CN104226191B - 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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- CN104226191B CN104226191B CN201410441745.1A CN201410441745A CN104226191B CN 104226191 B CN104226191 B CN 104226191B CN 201410441745 A CN201410441745 A CN 201410441745A CN 104226191 B CN104226191 B CN 104226191B
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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 room temperature of ethyl cellulose porous particle
Preparation method.
Background technology
Ethyl cellulose is the derivant that ethyoxyl displacement hydroxyl is formed in cellulose molecular chain, with small toxicity, surely
Fixed, inactive, viscosity is big, filming performance is good, while it has the characteristics of being permeated and be not dissolved by hydrone, extensively should
For the carrier of the sustained release pharmaceutical formulation of various ways.The surface area of pore type spheroidal particle is big, and mobility, dissolubility are more preferable,
The improvement of these physical property can more effectively control the release of medicine, improve curative effect.(the supercritical CO_2 antisolvent precipitations such as Zhang Yan
Prepare Ethylcellulose Microspheress, Chemical Engineering, 2005,33 (3)：63-67) by the supercritical CO of designed, designed2It is prepared by microsphere
Device, is prepared for surface smooth with the preferable Ethylcellulose Microspheress of sphericity using ethyl cellulose-acetone mixed solution.Can
In interior regulation and control microsphere size in a big way.
But the device structure used by this kind of method is complicated, processing step is more, completes to prepare under high pressure, manufacturing cost
It is very high, it is unsuitable for mass production.
The content of the invention
It is an object of the invention to provide a kind of preparation method of porous polymer materials, particularly a kind of second of low cost
The normal temperature preparation method of base cellulose porous particle.
The technical solution for realizing the object of the invention is：A kind of normal temperature preparation method of ethyl cellulose porous particle,
Comprise the following steps：
Step 1, ethyl cellulose is dissolved in solvent obtains solvent-laden ethyl cellulose colloidal sol；Described solvent is
Ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, methanol, ethanol, dichloromethane, tetrahydrofuran, isopropanol, fourth
One or more mixture in alcohol, Hexalin, acetone, butanone, Ketohexamethylene；Solvent load is ethyl cellulose quality
5-20 times.
Step 2, by water or aqueous solution containing surfactant using general emulsification method emulsifying to the second described in step 1
In base cellulose sol, interior phase is obtained for water or aqueous solution, the macromolecule emulsion that foreign minister is ethyl cellulose colloidal sol；
The described aqueous solution containing surfactant is to live for the general surfaces of 0.001%-0.2% containing mass concentration scope
The aqueous solution of property agent；Described water or the amount of aqueous solution used containing surfactant are the 0.1～1.0 of step 1 solvent for use volume
Times.
Step 3, the macromolecule emulsion for obtaining step 2 are distributed to water or the aqueous solution containing dispersant under stirring
In, macromolecule emulsion is dispersed into spherical droplets；
The described aqueous solution containing dispersant is arabic gum, the bone containing mass concentration scope for 0.02%-0.5%
Glue, methylcellulose, Polyethylene Glycol, polyvinyl alcohol, the aqueous solution of gelatin；The consumption of water or the aqueous solution containing dispersant is step
1.0～2.0 times of 1 solvent for use volume.
Step 4, the material that step 3 is obtained and water or the aqueous solution containing dispersant, disperse ball in aqueous
Shape drop is progressively hardened and is transformed into solid spherical particles；The species and concentration and step of water used or the aqueous solution containing dispersant
It is identical in 3；The consumption of the water or the aqueous solution containing dispersant is 10～40 times of step 1 solvent for use volume.
Step 5, solid-liquid separation is carried out using general method, the solid particle to isolating is dried, and obtains ethyl
Cellulose porous particle, the aqueous solution separated carries out solvent recovery.
Above-mentioned steps 1 are to carry out at normal temperatures to step 4.
The present invention compared with prior art, with advantages below：1) method of the present invention technique is simpler, it is not necessary in height
Prepare under the conditions of pressure, preparation technology is safer, and production efficiency is greatly improved, can be with industrialized production；2) side of the invention
Method is distilled without solvent, is plastic only by adding aqueous dispersion, and solvent can be recycled, cost-effective, operation
Simply；3) method of the present invention only adjusts the grain that just can well control finished particle by solvent ratios and emulsification condition
Footpath, porosity, easily control than traditional handicraft；4) the ethyl cellulose porous particle ball prepared using the method for the present invention
Shape Du Genggao, internal pore structure is evenly.
Description of the drawings
Fig. 1 is that ethyl cellulose porous particle prepared by embodiment 1 measures granule-morphology figure by optical microscope.
Fig. 2 is the section pore structure pattern that the ethyl cellulose porous particle prepared by embodiment 2 is obtained by SEM tests
Figure.
Fig. 3 is the section pore structure pattern that the ethyl cellulose porous particle prepared by embodiment 3 is obtained by SEM tests
Figure.
Fig. 4 is the section pore structure pattern that the ethyl cellulose porous particle prepared by embodiment 4 is obtained by SEM tests
Figure.
Fig. 5 is the section pore structure pattern that the ethyl cellulose porous particle prepared by embodiment 5 is obtained by SEM tests
Figure.
Specific embodiment
A kind of normal temperature preparation method 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
Ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, methanol, ethanol, dichloromethane, tetrahydrofuran, isopropanol, fourth
One or more mixture in alcohol, Hexalin, acetone, butanone, Ketohexamethylene；Solvent load is ethyl cellulose quality
5-20 times.
Step 2, by water or aqueous solution containing surfactant using general emulsification method emulsifying to the second described in step 1
In base cellulose sol, interior phase is obtained for water or aqueous solution, the macromolecule emulsion that foreign minister is ethyl cellulose colloidal sol；Described contains
The aqueous solution of surfactant is the aqueous solution containing mass concentration scope for 0.001%-0.2% general-purpose surfactants；Institute
The water stated or the amount of aqueous solution used containing surfactant are 0.1～1.0 times of step 1 solvent for use volume.
Step 3, the macromolecule emulsion for obtaining step 2 are distributed to water or the aqueous solution containing dispersant under stirring
In, macromolecule emulsion is dispersed into spherical droplets；The described aqueous solution containing dispersant is to be containing mass concentration scope
The arabic gum of 0.02%-0.5%, osseocolla, methylcellulose, Polyethylene Glycol, polyvinyl alcohol, the aqueous solution of gelatin；Water contains
The consumption of the aqueous solution of dispersant is 1.0～2.0 times of step 1 solvent for use volume.
Step 4, the material that step 3 is obtained and water or the aqueous solution containing dispersant, disperse ball in aqueous
Shape drop is progressively hardened and is transformed into solid spherical particles；The species and concentration and step of water used or the aqueous solution containing dispersant
It is identical in 3；The consumption of water or the aqueous solution containing dispersant is 10～40 times of step 1 solvent for use volume.
Step 5, solid-liquid separation is carried out using general method, the solid particle to isolating is dried, and obtains ethyl
Cellulose porous particle, the aqueous solution separated carries out solvent recovery.
Above-mentioned steps 1 are to carry out at normal temperatures to step 4.
It is described in more detail below：
A kind of normal temperature preparation method of ethyl cellulose porous particle of the present invention, is described in detail below：
(1) step 1 is material dissolution process, under stirring, will be dissolved in solvent containing ethyl cellulose and be formed
Ethyl cellulose colloidal sol.First, in material dissolution groove or balling-up reactor being added to containing ethyl cellulose, add ethyl fine
The solvent of 5-20 times of dimension quality amount carries out material dissolution.Before solvent is added, can first add a small amount of water or aqueous solution pair
Ethyl cellulose is disperseed, with prevent material reunite and on wall bond, add water or aqueous solution ratio be ethyl fibre
0-2 times of dimension quality amount.The material dissolution time determines that at normal temperatures dissolution time is according to raw material type and granular size
10-180min, preferably 20-90min.The addition of material dissolution process ethyl cellulose and solvent can once be added or also may be used
Repeatedly add in batches.Further, it is also possible to prepare using single dissolver batch process or continuously ethyl cellulose colloidal sol.
Described solvent is ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, methanol, ethanol, dichloromethane, tetrahydrochysene furan
Mutter, one or more the mixture in isopropanol, butanol, Hexalin, acetone, butanone, Ketohexamethylene.
(2) step 2 is macromolecule emulsion preparation process, by water or aqueous solution containing surfactant under stirring
Being added in ethyl cellulose colloidal sol carries out emulsifying, and it is mutually water or the macromolecule emulsion of aqueous solution to be formed interior.The surface activity
Agent refers to conventional surfactant.Described surfactant can be nonionic surfactant, such as OP or TX systems
Row；Can also be anionic surfactant, such as sodium lauryl sulphate or dodecylbenzene sodium sulfonate；Can also select
Cationic surface active agent, such as Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide.Containing surfactant
Aqueous solution mass concentration be 0.001-0.2%, water or amount of aqueous solution used are 0.1-1.0 times of the solvent volume described in step 1.
The addition of described water or aqueous solution can once be added or repeatedly added, and can also be added continuously.Emulsion process can be
Carry out in balling-up equipment, can be to complete in other emulsifying devices, material is proceeded in balling-up equipment after the completion of emulsifying.
(3) step 3 for dispersion globulation, under agitation by macromolecule emulsion obtained in the previous step be distributed to water or
Aqueous solution containing dispersant is disperseed, and the macromolecule emulsion containing ethyl cellulose forms spherical liquid due to the effect of interfacial tension
Drop；One kind that the dispersant can be selected in arabic gum, osseocolla, methylcellulose, Polyethylene Glycol, polyvinyl alcohol, gelatin.
The mass concentration of dispersant is 0.02%-0.5% in aqueous solution containing dispersant.Aqueous solution containing dispersant can also be last time
Mother solution after the desolvation reclaimed in Ethylcellulose Microspheress molding preparation process, adds dispersant to spherical liquid in aqueous solution
Drop is protected to prevent mutually aggregation.The water of dispersion emulsion or the amount of aqueous solution used containing dispersant are solvent volume in step 1
1.0-2.0 times, can disposably add, it is also possible to be dividedly in some parts.Dispersant can with dispersion balling-up during directly plus
To in system.Time used by dispersion globulation is preferably in 10min-90min；The temperature remains within the normal range for the process system temperature i.e.
Can.Mixing speed determines according to the spherical particle size of the volume of balling head, the shape of stirrer paddle and needs, needs little
The granule of particle diameter can be carried out under higher mixing speed, otherwise then be carried out under relatively low mixing speed.
(4) step 4 is solvent leaching processes, completes to disperse after balling-up, the material that step 3 is obtained and more water or is contained
The aqueous solution of dispersant, the drop of macromolecule emulsion progressively hardens to form spheroidal particle, on described aqueous solution can be
Reclaim in ethylidine cellulose microsphere molding preparation process and the mother solution after desolvation.The step of water or amount of aqueous solution used are 1
10-40 times of middle solvent for use volume, it is ensured that the solvent in spherical droplets is sufficiently diffused in water phase.Step 1 arrives step 4 all
It is to carry out at normal temperatures.
(5) step 5 is feed separation and drying course, by the way of common centrifugation or filtration by aqueous solution and
Solid spherical particles are separated, and the filtrate separated is referred to as mother solution after solvent removal, and a small amount of dispersant is contained in mother solution
And surfactant, can be saved in fixed container and be recycled as disperse medium in next balling-up, it is also possible to collect
The middle qualified discharge after process is qualified.Solvent removal mode in filtrate can adopt what air-distillation or evacuation distilled
Mode is carried out, and recovered solvent can be circulated utilization.
In order to the implementation condition of the present invention is better described, citing elaboration is carried out below, these processes and process conditions are simultaneously
The whole of invention is not represented, can be used as long as not violating the measure of innovative point of the present invention.
Embodiment 1
Using 2 liters of there-necked flasks as balling-up reactor, it is from powder ethyl cellulose of the relative viscosity for 40-70
Raw material, 4.0 grams of ethyl celluloses are added in reactor, and the acetic acid of 20 times of ethyl cellulose quality is added under stirring
The mixed solvent of ethyl ester and ethanol, i.e. solvent ratio are 20, and ethyl acetate mass percent accounts for 75% in mixed solvent, dissolving
After 30min, the colloidal sol containing ethyl cellulose is obtained.Then, under agitation continuously toward system add 20ml distilled water,
The water volume that i.e. emulsifying is entered is about 0.25 times of solvent volume, and aqueous solution continues to stir 30min after adding, and forms uniform high
Molecule emulsion.Next, macromolecule emulsion is distributed under agitation in the aqueous solution containing dispersant carrying out balling-up.Using
Used as dispersant, the concentration of aqueous solution of dispersant is 0.5% to arabic gum, and the consumption of 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,
Add the water of 10 times of solvent volumes toward system again, spherical droplets is gradually hardened, continue to stir 30 minutes at normal temperatures, will
Solid particle and aqueous solution are separated, and the aqueous solution separated adopts air-distillation mode recycling design, the mother solution of recovery
Save and balling-up disperse medium is used as in next group preparation process.Put down after the spheroidal particle drying separated
Particle diameter is 560 μm of ethyl cellulose porous particle, porosity about 80%, and the pore diameter range of internal pore structure concentrates on 5-10
μm, granule-morphology is as shown in Figure 1.As shown in Figure 1, the size of the ethyl cellulose porous particle prepared is more uniform, sphericity
It is higher.
Embodiment 2
Using 2 liters of there-necked flasks as balling-up reactor, it is from powder ethyl cellulose of the relative viscosity for 40-70
Raw material, 8.0 grams of ethyl celluloses are added in reactor, and the acetic acid of 10 times of ethyl cellulose quality is added under stirring
Ethyl ester solvent, i.e. solvent ratio is 10, after dissolving 30min, obtains the colloidal sol containing ethyl cellulose.Then, connect under agitation
Continuous ground emulsifying volume of entering is about 0.4 times of solvent volume of distilled water, and aqueous solution continues to stir 30min after adding, and forms equal
Even macromolecule emulsion.Next, macromolecule emulsion is distributed in the aqueous solution containing dispersant carrying out balling-up.Using Arab
Used as dispersant, the concentration of aqueous solution of dispersant is 0.2% to glue, and the consumption of aqueous solution is 2 times of solvent volume.200rpm's
Disperse 30 minutes under speed of agitator, the macromolecule emulsion containing ethyl cellulose is progressively dispersed into spherical drop.Then, then toward system
The water of 20 times of solvent volumes of middle addition, makes spherical droplets gradually harden, and continues to stir 30 minutes at normal temperatures, by solid particle
Separated with aqueous solution, the aqueous solution separated adopts air-distillation mode recycling design, the mother solution of recovery to save
Balling-up disperse medium is used as in next group preparation process.Obtaining mean diameter after the spheroidal particle drying separated is
1200 μm of ethyl cellulose porous particle, the porosity inside granule about 70%, the pore diameter range of internal pore structure is concentrated on
1-10 μm, the granule internal pore structure form obtained by SEM tests is as shown in Figure 2.As seen from the figure, the ethyl cellulose prepared
The porosity of porous particle is higher, and aperture is in micron level, and aperture is less.
Embodiment 3
Using raw material same as Example 2 and technical process, only solvent ratio is risen to into 20 times, in water in emulsion process
Addition be 0.25 times of solvent volume, leaching processes add the aqueous solution containing dispersant of 10 times of dicyandiamide solutions, the water
Solution is the mother solution that the aqueous solution reclaimed by embodiment 1 is obtained Jing after solvent distillation, and other conditions are same as Example 2, prepare
The internal pore structure of ethyl cellulose porous particle is as shown in figure 3, aperture is concentrated mainly on 4-10 μm.From the figure 3, it may be seen that preparing
Ethyl cellulose porous particle porosity it is higher, aperture is in micron level, and aperture is less.
Embodiment 4
Using 2 liters of there-necked flasks as balling-up reactor, it is from powder ethyl cellulose of the relative viscosity for 40-70
Raw material, 8.0 grams of ethyl celluloses are added in reactor, and the acetic acid of 10 times of ethyl cellulose quality is added under stirring
Ethyl ester solvent, i.e. solvent ratio is 10, after dissolving 30min, obtains the colloidal sol containing ethyl cellulose.Then, connect under agitation
The concentration of continuous ground emulsifying enter that volume is about solvent volume 0.4 times is 0.2%OP-10 type nonionic surfactant water-solubles
Liquid, emulsion process continues 30min, forms uniform macromolecule emulsion.Next, macromolecule emulsion is distributed to containing dispersant
Balling-up is carried out in aqueous solution.Using arabic gum as dispersant, the concentration of aqueous solution of dispersant is 0.3%, the use of aqueous solution
Measure as 1.5 times of solvent volume.Under the speed of agitator of 200rpm disperse 30 minutes, the macromolecule emulsion containing ethyl cellulose by
Step is dispersed into spherical drop.Then the water of 20 times of solvent volumes, then toward system is added, spherical droplets is gradually hardened, after
It is continuous to stir 30 minutes at normal temperatures, solid particle and aqueous solution are separated, the aqueous solution separated adopts air-distillation
Mode recycling design.The ethyl cellulose porous particle that mean diameter is 300 μm is obtained after the spheroidal particle drying separated,
Porosity inside granule about 75%, the pore diameter range of internal pore structure concentrates on 0.5-5 μm, the granule obtained by SEM tests
Internal pore structure form is as shown in figure 4,1.86 μm of average pore size.
As shown in Figure 4, the porosity of the ethyl cellulose porous particle prepared is higher, and aperture is in micron level, aperture
It is less.
Embodiment 5
Using raw material same as Example 2 and technical process, solvent ratio remains as 10 times, is only in water in emulsion process
It is middle to add 0.1% cationic surfactant hexadecyltrimethylammonium chloride as emulsifying agent, other process conditions and reality
Apply example 2 identical, prepare about 800 μm of ethyl cellulose porous particle mean diameter, the internal pore structure such as figure obtained by SEM tests
Shown in 5,2.7 μm of average pore size.
As shown in Figure 5, the porosity of the ethyl cellulose porous particle prepared is higher, and aperture is in micron level, aperture
It is less.
Embodiment 6-16
Using technical process same as Example 4, from ethyl acetate as the solvent of ethyl cellulose dissolved, disperse
Amount of aqueous solution used of the globulation containing dispersant is 1.8 times of solvent volume, and solvent ratio, aqueous surfactant solution are changed respectively
Parameter, other specification and the phase of embodiment 3 such as mass concentration, the mass concentration of aqueous dispersant, the water consumption of leaching processes
Together, mean diameter and the aperture that ethyl cellulose porous particle is obtained is as shown in the table.
Embodiment 17-22
Using technical process same as Example 3, from ethyl acetate as the solvent of ethyl cellulose dissolved, disperse
Amount of aqueous solution used of the globulation containing dispersant is 2 times of solvent volume, only changes the species of dispersant, other specification and enforcement
Example 3 is identical, and mean diameter and the aperture that ethyl cellulose porous particle is obtained is as shown in the table.
From upper contrast effect, the method for the present invention is to operate at normal temperatures, while preparation technology is simpler, into moral character
Can be stable, production efficiency can be increased substantially, additionally, processing medium is all recycled, do not result in environmental pollution.
Embodiment 23
Using 2 liters of there-necked flasks as balling-up reactor, it is from powder ethyl cellulose of the relative viscosity for 40-70
Raw material, 8.0 grams of ethyl celluloses are added in reactor, and the acetic acid of 10 times of ethyl cellulose quality is added under stirring
Ethyl ester solvent, i.e. solvent ratio is 10, after dissolving 30min, obtains the colloidal sol containing ethyl cellulose.Then, connect under agitation
The concentration of continuous ground emulsifying enter that volume is about solvent volume 0.1 times is 0.2%OP-10 type nonionic surfactant water-solubles
Liquid, emulsion process continues 30min, forms uniform macromolecule emulsion.Next, macromolecule emulsion is distributed to containing dispersant
Balling-up is carried out in aqueous solution.Using arabic gum as dispersant, the concentration of aqueous solution of dispersant is 0.3%, the use of aqueous solution
Measure as 1.5 times of solvent volume.Under the speed of agitator of 200rpm disperse 30 minutes, the macromolecule emulsion containing ethyl cellulose by
Step is dispersed into spherical drop.Then the water of 20 times of solvent volumes, then toward system is added, spherical droplets is gradually hardened, after
It is continuous to stir 30 minutes at normal temperatures, solid particle and aqueous solution are separated, the aqueous solution separated adopts air-distillation
Mode recycling design.The ethyl cellulose porous particle that mean diameter is 300 μm is obtained after the spheroidal particle drying separated,
Porosity inside granule about 15%, the pore diameter range of internal pore structure concentrates on 0.5-5 μm.The ethyl cellulose prepared is more
The porosity of hole granule is higher, and aperture is in micron level, and aperture is less.
Embodiment 24
Using 2 liters of there-necked flasks as balling-up reactor, it is from powder ethyl cellulose of the relative viscosity for 40-70
Raw material, 8.0 grams of ethyl celluloses are added in reactor, and the acetic acid of 10 times of ethyl cellulose quality is added under stirring
Ethyl ester solvent, i.e. solvent ratio is 10, after dissolving 30min, obtains the colloidal sol containing ethyl cellulose.Then, connect under agitation
The concentration of continuous ground emulsifying enter that volume is about solvent volume 1.0 times is 0.2%OP-10 type nonionic surfactant water-solubles
Liquid, emulsion process continues 30min, forms uniform macromolecule emulsion.Next, macromolecule emulsion is distributed to containing dispersant
Balling-up is carried out in aqueous solution.Using arabic gum as dispersant, the concentration of aqueous solution of dispersant is 0.3%, the use of aqueous solution
Measure as 1.5 times of solvent volume.Under the speed of agitator of 200rpm disperse 30 minutes, the macromolecule emulsion containing ethyl cellulose by
Step is dispersed into spherical drop.Then the water of 20 times of solvent volumes, then toward system is added, spherical droplets is gradually hardened, after
It is continuous to stir 30 minutes at normal temperatures, solid particle and aqueous solution are separated, the aqueous solution separated adopts air-distillation
Mode recycling design.The ethyl cellulose porous particle that mean diameter is 300 μm is obtained after the spheroidal particle drying separated,
Porosity inside granule about 92%, the pore diameter range of internal pore structure concentrates on 0.5-10 μm.The ethyl cellulose prepared
The porosity of porous particle is higher, and aperture is in micron level, and aperture is less.
From the foregoing, it will be observed that the method for the present invention just can be with by emulsification condition, solvent ratios, dosage of surfactant and species
Particle diameter and the aperture of finished particle are controlled well, are easily controlled than traditional handicraft.
Claims (2)
1. a kind of normal temperature preparation method of ethyl cellulose porous particle, it is characterised in that comprise the following steps：
Step 1, ethyl cellulose is dissolved in solvent obtains solvent-laden ethyl cellulose colloidal sol, described solvent is acetic acid
Ethyl ester, butyl acetate, dimethyl carbonate, diethyl carbonate, methanol, ethanol, dichloromethane, tetrahydrofuran, isopropanol, butanol,
One or more mixture in Hexalin, acetone, butanone, Ketohexamethylene；Solvent load is ethyl cellulose quality
5-20 times；
Step 2, by water or aqueous solution containing surfactant using general emulsification method emulsifying to the ethyl fibre described in step 1
In the plain colloidal sol of dimension, interior phase is obtained for water or aqueous solution, the macromolecule emulsion that foreign minister is ethyl cellulose colloidal sol；It is described containing surface
The aqueous solution of activating agent is the aqueous solution containing mass concentration scope for 0.001%-0.2% general-purpose surfactants；Described
Water or the amount of aqueous solution used containing surfactant are 0.1～1.0 times of step 1 solvent for use volume；
Step 3, the macromolecule emulsion for obtaining step 2 are distributed in water or the aqueous solution containing dispersant under stirring, high
Molecule emulsion is dispersed into spherical droplets；The described aqueous solution containing dispersant be containing mass concentration scope be 0.02%-
The aqueous solution of 0.5% arabic gum or osseocolla or methylcellulose or Polyethylene Glycol or polyvinyl alcohol or gelatin；Water or containing point
The consumption of the aqueous solution of powder is 1.0～2.0 times of step 1 solvent for use volume；
Step 4, the material that step 3 is obtained and water or the aqueous solution containing dispersant, disperse spherical liquid in aqueous
Drop is progressively hardened and is transformed into solid spherical particles；In the species and concentration and step 3 of water used or the aqueous solution containing dispersant
It is identical；The consumption of water or the aqueous solution containing dispersant is 10～40 times of step 1 solvent for use volume；
Step 5, solid-liquid separation is carried out using general method, the solid particle to isolating is dried, and obtains ethyl cellulose
Plain 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 characterised in that step 1 is arrived
Step 4 is to carry out at normal temperatures.
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| EP3369749A4 (en) * | 2015-10-30 | 2019-08-07 | Toray Industries, Inc. | Cellulose ether derivative fine particles |
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| EP1210942A2 (en) * | 1996-05-07 | 2002-06-05 | Alkermes Controlled Therapeutics Inc. II | Microparticles |
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| JP3480519B2 (en) * | 1994-09-06 | 2003-12-22 | 日本化薬株式会社 | Method for producing microencapsulated phosphorus-based curing accelerator |
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| CN103933910B (en) * | 2014-04-11 | 2016-01-20 | 浙江大学 | The preparation method of polyalcohol stephanoporate microballoons |
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| 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 |
| CN101053814A (en) * | 2007-04-26 | 2007-10-17 | 上海交通大学 | Multiple responsive high molecular microcapsule and preparation method thereof |
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