CN114534648B - Device for preparing photo-curing water-carrying capsule and preparation method of photo-curing water-carrying capsule - Google Patents
Device for preparing photo-curing water-carrying capsule and preparation method of photo-curing water-carrying capsule Download PDFInfo
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- 239000007789 gas Substances 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The present disclosure provides an apparatus for preparing a photo-curable water-carrying capsule, comprising: the three-layer coaxial needle head (7) and the forming tube (11), wherein one end of the three-layer coaxial needle head is vertically connected with one end of the forming tube, so that substances extruded from the three-layer coaxial needle head are subjected to further forming reaction in the forming tube; the three-layer coaxial needle comprises: the inner phase pump (1), the intermediate phase pump (2), the outer phase pump (3), the inner layer needle head (4), the intermediate layer needle head (5) and the outer layer needle head (6), wherein the inner layer needle head is arranged on the innermost layer, the intermediate layer needle head is sleeved on the outer layer of the inner layer needle head, and the outer layer needle head is sleeved on the outer layer of the intermediate layer needle head, so that the inner layer needle head, the intermediate layer needle head and the outer layer needle head jointly form a three-layer coaxial needle head. Further, the method of preparing a photo-curing water-carrying capsule may be applied to an apparatus for preparing a photo-curing water-carrying capsule. The device can realize one-step molding of the water-carrying capsule, and the water-carrying capsule prepared by the method can improve the concentricity and sphericity of the water-carrying capsule, and effectively improve the storage stability of the water-carrying capsule.
Description
Technical Field
The invention belongs to the technical field of capsules, and particularly relates to a device for preparing a photo-curing water-carrying capsule and a preparation method of the photo-curing water-carrying capsule.
Background
Because of its large embedding rate, good monodispersity and dimensional stability, the water-carrying capsule has wide application in various industries, such as capsule skin care products in daily chemical industry, drug-carrying capsules in medical and sanitary industry, water-soluble food coating in food industry, capsule-type food additives, and cigarette bursting beads in tobacco industry.
The cigarette explosion beads take natural polymer materials or synthetic polymer materials as wall materials, various tobacco essences are wrapped in a tiny airtight spherical capsule in the form of solid, liquid or gas, one or more easily-pinched fragrant capsules are implanted in the production process of the filter tip, the release of the characteristic fragrance which is manually controllable in the smoking process of the cigarette is realized, the influence of the external environment on the smoking flavor and the loss of the essences caused by the influence are reduced, and the effects of increasing the humidity of the smoke and improving the fragrance interception effect of the filter stick are achieved. Meanwhile, the aroma components in the capsules volatilize, so that the functions of enhancing the aroma and enriching the taste level of the cigarettes can be realized.
In the prior art, the water-carrying capsules are generally prepared by a pill dropping machine, the conventional pill dropping machine is generally provided with only two layers of coaxial needles, namely, a core material is extruded through the innermost layer of needles, and a wall material is extruded through the outer layer of needles, but the quality of the water-carrying capsules prepared by the device is to be improved, such as the sphericity, concentricity and the like of the obtained water-carrying capsules are not high, or the water-holding performance of the used raw materials is limited and the water-carrying capsules cannot be stored for a long time.
At present, the disclosed technology discloses a one-step molding process, which adopts a high polymer material with low water permeability to solve the problem of low water retention rate. The application numbers CN201910090596.1 and CN201811372831.6 are respectively used for preparing the water-carrying capsules by adopting hydrophobic wall materials such as polylactic acid or polyethylene through a coagulation bath method, but the water-carrying capsules can not be applied to the field of foods because organic solvents such as methylene dichloride or acetone are needed, and are not environment-friendly. The application number CN202010841260.7 adopts light-cured resin as a wall material to prepare the water-carrying capsule in a self-assembly mode, but the resin needs to be dissolved by using an organic solvent, and the photoinitiator is added into the water core, so that the water-carrying capsule has higher biotoxicity and cannot be applied to the field of foods. The application number CN201820575981.6 prepares the water-carrying capsule by three-dimensionally copolymerizing Jiao Ruhua liquid drops to generate a channel and a light curing device, and adopts light curing resin as a wall material, because the device is in a horizontal flow mode, emulsified liquid drops adhere to the wall of the tube due to unbalance of gravity and buoyancy, and the method uses ultraviolet radiation to cure when collecting the water-carrying capsule, and the water-carrying capsules are easy to adhere to each other before curing. The application number CN201910618136.1 is used for preparing a multi-layer UV light-cured water-carrying capsule by coaxially dripping and forming, light-cured resin is used as a wall material, but when liquid drops drop to the liquid level of the protective liquid, the liquid drops are impacted by the liquid level to deform, so that the sphericity of the water-carrying capsule is difficult to control, the dropping speed of the liquid drops is not controllable, the light-cured time is difficult to be ensured, and the problem of incomplete curing is easily caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims at providing a device for preparing a photo-curing water-carrying capsule and a preparation method of the photo-curing water-carrying capsule. The water-carrying capsule can be molded in one step by the device, concentricity and sphericity of the water-carrying capsule can be improved by the device, and meanwhile, the water-holding time of the water-carrying capsule is long, so that the storage stability of the water-carrying capsule is effectively improved.
To achieve the above object, the present disclosure provides an apparatus for preparing a photo-curable water-carrying capsule, the apparatus comprising at least:
a three-layer coaxial needle (7) and a forming tube (11), wherein one end of the three-layer coaxial needle (7) is vertically connected with one end of the forming tube (11), so that substances extruded from the three-layer coaxial needle (7) are subjected to further forming reaction in the forming tube (11);
Wherein the three-layer coaxial needle (7) comprises: the device comprises an internal phase pump (1), an intermediate phase pump (2), an external phase pump (3), an internal layer needle (4), an intermediate layer needle (5) and an external layer needle (6), wherein the internal phase pump (1) is connected with the internal layer needle (4), the intermediate phase pump (2) is connected with the intermediate layer needle (5), and the external phase pump (3) is connected with the external layer needle (6);
The inner-layer needle head (4) is arranged on the innermost layer, the middle-layer needle head (5) is sleeved on the outer layer of the inner-layer needle head (4), and the outer-layer needle head (6) is sleeved on the outer layer of the middle-layer needle head (5), so that the inner-layer needle head (4), the middle-layer needle head (5) and the outer-layer needle head (6) jointly form the three-layer coaxial needle head (7).
In some embodiments, the apparatus further comprises: a valve (15), an exhaust device (16);
a branch pipe is arranged at the upper part of the forming pipe (11) near the end connected with the three-layer coaxial needle head (7) so as to connect the exhaust device (16) and the valve (15). In some embodiments, the apparatus further comprises: a light curing device (9) and ultraviolet lamp beads (10);
The ultraviolet lamp beads (10) are arranged in the light curing device (9), and the light curing device (9) is arranged outside the forming tube (11) so that the ultraviolet lamp beads (10) uniformly irradiate light on the forming tube (11);
the ultraviolet lamp beads (10) can be arranged in a ring shape, a spiral shape or a parallel shape.
In some embodiments, the apparatus further comprises: a collector (8);
The other end of the forming tube (11) is connected to the collector (8) such that the other end of the forming tube (11) is immersed in the external phase liquid of the collector (8).
In some embodiments, the material of the forming tube (11) is selected to be a material that can transmit ultraviolet light, and preferably, the ultraviolet transmittance of the material of the forming tube (11) is not less than 80%.
The invention also provides a method for preparing the photo-curing water-carrying capsule, which is applied to any aspect of the device for preparing the photo-curing water-carrying capsule, and comprises the following steps:
The prepared internal phase liquid, the prepared intermediate phase liquid and the prepared external phase liquid are correspondingly filled into an internal phase pump (1), an intermediate phase pump (2) and an external phase pump (3);
extruding the liquids in the internal phase pump (1), the intermediate phase pump (2) and the external phase pump (3) simultaneously through a three-layer coaxial needle (7) to form emulsion droplets;
when the emulsion droplets pass through the forming tube (11), the emulsion droplets form water-carrying capsules under the curing condition of the photo-curing device (9).
In some embodiments, the internal phase liquid is predominantly water, the intermediate phase liquid is a photocurable mixture, and the external phase liquid is a liquid substance that is immiscible with the intermediate phase liquid.
In some embodiments, the internal phase liquid may further comprise one or more of a surfactant, a plant extractant, a fragrance additive, a phase change material, or a functional material.
In this embodiment, the surfactant comprises one or more of tween 80, apg 0810, or poloxamer 407. It is further preferred that the surfactant is present in the internal phase liquid in an amount of 0wt% to 5wt%.
In some embodiments, the photocurable mixture comprises 60wt% to 99wt% of the prepolymer, 0wt% to 30wt% of the diluent, and 1wt% to 10wt% of the photoinitiator, the photocurable mixture having a viscosity of 1000 mPa-s to 15000 mPa-s;
The external phase liquid is one of sodium alginate solution, carboxymethyl cellulose solution, chitosan solution, polyvinyl alcohol solution, silicone oil, vegetable oil or mineral oil, and the viscosity of the external phase liquid is 10 mPa.s-350 mPa.s.
In this embodiment, the prepolymer is one or more of a urethane acrylate prepolymer, an epoxy modified urethane prepolymer, and the like.
The diluent is one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate and the like
The photoinitiator is one or more of diphenyl- (2, 4, 6-trimethyl benzoyl) phosphorus oxide, 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxy cyclohexyl phenyl ketone, diphenyl- (4-phenylthio) phenyl sulfonium hexafluoroantimonate and the like.
In this example, the viscosity of the mesophase liquid is 1000 mPas-15000 mPas (25 ℃); more preferably 8000 mPas to 10000 mPas. By setting the viscosity of the mesophase liquid in a proper viscosity range, the wall material of the water-carrying capsule can be extruded from the millifluidic needle head, and the water-carrying capsule has high water content and moderate crushing strength.
In some embodiments, the flow rates of the inner phase liquid, the intermediate liquid, and the outer phase liquid are from 0.05mL/min to 30mL/min.
In this embodiment, the flow rates of the liquids in the internal phase, intermediate phase and external phase pumps are 0.05mL/min to 30mL/min; preferably, the flow rate of the internal phase is 0.05mL/min-1.00mL/min, the flow rate of the intermediate phase is 0.01mL/min-0.20mL/min, and the flow rate of the external phase is 1mL/min-30mL/min.
The particle size of the water-carrying capsules prepared by the method of the embodiment of the disclosure is about 2.0mm-4.5mm, and further about 2.6mm, 2.7mm, 2.8mm, 2.9mm, 3.0mm, 3.1mm, 3.2mm, 3.4mm and the like.
The crushing strength of the water-carrying capsule is about 1N-25N, and further can be 8N-13N, 9N-12N, 10N-11N, 10N-15N, etc. In the crushing strength range of the present disclosure, the water-carrying capsule product has both good mechanical strength, is suitable for transportation and storage, and is also convenient for crushing during use, and has good application experience.
The water content of the water-carrying capsule prepared by the method disclosed by the embodiment of the invention can reach 100wt%. The initial water carrying rate can reach 70wt percent or more than 80wt percent, and further can exceed 95 percent; the seven-day water retention exceeds 70wt%, further may exceed 80%, or exceeds 90%.
The water-carrying capsules prepared by the method disclosed by the embodiment of the invention are spherical, the sphericity is more than 90%, and further more than 96% and more than 97%. Meanwhile, the concentricity of the water-carrying capsule is more than 60 percent, and can be more than 70 percent, or more than 80 percent, or more than 90 percent.
The invention has the beneficial effects that:
The water-carrying capsule can be molded in one step by the coaxial millifluidic device and the photo-curing method which are vertically arranged. The vertical arrangement can avoid the phenomenon that liquid drops adhere to the pipe wall due to gravity; the coaxial millifluidic method submerges the needle head in the external phase liquid, so that the impact of the external phase liquid when the liquid drops drop is avoided. This has the water-carrying capsule that makes the device preparation more thin wall to make the water-carrying capsule that the preparation obtained can obtain higher water-carrying capacity, still improved concentricity and sphericity simultaneously.
Drawings
The present disclosure will be described in further detail below in conjunction with the drawings and preferred embodiments, but those skilled in the art will appreciate that these drawings are drawn for the purpose of illustrating the preferred embodiments only and thus should not be taken as limiting the scope of the present disclosure.
Fig. 1: preparing a schematic diagram of a device for the water-carrying capsule which can be photo-cured and has high water retention by a dripping method; the list of structures in the figure is as follows: 1: an internal phase pump; 2: an external phase pump; 7: a coaxial needle; 8: a collector; 9: a light curing device; 10: ultraviolet light lamp beads.
Fig. 2: a schematic structural view of the coaxial needle 7; the list of structures in the figure is as follows: 7: a coaxial needle; 4: an outlet of the inner layer of the coaxial needle; 5: an outer outlet of the coaxial needle.
Fig. 3: preparing a schematic diagram of a water-carrying capsule device capable of photo-curing and high in water retention by millifluidic method; the list of structures in the figure is as follows: 1: an internal phase pump; 2: a mesophase pump; 3: an external phase pump; 7: a coaxial needle; 8: a collector; 9: a light curing device; 10: ultraviolet light lamp beads; 11: forming a tube; 15: a valve; 16: and an exhaust device.
Fig. 4: a schematic structural view of the coaxial needle 7; the list of structures in the figure is as follows: 7: a coaxial needle; 4: an outlet of the inner layer of the coaxial needle; 5: an outlet of the middle layer of the coaxial needle head; 6: an outer outlet of the coaxial needle.
Fig. 5: a schematic structural view of the forming tube 11; the list of structures in the figure is as follows: 11: forming a tube; 12: a forming tube inlet; 13: an outlet of the forming tube; 14: forming the branch pipe orifice.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In this embodiment, the present invention provides an apparatus for preparing a photocurable water-carrying capsule, which at least includes: a three-layer coaxial needle (7) and a forming tube (11), wherein one end of the three-layer coaxial needle (7) is vertically connected with one end of the forming tube (11), so that substances extruded from the three-layer coaxial needle (7) are subjected to further forming reaction in the forming tube (11);
The three-layer coaxial needle comprises: the device comprises an internal phase pump (1), an intermediate phase pump (2), an external phase pump (3), an internal layer needle (4), an intermediate layer needle (5) and an external layer needle (6), wherein the internal phase pump is connected with the internal layer needle, the intermediate phase pump is connected with the intermediate layer needle, and the external phase pump is connected with the external layer needle; the inner layer needle is arranged on the innermost layer, the middle layer needle is sleeved on the outer layer of the inner layer needle, and the outer layer of the middle layer needle is sleeved on the outer layer of the outer layer needle, so that the inner layer needle, the middle layer needle and the outer layer needle jointly form the three-layer coaxial needle.
Through the setting of three-layer coaxial syringe needle, can avoid the interference of different prefabricated liquids at the device, and can be favorable to optimizing the demand that different kinds of prefabricated liquids formed the emulsion liquid drop. Further, in this public, can be through the direct connection of three-layer coaxial syringe needle and shaping pipe, can avoid the emulsion liquid droplet can glue the pipe wall because of gravity and buoyancy's unbalance when flowing. Thus, the one-step molding process of the substance directly in the device after being sucked through each pump can be accomplished using the device of the present disclosure.
In some embodiments, the apparatus further comprises: a valve (15), an exhaust device (16);
And a branch pipe is arranged at the upper part of the forming pipe near the end connected with the three-layer coaxial needle head so as to be connected with an exhaust device and a valve.
Wherein the exhaust device is used for removing air in the pipeline, and the valve is used for preventing gas from flowing back.
In some embodiments, the apparatus further comprises: a light curing device (9) and ultraviolet lamp beads (10);
the ultraviolet lamp beads are arranged in the light curing device, and the light curing device is arranged outside the forming tube, so that the ultraviolet lamp beads uniformly irradiate the forming tube.
The ultraviolet lamp beads can be arranged in a ring shape, a spiral shape or a parallel type.
The curing device is arranged on the outer layer of the forming tube, and ultraviolet light beads which are uniformly arranged are arranged in the photo-curing device, so that ultraviolet light can uniformly irradiate on the forming tube.
In some embodiments, the apparatus further comprises: a collector (8); the other end of the forming tube is connected to the collector such that the other end of the forming tube is immersed in the collected external phase liquid.
The collector is internally provided with an external phase liquid, and when the other end of the forming tube is connected with the collector, the other end of the forming tube is immersed in the collected external phase liquid. Therefore, when the liquid drops in the three-layer coaxial needle head drop into the collector towards the photo-curing device, the liquid drops can not be impacted by the liquid level to deform, the sphericity of the water-carrying capsule is more controllable,
In this embodiment, the material of the forming tube is selected to be transparent to ultraviolet light, and preferably the ultraviolet transmittance of the material of the forming tube is not less than 80%. Thus, the time and efficiency of the photo-curing can be controlled more effectively to some extent.
The device of any of the above embodiments is used in combination with a method of preparing a light-curable water-borne capsule, the method comprising:
The prepared internal phase liquid, the prepared intermediate phase liquid and the prepared external phase liquid are correspondingly filled into an internal phase pump (1), an intermediate phase pump (2) and an external phase pump (3);
simultaneously extruding the liquid in the internal phase pump, the middle phase pump and the external phase pump through a three-layer coaxial needle (7) to form emulsion liquid drops;
When the emulsion droplets pass through the forming tube (11), the emulsion droplets form water-carrying capsules under the curing condition of the photo-curing device (9).
The method is applied to a photo-curing device with a three-layer coaxial needle and is applied to the corresponding embodiment described below
Comparative example 1:
the water-carrying capsules were prepared using a two-layer coaxial dropping device, as shown in fig. 1 and 2.
Pumping by an internal phase pump 1 with a flow rate set to 0.20mL/min and extruding from a double-layer coaxial needle inner layer outlet 4 (inner diameter 0.67mm, outer diameter 1.07 mm) with 1wt% Tween 80 as an internal phase;
a photocurable mixture of 82% by weight of urethane acrylate prepolymer, 15% by weight of hydroxyethyl methacrylate, 3% by weight of diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus as an external phase (external phase viscosity 1000 mPa.s, 25 ℃ C.) was pumped by an external phase pump 2 at a flow rate of 0.04mL/min and extruded from a double layer coaxial needle external layer outlet 5 (inner diameter 1.6mm, outer diameter 2.1 mm).
After dropping into a collector 8 containing a polyvinyl alcohol solution having a viscosity of 350 mPas, emulsion droplets are formed, the droplets are allowed to sink into a photo-curing device 9, and the photo-curing mixture is cured by ultraviolet irradiation to form a water-carrying capsule, which is taken out from the collector 8, washed and dried.
Example 1:
the water-carrying capsule is prepared by millifluidic method, and millifluidic device is shown in figure 3.
Pumping by an internal phase pump 1 with a flow rate set to 0.20mL/min and extruding from an internal layer outlet 4 (inner diameter 0.67mm, outer diameter 1.07 mm) of a three-layer coaxial needle 7 by taking 1wt% of Tween 80 as an internal phase;
82% of polyurethane acrylate prepolymer, 15% of hydroxyethyl methacrylate and 3% of diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus are taken as intermediate phases (viscosity of the intermediate phases is 1000 mPa.s and 25 ℃), the mixture is pumped by an intermediate phase pump 2, the flow rate is set to be 0.04mL/min, and the mixture is extruded from a three-layer coaxial needle intermediate outlet 5 (the inner diameter is 1.6mm and the outer diameter is 2.1 mm); a3 wt% polyvinyl alcohol solution (viscosity: 100 mPa.s) was used as an external phase, and the solution was pumped by an external phase pump 3 at a flow rate of 8mL/min, sucked from a collector 8, and extruded from a three-layer coaxial needle outer layer outlet 6 (inner diameter: 3mm, outer diameter: 3.5 mm).
The three-phase liquid is simultaneously extruded to a forming tube with an inner diameter of 7.5mm through a needle to form emulsion droplets. After the droplets flow to the area of the photo-curing means 9, the mesophase is cured under irradiation of ultraviolet radiation, and water-carrying capsules are produced, which are taken out from the collector 8, washed and dried.
Example 2:
The water-carrying capsule is prepared by millifluidic method, and millifluidic device is shown in figures 3-5.
Pumping through an internal phase pump 1 with water as an internal phase, wherein the flow rate is set to be 0.20mL/min, and extruding from an inner layer outlet 4 (with the inner diameter of 0.67mm and the outer diameter of 1.07 mm) of a three-layer coaxial needle 7; 97% polyurethane acrylate prepolymer (viscosity 14000 mPa.s, 25 ℃) and 3% diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide are taken as intermediate phases, pumped by an intermediate phase pump 2, the flow rate is set to be 0.04mL/min, and extruded from a three-layer coaxial needle intermediate outlet 5 (inner diameter 1.6mm and outer diameter 2.1 mm); a3 wt% polyvinyl alcohol solution (viscosity: 100 mPa.s) was used as an external phase, and the solution was pumped by an external phase pump 3 at a flow rate of 8mL/min, sucked from a collector 8, and extruded from a three-layer coaxial needle outer layer outlet 6 (inner diameter: 3mm, outer diameter: 3.5 mm). The three-phase liquid is simultaneously extruded to a forming tube with an inner diameter of 7.5mm through a needle to form emulsion droplets. After the droplets flow to the area of the photo-curing means 9, the mesophase is cured under irradiation of ultraviolet radiation, and water-carrying capsules are produced, which are taken out from the collector 8, washed and dried.
Example 3:
the same as in example 1, except that 95% by weight of an epoxy acrylate prepolymer (viscosity 10000 mPa.s, 25 ℃ C.) and 5% by weight of diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus were used as an intermediate phase.
Example 4:
the water-carrying capsule is prepared by millifluidic method, and millifluidic device is shown in figure 3.
Pumping through an internal phase pump 1 with water as an internal phase, wherein the flow rate is set to be 0.20mL/min, and extruding from an inner layer outlet 4 (with the inner diameter of 0.67mm and the outer diameter of 1.07 mm) of a three-layer coaxial needle 7;
97% polyurethane acrylate prepolymer (viscosity 8000 mPa.s, 25 ℃) and 3% diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide are taken as intermediate phases, pumped by an intermediate phase pump 2, the flow rate is set to be 0.04mL/min, and extruded from a three-layer coaxial needle intermediate outlet 5 (inner diameter 1.6mm and outer diameter 2.1 mm);
The silicone oil having a viscosity of 100 mPas was used as an external phase and pumped by an external phase pump 3 at a flow rate of 8mL/min, sucked from a collector 8, and extruded from a three-layer coaxial needle external layer outlet 6 (inner diameter 3mm, outer diameter 3.5 mm).
The three-phase liquid is simultaneously extruded to a forming tube with an inner diameter of 7.5mm through a needle to form emulsion droplets. After the droplets flow to the area of the photo-curing means 9, the mesophase is cured under irradiation of ultraviolet radiation, and water-carrying capsules are produced, which are taken out from the collector 8, washed and dried.
Example 5:
the same as in example 4, except that the inner diameter of the forming tube was 4mm. The flow rate of the external phase was 2mL/min.
Example 6:
The same as in example 4, except that the inner layer outlet had an inner diameter of 0.4mm, an outer diameter of 0.7mm, the intermediate layer outlet had an inner diameter of 1.07mm and an outer diameter of 1.47mm.
Example 7:
The same as in example 4, except that the internal phase flow rate was 0.225mL/min and the intermediate phase flow rate was 0.015mL/min.
Example 8:
the procedure is as in example 4, except that the flow rate of the external phase is 14mL/min.
Example 9:
The same as in example 4, except that the external phase viscosity was 10 mPas (25 ℃ C.).
Specific test method
Mass: 50 water-carrying capsules were randomly taken, and the mass of the water-carrying capsules was weighed by using an electronic balance and then averaged.
Particle size: 10 water-carrying capsules are randomly taken, photographed by a microscope, 12 point coordinates of the outer contour of the water-carrying capsule shell are marked by Image-Pro Plus software, a circle is fitted by a least square method, and the diameter of the circle is fitted to be used as the particle size of the water-carrying capsule.
Shell thickness: 10 water-carrying capsules were randomly taken, photographed by a microscope, and the shell thicknesses of 12 parts were measured using Image-Pro Plus software, and the average value thereof was used as the shell thickness of the water-carrying capsules.
Sphericity degree: taking 10 water-carrying capsules at random, photographing by using a microscope, marking 12 point coordinates of the outer contour of the water-carrying capsule shell by using Image-Pro Plus software, and fitting a circle by using a least square method to obtain the radius R_1 of the circle and the coordinate O of the circle center. Calculating the distance from the coordinates of 12 points of the outer contour of the water-carrying capsule shell to the coordinates O of the circle center by using Image-Pro Plus software, wherein the maximum distance is d_max, the minimum distance is d_min, and the sphericity s of the water-carrying capsule can be calculated by the following formula:
s＝(1-(d_max-d_min)/R_1)×100％
Concentricity: taking 10 water-carrying capsules at random, photographing by using a microscope, marking 12 point coordinates of the outer contour of the water-carrying capsule shell and 12 point coordinates of the inner contour of the water-carrying capsule shell by using Image-Pro Plus software, fitting out an inner circle and an outer circle by using a least square method to obtain the radius R_1 of the outer circle, the radius R_2 of the inner circle and the distance d_o between two circle centers, wherein the concentricity c of the water-carrying capsule can be calculated by the following formula:
c＝(1-d_o/(R_1-R_2))×100％
crushing strength: randomly taking 20 water-carrying capsules, and testing the crushing strength of the water-carrying capsules by using a capsule comprehensive tester.
Water carrying rate: the total mass of the water-carrying capsule is m, and the mass of water is m water, so that the water-carrying rate formula of the water-carrying capsule can be calculated by the following formula:
Water carrying rate = m_water/m x 100%
Water content: the mass of the core liquid of the water-carrying capsule is m cores, and the mass of the water is m water, so that the water content formula of the water-carrying capsule can be calculated by the following formula:
Water content = m_water/m_core x 100%
Seven days of water retention rate: 50 water-carrying capsules were randomly placed in a petri dish and placed in a constant temperature and humidity box at 25 ℃ and 35% RH for 7 days. The weight of the water-carrying capsule at the starting moment is m_0, the weight of the water-carrying capsule after weighing for 7 days is m_7, the weight of the shell layer of the water-carrying capsule after weighing and completely drying is m_shell, and a 7-day water retention formula of the water-carrying capsule can be calculated by the following formula:
Seven days water retention = (1- (m_0-m_7)/(m_0-m_shell)) ×100%
The products obtained in examples and comparative examples were measured for weight and particle size, and the detection results are shown in Table 1 below.
| Detecting content | Comparative example 1 | Example 1 | Example 2 | Example 3 | Example 4 |
| Mass/g | 0.0163 | 0.0133 | 0.0141 | 0.0160 | 0.0135 |
| Particle size/mm | 3.43 | 2.87 | 3.06 | 3.46 | 2.92 |
| Shell thickness/mm | 0.25 | 0.13 | 0.17 | 0.15 | 0.14 |
| Sphericity/% | 90.88 | 94.40 | 96.19 | 96.23 | 95.59 |
| Concentricity/% | 34.11 | 91.23 | 92.29 | 89.71 | 89.67 |
| Crushing strength/N | 18.38 | 11.97 | 15.51 | 13.22 | 12.34 |
| Water carrying rate/% | 63.10 | 82.09 | 79.89 | 81.54 | 80.45 |
| Seven days water retention/% | 82.99 | 71.58 | 95.05 | 78.29 | 88.07 |
According to the application, the transparent collector is added in the dripping device, and the specific detection data of the embodiment and the comparative example show that the transparent collector is used for preparing the water-carrying capsule by the one-step method, compared with the prior art, the three-layer coaxial needle structure is changed, the silicone oil external phase is added in the needle, the concentricity and sphericity of the water-carrying capsule are improved by the arrangement of the structure, the concentricity of the prepared water-carrying capsule is higher compared with the two-layer coaxial dripping device, and the corresponding water content and water retention performance of the water-carrying capsule can be maintained by the three-layer coaxial device compared with the traditional device.
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (8)
1. A device for preparing a photo-curing water-carrying capsule is characterized in that,
The device comprises at least:
The three-layer coaxial needle (7) and a forming tube (11), wherein one end of the three-layer coaxial needle (7) is vertically connected with one end of the forming tube (11), and the three-layer coaxial needle is directly connected with the forming tube, so that substances extruded from the three-layer coaxial needle (7) are subjected to further forming reaction in the forming tube (11);
Wherein the three-layer coaxial needle (7) comprises: the internal phase pump (1), the intermediate phase pump (2), the external phase pump (3), an internal layer needle (4), an intermediate layer needle (5) and an external layer needle (6), wherein the internal phase pump (1) is connected with the internal layer needle (4), the intermediate phase pump (2) is connected with the intermediate layer needle (5), and the external phase pump (3) is connected with the external layer needle (6);
The inner-layer needle head (4) is arranged on the innermost layer, the middle-layer needle head (5) is sleeved on the outer layer of the inner-layer needle head (4), and the outer-layer needle head (6) is sleeved on the outer layer of the middle-layer needle head (5), so that the inner-layer needle head (4), the middle-layer needle head (5) and the outer-layer needle head (6) jointly form the three-layer coaxial needle head (7);
the apparatus further comprises: a valve (15), an exhaust device (16);
A branch pipe is arranged at the upper part of the forming pipe (11) close to the end connected with the three-layer coaxial needle head (7) so as to connect the exhaust device (16) and the valve (15);
The apparatus further comprises: a light curing device (9) and ultraviolet lamp beads (10);
The ultraviolet lamp beads (10) are arranged in the light curing device (9), and the light curing device (9) is arranged outside the forming tube (11) so that the ultraviolet lamp beads (10) uniformly irradiate light on the forming tube (11);
the ultraviolet light lamp beads (10) are arranged in a ring shape, a spiral shape or a parallel type.
2. An apparatus for preparing a photocurable water-bearing capsule according to claim 1, characterized in that said apparatus further comprises: a collector (8);
The other end of the forming tube (11) is connected to the collector (8) such that the other end of the forming tube (11) is immersed in the external phase liquid of the collector (8).
3. A device for preparing a water-carrying photo-curing capsule according to any one of claims 1-2, wherein the forming tube (11) is made of a material which can transmit ultraviolet light, and the ultraviolet light transmittance of the material of the forming tube (11) is not less than 80%.
4. A method of preparing a photocurable water-carrying capsule for use in an apparatus for preparing a photocurable water-carrying capsule according to any one of claims 1-3, the method comprising:
The prepared internal phase liquid, the prepared intermediate phase liquid and the prepared external phase liquid are correspondingly filled into an internal phase pump (1), an intermediate phase pump (2) and an external phase pump (3);
extruding the liquids in the internal phase pump (1), the intermediate phase pump (2) and the external phase pump (3) simultaneously through a three-layer coaxial needle (7) to form emulsion droplets;
when the emulsion droplets pass through the forming tube (11), the emulsion droplets form water-carrying capsules under the curing condition of the photo-curing device (9).
5. A method of preparing a photocurable water-bearing capsule according to claim 4, wherein said inner phase liquid is predominantly water, said intermediate phase liquid is a photocurable mixture, and said outer phase liquid is a liquid substance that is immiscible with said intermediate phase liquid.
6. The method of claim 5, wherein the internal phase liquid further comprises one or more of a surfactant, a plant extractant, a fragrance additive, and a phase change material.
7. A method of preparing a photocurable water-bearing capsule in accordance with claim 5,
The photocurable mixture comprises 60-99 wt% of prepolymer, 0-30 wt% of diluent and 1-10 wt% of photoinitiator, and the viscosity of the photocurable mixture is 1000-15000 mPa.s;
The external phase liquid is one of sodium alginate solution, carboxymethyl cellulose solution, chitosan solution, polyvinyl alcohol solution, silicone oil, vegetable oil or mineral oil, and the viscosity of the external phase liquid is 10 mPa.s-350 mPa.s.
8. A method of preparing a photocurable water-bearing capsule according to claim 6, wherein the flow rates of said inner phase liquid, said intermediate liquid and said outer phase liquid are in the range of 0.05mL/min to 30mL/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04322741A (en) * | 1991-04-19 | 1992-11-12 | Freunt Ind Co Ltd | Formation of seamless capsule and device therefor |
| CN1856354A (en) * | 2003-08-01 | 2006-11-01 | 宝洁公司 | Microcapsules |
| JP2008161817A (en) * | 2006-12-28 | 2008-07-17 | National Institute Of Advanced Industrial & Technology | Method for manufacturing hollow microcapsule |
| CN111602847A (en) * | 2020-05-12 | 2020-09-01 | 武汉市昱宸峰科技有限公司 | Water-based blasting bead for cigarettes and preparation method thereof |
| CN112265196A (en) * | 2020-10-30 | 2021-01-26 | 云南南中科技有限公司 | Ultraviolet curing water-based capsule production facility |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0211706B1 (en) * | 2001-08-03 | 2013-11-26 | METHOD FOR ENCLOSURING A PRODUCT FOR MAKING CAPSULES, AND, CAPSULE |
-
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- 2022-01-26 CN CN202210092787.3A patent/CN114534648B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04322741A (en) * | 1991-04-19 | 1992-11-12 | Freunt Ind Co Ltd | Formation of seamless capsule and device therefor |
| CN1856354A (en) * | 2003-08-01 | 2006-11-01 | 宝洁公司 | Microcapsules |
| JP2008161817A (en) * | 2006-12-28 | 2008-07-17 | National Institute Of Advanced Industrial & Technology | Method for manufacturing hollow microcapsule |
| CN111602847A (en) * | 2020-05-12 | 2020-09-01 | 武汉市昱宸峰科技有限公司 | Water-based blasting bead for cigarettes and preparation method thereof |
| CN112265196A (en) * | 2020-10-30 | 2021-01-26 | 云南南中科技有限公司 | Ultraviolet curing water-based capsule production facility |
Non-Patent Citations (1)
| Title |
|---|
| 基于微流控装置制备聚丙烯腈靶用微胶囊;施展, 葛丽芹;强激光与粒子束;第25卷(第8期);第1979-1983页 * |
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