind of normal temperature preparation method of ethyl cellulose porous particle, comprises the following steps:
Step 1, ethyl cellulose is dissolved in solvent obtains solvent-laden ethyl cellulose colloidal sol; Described solvent is one or more the mixture in ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, methyl alcohol, ethanol, carrene, oxolane, isopropyl alcohol, butanols, cyclohexanol, acetone, butanone, cyclohexanone; Solvent load is 5-20 times of ethyl cellulose quality.
Step 2, adopt in the ethyl cellulose colloidal sol described in general emulsification method emulsification to step 1 by water or containing the aqueous solution of surfactant, obtaining interior is macromolecule emulsion that water or the aqueous solution, foreign minister are ethyl cellulose colloidal sol mutually;
The described aqueous solution containing surfactant is be the aqueous solution of 0.001%-0.2% general-purpose surfactant containing mass concentration scope; Described water or be 0.1 ~ 1.0 times of step 1 solvent for use volume containing the amount of aqueous solution used of surfactant.
Step 3, macromolecule emulsion step 2 obtained under stirring, are distributed to water or containing in the aqueous solution of dispersant, macromolecule emulsion is dispersed into spherical droplets;
The described aqueous solution containing dispersant is be the aqueous solution of the Arabic gum of 0.02%-0.5%, gelatine, methylcellulose, polyethylene glycol, polyvinyl alcohol, gelatin containing mass concentration scope; Water or be 1.0 ~ 2.0 times of step 1 solvent for use volume containing the consumption of the aqueous solution of dispersant.
Step 4, the material that step 3 is obtained and water or the aqueous solution containing dispersant, dispersion spherical droplets in aqueous is progressively hardened and is transformed into solid spherical particles; Water used or containing kind and the concentration of the aqueous solution of dispersant and identical in step 3; Described water or be 10 ~ 40 times of step 1 solvent for use volume containing the consumption of the aqueous solution of dispersant.
Step 5, adopt general method to carry out Separation of Solid and Liquid, dry isolated solid particle, obtain ethyl cellulose porous particle, the aqueous solution separated carries out solvent recovery.
Above-mentioned steps 1 is all carry out at normal temperatures to step 4.
The present invention compared with prior art, has the following advantages: 1) method technique of the present invention is simpler, and do not need to prepare under elevated pressure conditions, preparation technology is safer, has increased substantially production efficiency, can suitability for industrialized production; 2) method of the present invention is distilled without solvent, and by means of only adding aqueous dispersion and plastic, solvent can recycle, cost-saving, simple to operate; 3) method of the present invention regulates particle diameter, the porosity that just can control finished particle well by means of only solvent ratios and emulsification condition, easilier than traditional handicraft controls; 4) the ethyl cellulose porous particle sphericity utilizing method of the present invention to prepare is higher, inner pore structure evenly.
Accompanying drawing explanation
Fig. 1 is that ethyl cellulose porous particle prepared by embodiment 1 records granule-morphology figure by light microscope.
The ethyl cellulose porous particle of Fig. 2 prepared by embodiment 2 is tested the section pore structure shape appearance figure obtained by SEM.
The ethyl cellulose porous particle of Fig. 3 prepared by embodiment 3 is tested the section pore structure shape appearance figure obtained by SEM.
The ethyl cellulose porous particle of Fig. 4 prepared by embodiment 4 is tested the section pore structure shape appearance figure obtained by SEM.
The ethyl cellulose porous particle of Fig. 5 prepared by embodiment 5 is tested the section pore structure shape appearance figure obtained by SEM.
Detailed description of the invention
The normal temperature preparation method of a kind of ethyl cellulose porous particle of the present invention, comprises the following steps:
Step 1, ethyl cellulose is dissolved in solvent obtains solvent-laden ethyl cellulose colloidal sol; Described solvent is one or more the mixture in ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, methyl alcohol, ethanol, carrene, oxolane, isopropyl alcohol, butanols, cyclohexanol, acetone, butanone, cyclohexanone; Solvent load is 5-20 times of ethyl cellulose quality.
Step 2, adopt in the ethyl cellulose colloidal sol described in general emulsification method emulsification to step 1 by water or containing the aqueous solution of surfactant, obtaining interior is macromolecule emulsion that water or the aqueous solution, foreign minister are ethyl cellulose colloidal sol mutually; The described aqueous solution containing surfactant is be the aqueous solution of 0.001%-0.2% general-purpose surfactant containing mass concentration scope; Described water or be 0.1 ~ 1.0 times of step 1 solvent for use volume containing the amount of aqueous solution used of surfactant.
Step 3, macromolecule emulsion step 2 obtained under stirring, are distributed to water or containing in the aqueous solution of dispersant, macromolecule emulsion is dispersed into spherical droplets; The described aqueous solution containing dispersant is be the aqueous solution of the Arabic gum of 0.02%-0.5%, gelatine, methylcellulose, polyethylene glycol, polyvinyl alcohol, gelatin containing mass concentration scope; Water or be 1.0 ~ 2.0 times of step 1 solvent for use volume containing the consumption of the aqueous solution of dispersant.
Step 4, the material that step 3 is obtained and water or the aqueous solution containing dispersant, dispersion spherical droplets in aqueous is progressively hardened and is transformed into solid spherical particles; Water used or containing kind and the concentration of the aqueous solution of dispersant and identical in step 3; Water or be 10 ~ 40 times of step 1 solvent for use volume containing the consumption of the aqueous solution of dispersant.
Step 5, adopt general method to carry out Separation of Solid and Liquid, dry isolated solid particle, obtain ethyl cellulose porous particle, the aqueous solution separated carries out solvent recovery.
Above-mentioned steps 1 is all carry out at normal temperatures to step 4.
Described in more detail below:
The normal temperature preparation method of a kind of ethyl cellulose porous particle of the present invention, specifically describes as follows:
(1) step 1 is material dissolution process, under stirring, will be dissolved in solvent form ethyl cellulose colloidal sol containing ethyl cellulose.First, will join in material dissolution groove or balling-up reactor containing ethyl cellulose, the 5-20 solvent doubly adding ethyl cellulose quality carries out material dissolution.Before adding solvent, can first add a small amount of water or the aqueous solution disperses ethyl cellulose, to prevent material from reuniting and boning on wall, institute adds water or the ratio of the aqueous solution is 0-2 times of ethyl cellulose quality.The material dissolution time is determined according to raw material type and granular size, and dissolution time is 10-180min at normal temperatures, is preferably 20-90min.Material dissolution process ethyl cellulose and adding of solvent once can add or also can repeatedly add in batches.In addition, independent dissolver batch process can also be adopted or prepare ethyl cellulose colloidal sol continuously.Described solvent is one or more the mixture in ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, methyl alcohol, ethanol, carrene, oxolane, isopropyl alcohol, butanols, cyclohexanol, acetone, butanone, cyclohexanone.
(2) step 2 is macromolecule emulsion preparation process, and water or the aqueous solution containing surfactant being joined in ethyl cellulose colloidal sol under stirring and carry out emulsification, is the macromolecule emulsion of water or the aqueous solution mutually in formation.Described surfactant refers to conventional surfactant.Described surfactant can be nonionic surface active agent, as waited OP or TX series; Can also be anionic surfactant, as lauryl sodium sulfate or neopelex etc.; Cationic surface active agent can also be selected, as DTAC, softex kw etc.Aqueous solution mass concentration containing surfactant is 0.001-0.2%, and the 0.1-1.0 that water or amount of aqueous solution used are the solvent volume described in step 1 doubly.Described water or adding of the aqueous solution can once add or repeatedly add, and can also add continuously.Emulsion process can be carried out in balling-up equipment, and can also complete in other emulsifying devices, after emulsification completes, material proceeds in balling-up equipment.
(3) step 3 is dispersion globulation, under agitation macromolecule emulsion obtained in the previous step is distributed to water or disperses containing the aqueous solution of dispersant, and the macromolecule emulsion containing ethyl cellulose forms spherical droplets due to the effect of interfacial tension; Described dispersant can select the one in Arabic gum, gelatine, methylcellulose, polyethylene glycol, polyvinyl alcohol, gelatin.Be 0.02%-0.5% containing the mass concentration of dispersant in the aqueous solution of dispersant.Containing the mother liquor that the aqueous solution of dispersant can also be after the desolvation reclaimed in the shaping preparation process of Ethylcellulose Microspheres last time, add dispersant in the aqueous solution and mutual gathering is prevented to spherical droplets protection.The water of dispersion emulsion or containing the amount of aqueous solution used of dispersant be the 1.0-2.0 of solvent volume in step 1 doubly, disposablely can add, also can add in batches.Dispersant directly can also be added in system in dispersion globulation.The time of disperseing globulation used is preferably at 10min-90min; The temperature remains within the normal range for this process system temperature.Mixing speed is determined according to the spherical particle size of the volume of balling head, the shape of stirrer paddle and needs, needs the particle of small particle diameter can carry out under higher mixing speed, otherwise then carries out under lower mixing speed.
(4) step 4 is solvent leaching processes, after completing dispersion balling-up, the material that step 3 is obtained and more water or the aqueous solution containing dispersant, the drop of macromolecule emulsion progressively hardens formation spheric granules, and the described aqueous solution can be reclaim in the shaping preparation process of Ethylcellulose Microspheres last time and mother liquor after desolvation.In the step 1 that water or amount of aqueous solution used are, the 10-40 of solvent for use volume doubly, guarantees that the solvent in spherical droplets is diffused in aqueous phase fully.Step 1 is all carry out at normal temperatures to step 4.
(5) step 5 is feed separation and drying course, the mode of common centrifugation or filtration is adopted to be separated with solid spherical particles by the aqueous solution, the filtrate of separating is called mother liquor after solvent removal, containing a small amount of dispersant and surfactant in mother liquor, can be saved in fixing container and recycle as decentralized medium when next balling-up, also can concentrate through process qualified after qualified discharge.The mode that solvent removal mode in filtrate can adopt air-distillation or vacuumize distillation is carried out, and recovered solvent can recycle.
In order to implementation condition of the present invention is described better, carry out citing below and set forth, these processes and process conditions do not represent the whole of invention, only otherwise the measure of violating innovative point of the present invention can be used.
Embodiment 1
Adopt the there-necked flask of 2 liters as balling-up reactor, selecting relative viscosity to be the Powdered ethyl cellulose of 40-70 is raw material, 4.0 grams of ethyl celluloses are joined in reactor, 20 times are added to the ethyl acetate of ethyl cellulose quality and the mixed solvent of ethanol under stirring, namely ratio of solvent is 20, in mixed solvent, ethyl acetate mass percent accounts for 75%, after dissolving 30min, obtains the colloidal sol containing ethyl cellulose.Then, in system, add 20ml distilled water continuously under agitation, the water volume that namely emulsification is entered is about 0.25 times of solvent volume, and the aqueous solution adds rear continuation and stirs 30min, forms uniform macromolecule emulsion.Next, macromolecule emulsion is distributed under agitation in the aqueous solution containing dispersant and carries out balling-up.Adopt Arabic gum as dispersant, the concentration of aqueous solution of dispersant is 0.5%, and the consumption of the aqueous solution is 1 times of solvent volume.Disperse 30 minutes under the speed of agitator of 200rpm, the macromolecule emulsion containing ethyl cellulose is progressively dispersed into spherical drop.Then, 10 times are added again to the water of solvent volume in system, spherical droplets is hardened gradually, continue to stir 30 minutes at normal temperatures, solid particle is separated with the aqueous solution, the aqueous solution separated adopts air-distillation mode recycling design, and the mother liquor of recovery saves and be used as balling-up decentralized medium in next group preparation process.The spheric granules separated obtains the ethyl cellulose porous particle that average grain diameter is 560 μm, porosity about 80% after drying, and the pore diameter range of internal pore structure concentrates on 5-10 μm, and granule-morphology as shown in Figure 1.As shown in Figure 1, the size of the ethyl cellulose porous particle prepared is comparatively even, and sphericity is higher.
Embodiment 2
Adopt the there-necked flask of 2 liters as balling-up reactor, selecting relative viscosity to be the Powdered ethyl cellulose of 40-70 is raw material, 8.0 grams of ethyl celluloses are joined in reactor, 10 times are added to the ethyl acetate solvent of ethyl cellulose quality under stirring, namely ratio of solvent is 10, after dissolving 30min, obtain the colloidal sol containing ethyl cellulose.Then, emulsification volume of entering is about the distilled water of 0.4 times of solvent volume continuously under agitation, and the aqueous solution adds rear continuation and stirs 30min, forms uniform macromolecule emulsion.Next, macromolecule emulsion is distributed in the aqueous solution containing dispersant and carries out balling-up.Adopt Arabic gum as dispersant, the concentration of aqueous solution of dispersant is 0.2%, and the consumption of the aqueous solution is 2 times of solvent volume.Disperse 30 minutes under the speed of agitator of 200rpm, the macromolecule emulsion containing ethyl cellulose is progressively dispersed into spherical drop.Then, 20 times are added again to the water of solvent volume in system, spherical droplets is hardened gradually, continue to stir 30 minutes at normal temperatures, solid particle is separated with the aqueous solution, the aqueous solution separated adopts air-distillation mode recycling design, and the mother liquor of recovery saves and be used as balling-up decentralized medium in next group preparation process.The spheric granules separated obtains the ethyl cellulose porous particle that average grain diameter is 1200 μm after drying, the porosity about 70% of granule interior, the pore diameter range of internal pore structure concentrates on 1-10 μm, tests the granule interior Pore structure and morphology that obtains as shown in Figure 2 by SEM.As seen from the figure, the porosity of the ethyl cellulose porous particle prepared is higher, and aperture is in micron level, and aperture is less.
Embodiment 3
Adopt and embodiment 2 same materials and technical process, only ratio of solvent is risen to 20 times, be 0.25 times of solvent volume in the addition of water in emulsion process, leaching processes adds 10 times to the aqueous solution containing dispersant of dicyandiamide solution, this aqueous solution is the mother liquor that the aqueous solution reclaimed by embodiment 1 obtains after solvent distillation, other conditions are identical with embodiment 2, and prepare the internal pore structure of ethyl cellulose porous particle as shown in Figure 3, aperture mainly concentrates on 4-10 μm.As shown in Figure 3, the porosity of the ethyl cellulose porous particle prepared is higher, and aperture is in micron level, and aperture is less.
Embodiment 4
Adopt the there-necked flask of 2 liters as balling-up reactor, selecting relative viscosity to be the Powdered ethyl cellulose of 40-70 is raw material, 8.0 grams of ethyl celluloses are joined in reactor, 10 times are added to the ethyl acetate solvent of ethyl cellulose quality under stirring, namely ratio of solvent is 10, after dissolving 30min, obtain the colloidal sol containing ethyl cellulose.Then, the emulsification concentration that volume is about 0.4 times of solvent volume of entering is 0.2%OP-10 type nonionic surfactant water-soluble liquid continuously under agitation, and emulsion process continues 30min, forms uniform macromolecule emulsion.Next, macromolecule emulsion is distributed in the aqueous solution containing dispersant and carries out balling-up.Adopt Arabic gum as dispersant, the concentration of aqueous solution of dispersant is 0.3%, and the consumption of the aqueous solution is 1.5 times of solvent volume.Disperse 30 minutes under the speed of agitator of 200rpm, the macromolecule emulsion containing ethyl cellulose is progressively dispersed into spherical drop.Then, then in system, add 20 times to the water of solvent volume, spherical droplets is hardened gradually, continue to stir 30 minutes at normal temperatures, be separated by solid particle with the aqueous solution, the aqueous solution separated adopts air-distillation mode recycling design.The spheric granules separated obtains the ethyl cellulose porous particle that average grain diameter is 300 μm after drying, the porosity about 75% of granule interior, the pore diameter range of internal pore structure concentrates on 0.5-5 μm, the granule interior Pore structure and morphology that obtains is tested as shown in Figure 4, average pore size 1.86 μm by SEM.
As shown in Figure 4, the porosity of the ethyl cellulose porous particle prepared is higher, and aperture is in micron level, and aperture is less.
Embodiment 5
Adopt and embodiment 2 same materials and technical process, ratio of solvent is still 10 times, be only in emulsion process, in water, add 0.1% cationic surfactant hexadecyltrimethylammonium chloride as emulsifying agent, other process conditions are identical with embodiment 2, prepare ethyl cellulose porous particle average grain diameter about 800 μm, the internal pore structure that obtains is tested as shown in Figure 5, average pore size 2.7 μm by SEM.
As shown in Figure 5, the porosity of the ethyl cellulose porous particle prepared is higher, and aperture is in micron level, and aperture is less.
Embodiment 6-16
Adopt the technical process identical with embodiment 4, select ethyl acetate as the solvent of ethyl cellulose dissolved, the amount of aqueous solution used of disperseing globulation to contain dispersant is 1.8 times of solvent volume, change the parameter such as mass concentration, the mass concentration of aqueous dispersant, the water consumption of leaching processes of ratio of solvent, aqueous surfactant solution respectively, other parameters are identical with embodiment 3, and average grain diameter and the aperture of obtained ethyl cellulose porous particle are as shown in the table.
Embodiment 17-22
Adopt the technical process identical with embodiment 3, select ethyl acetate as the solvent of ethyl cellulose dissolved, the amount of aqueous solution used of disperseing globulation to contain dispersant is 2 times of solvent volume, only change the kind of dispersant, other parameters are identical with embodiment 3, and average grain diameter and the aperture of obtained ethyl cellulose porous particle are as shown in the table.
From upper contrast effect, method of the present invention operates at normal temperatures, and preparation technology is simpler simultaneously, and end properties is stablized, and can increase substantially production efficiency, in addition, processing medium all recycles, and can not cause environmental pollution.
Embodiment 23
Adopt the there-necked flask of 2 liters as balling-up reactor, selecting relative viscosity to be the Powdered ethyl cellulose of 40-70 is raw material, 8.0 grams of ethyl celluloses are joined in reactor, 10 times are added to the ethyl acetate solvent of ethyl cellulose quality under stirring, namely ratio of solvent is 10, after dissolving 30min, obtain the colloidal sol containing ethyl cellulose.Then, the emulsification concentration that volume is about 0.1 times of solvent volume of entering is 0.2%OP-10 type nonionic surfactant water-soluble liquid continuously under agitation, and emulsion process continues 30min, forms uniform macromolecule emulsion.Next, macromolecule emulsion is distributed in the aqueous solution containing dispersant and carries out balling-up.Adopt Arabic gum as dispersant, the concentration of aqueous solution of dispersant is 0.3%, and the consumption of the aqueous solution is 1.5 times of solvent volume.Disperse 30 minutes under the speed of agitator of 200rpm, the macromolecule emulsion containing ethyl cellulose is progressively dispersed into spherical drop.Then, then in system, add 20 times to the water of solvent volume, spherical droplets is hardened gradually, continue to stir 30 minutes at normal temperatures, be separated by solid particle with the aqueous solution, the aqueous solution separated adopts air-distillation mode recycling design.The spheric granules separated obtains the ethyl cellulose porous particle that average grain diameter is 300 μm after drying, and the porosity about 15% of granule interior, the pore diameter range of internal pore structure concentrates on 0.5-5 μm.The porosity of the ethyl cellulose porous particle prepared is higher, and aperture is in micron level, and aperture is less.
Embodiment 24
Adopt the there-necked flask of 2 liters as balling-up reactor, selecting relative viscosity to be the Powdered ethyl cellulose of 40-70 is raw material, 8.0 grams of ethyl celluloses are joined in reactor, 10 times are added to the ethyl acetate solvent of ethyl cellulose quality under stirring, namely ratio of solvent is 10, after dissolving 30min, obtain the colloidal sol containing ethyl cellulose.Then, the emulsification concentration that volume is about 1.0 times of solvent volume of entering is 0.2%OP-10 type nonionic surfactant water-soluble liquid continuously under agitation, and emulsion process continues 30min, forms uniform macromolecule emulsion.Next, macromolecule emulsion is distributed in the aqueous solution containing dispersant and carries out balling-up.Adopt Arabic gum as dispersant, the concentration of aqueous solution of dispersant is 0.3%, and the consumption of the aqueous solution is 1.5 times of solvent volume.Disperse 30 minutes under the speed of agitator of 200rpm, the macromolecule emulsion containing ethyl cellulose is progressively dispersed into spherical drop.Then, then in system, add 20 times to the water of solvent volume, spherical droplets is hardened gradually, continue to stir 30 minutes at normal temperatures, be separated by solid particle with the aqueous solution, the aqueous solution separated adopts air-distillation mode recycling design.The spheric granules separated obtains the ethyl cellulose porous particle that average grain diameter is 300 μm after drying, and the porosity about 92% of granule interior, the pore diameter range of internal pore structure concentrates on 0.5-10 μm.The porosity of the ethyl cellulose porous particle prepared is higher, and aperture is in micron level, and aperture is less.
As from the foregoing, method of the present invention just can control particle diameter and the aperture of finished particle well by emulsification condition, solvent ratios, dosage of surfactant and kind, easilier than traditional handicraft controls.
Claims (6)
1. a normal temperature preparation method for ethyl cellulose porous particle, is characterized in that, comprises the following steps:
Step 1, ethyl cellulose is dissolved in solvent obtains solvent-laden ethyl cellulose colloidal sol;
Step 2, adopt in the ethyl cellulose colloidal sol described in general emulsification method emulsification to step 1 by water or containing the aqueous solution of surfactant, obtaining interior is macromolecule emulsion that water or the aqueous solution, foreign minister are ethyl cellulose colloidal sol mutually;
Step 3, macromolecule emulsion step 2 obtained under stirring, are distributed to water or containing in the aqueous solution of dispersant, macromolecule emulsion is dispersed into spherical droplets;
Step 4, the material that step 3 is obtained and water or the aqueous solution containing dispersant, dispersion spherical droplets in aqueous is progressively hardened and is transformed into solid spherical particles; Water used or containing kind and the concentration of the aqueous solution of dispersant and identical in step 3;
Step 5, adopt general method to carry out Separation of Solid and Liquid, dry isolated solid particle, obtain ethyl cellulose porous particle, the aqueous solution separated carries out solvent recovery.
2. the normal temperature preparation method of ethyl cellulose porous particle according to claim 1, it is characterized in that, the solvent described in step 1 is one or more the mixture in ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, methyl alcohol, ethanol, carrene, oxolane, isopropyl alcohol, butanols, cyclohexanol, acetone, butanone, cyclohexanone; Solvent load is 5-20 times of ethyl cellulose quality.
3. the normal temperature preparation method of ethyl cellulose porous particle according to claim 1, is characterized in that, described in step 2 is be the aqueous solution of 0.001%-0.2% general-purpose surfactant containing mass concentration scope containing the aqueous solution of surfactant; Described water or be 0.1 ~ 1.0 times of step 1 solvent for use volume containing the amount of aqueous solution used of surfactant.
4. the normal temperature preparation method of ethyl cellulose porous particle according to claim 1, it is characterized in that, described in step 3 is be the aqueous solution of the Arabic gum of 0.02%-0.5%, gelatine, methylcellulose, polyethylene glycol, polyvinyl alcohol, gelatin containing mass concentration scope containing the aqueous solution of dispersant; Water or be 1.0 ~ 2.0 times of step 1 solvent for use volume containing the consumption of the aqueous solution of dispersant.
5. the normal temperature preparation method of ethyl cellulose porous particle according to claim 1, is characterized in that, in step 4, water or the consumption containing the aqueous solution of dispersant are 10 ~ 40 times of step 1 solvent for use volume.
6. the normal temperature preparation method of ethyl cellulose porous particle according to claim 1, is characterized in that, step 1 is all carry out at normal temperatures to step 4.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608982A (en) * | 2015-10-27 | 2017-05-03 | 信越化学工业株式会社 | Porous water-soluble nonionic cellulose ether having excellent solubility and method for producing the same |
| CN108350091A (en) * | 2015-10-30 | 2018-07-31 | 东丽株式会社 | Ether series fiber element derivative particle |
| CN108366918A (en) * | 2015-09-30 | 2018-08-03 | 爱茉莉太平洋股份有限公司 | Scoria powder particle is impregnated in poromeric composite granule, contains its cosmetic composition and preparation method thereof |
| CN113083173A (en) * | 2021-04-16 | 2021-07-09 | 中国农业大学 | Water-in-oil Pickering emulsion gel and preparation method thereof |
| CN114106364A (en) * | 2021-11-24 | 2022-03-01 | 天津大学 | Preparation method of ethyl cellulose particles with different morphologies |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0873566A (en) * | 1994-09-06 | 1996-03-19 | Nippon Kayaku Co Ltd | Microencapsulated cure accelerator, epoxy resin composition containing same and cured product thereof |
| EP1210942A2 (en) * | 1996-05-07 | 2002-06-05 | Alkermes Controlled Therapeutics Inc. II | Microparticles |
| WO2003055470A1 (en) * | 2001-12-26 | 2003-07-10 | Takeda Chemical Industries, Ltd. | Novel microsphere and method for production thereof |
| US6932984B1 (en) * | 1999-11-17 | 2005-08-23 | Tagra Biotechnologies Ltd. | Method of microencapsulation |
| CN101053814A (en) * | 2007-04-26 | 2007-10-17 | 上海交通大学 | Multiple responsive high molecular microcapsule and preparation method thereof |
| CN103933910A (en) * | 2014-04-11 | 2014-07-23 | 浙江大学 | Preparation method of polymeric porous microsphere |
-
2014
- 2014-09-01 CN CN201410441745.1A patent/CN104226191B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0873566A (en) * | 1994-09-06 | 1996-03-19 | Nippon Kayaku Co Ltd | Microencapsulated cure accelerator, epoxy resin composition containing same and cured product thereof |
| EP1210942A2 (en) * | 1996-05-07 | 2002-06-05 | Alkermes Controlled Therapeutics Inc. II | Microparticles |
| US6932984B1 (en) * | 1999-11-17 | 2005-08-23 | Tagra Biotechnologies Ltd. | Method of microencapsulation |
| WO2003055470A1 (en) * | 2001-12-26 | 2003-07-10 | Takeda Chemical Industries, Ltd. | Novel microsphere and method for production thereof |
| CN101053814A (en) * | 2007-04-26 | 2007-10-17 | 上海交通大学 | Multiple responsive high molecular microcapsule and preparation method thereof |
| CN103933910A (en) * | 2014-04-11 | 2014-07-23 | 浙江大学 | Preparation method of polymeric porous microsphere |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108366918B (en) * | 2015-09-30 | 2021-07-27 | 爱茉莉太平洋股份有限公司 | Composite powder obtained by impregnating volcanic cinders powder particles in porous polymer, cosmetic composition containing same, and method for producing same |
| CN108366918A (en) * | 2015-09-30 | 2018-08-03 | 爱茉莉太平洋股份有限公司 | Scoria powder particle is impregnated in poromeric composite granule, contains its cosmetic composition and preparation method thereof |
| CN106608982A (en) * | 2015-10-27 | 2017-05-03 | 信越化学工业株式会社 | Porous water-soluble nonionic cellulose ether having excellent solubility and method for producing the same |
| KR102389495B1 (en) * | 2015-10-27 | 2022-04-22 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Porous water-soluble nonionic cellulose ether having excellent solubility and method for producing the same |
| TWI706962B (en) * | 2015-10-27 | 2020-10-11 | 日商信越化學工業股份有限公司 | Porous water-soluble nonionic cellulose ether having excellent solubility and method for producing the same |
| CN106608982B (en) * | 2015-10-27 | 2020-04-24 | 信越化学工业株式会社 | Porous water-soluble nonionic cellulose ether having excellent solubility and method for producing same |
| KR20170049430A (en) * | 2015-10-27 | 2017-05-10 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Porous water-soluble nonionic cellulose ether having excellent solubility and method for producing the same |
| US10767023B2 (en) | 2015-10-27 | 2020-09-08 | Shin-Etsu Chemical Co., Ltd. | Porous water-soluble nonionic cellulose ether having excellent solubility and method for producing the same |
| EP3369749A4 (en) * | 2015-10-30 | 2019-08-07 | Toray Industries, Inc. | Cellulose ether derivative fine particles |
| CN108350091A (en) * | 2015-10-30 | 2018-07-31 | 东丽株式会社 | Ether series fiber element derivative particle |
| CN113083173A (en) * | 2021-04-16 | 2021-07-09 | 中国农业大学 | Water-in-oil Pickering emulsion gel and preparation method thereof |
| CN114106364A (en) * | 2021-11-24 | 2022-03-01 | 天津大学 | Preparation method of ethyl cellulose particles with different morphologies |
| CN114106364B (en) * | 2021-11-24 | 2023-12-05 | 天津大学 | Preparation method of ethyl cellulose particles with different morphologies |
| CN115887285A (en) * | 2022-11-11 | 2023-04-04 | 无锡萃纯生物材料科技有限公司 | Process and equipment for preparing cellulose microspheres and application |
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