WO2013024452A1 - Method for encapsulating substances with formation of the capsule shell by interfacial reaction in the centrifugal reactor - Google Patents
Method for encapsulating substances with formation of the capsule shell by interfacial reaction in the centrifugal reactor Download PDFInfo
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- WO2013024452A1 WO2013024452A1 PCT/IB2012/054172 IB2012054172W WO2013024452A1 WO 2013024452 A1 WO2013024452 A1 WO 2013024452A1 IB 2012054172 W IB2012054172 W IB 2012054172W WO 2013024452 A1 WO2013024452 A1 WO 2013024452A1
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- phase
- emulsion
- starting material
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- water
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- 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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
Definitions
- the present invention relates to a method for encapsulating substances by interfacial reaction with formation of the capsule shell in a centrifugal reactor with rotating packing.
- a core material the disperse phase
- a continuous phase By bringing the two liquid, mutually immiscible phases into contact with one another, which in each case comprise the wall-forming reactive starting materials, the chemical reaction results at the interface of the emulsion droplets, with the formation of polymeric capsule walls.
- WO 03/101606 describes the encapsulation of hydrophobic organic substances in polyurea microcapsules by interfacial polymerization, during which an aqueous phase comprising di- or polyamines and a water-immiscible phase comprising di- or polyisocyanates are brought into contact.
- US 2007/0220686 describes the microencapsulation of pigments in polyurea or polyurethane microcapsules by interfacial polymerization.
- US 6,338,838 describes the production of encapsulated light protection compositions, where the outer capsule shell is likewise produced by interfacial polymerization.
- WO 2009/091726 describes the microencapsulation of hydrophobic cosmetic substances by means of interfacial polymerization of isocyanates and amines with the formation of polyureas.
- US 7,537,644 B2 describes the use of such a reactor type for the degassing of liquids.
- This document refers to numerous publications relating to other uses of this reactor type, for example the use for producing nanoparticles from calcium carbonate.
- the object of the present invention was to find a method for encapsulating substances which helps to overcome the described disadvantages, and leads, in a simple manner and with good yields, to encapsulated products with good properties. Accordingly, a method has been found for encapsulating substances where the capsule walls are obtained by reactions at interfaces, wherein the interfacial reaction is carried out in a centrifugal reactor with rotating packing.
- the interfacial reaction takes place in a disperse system of at least two immiscible phases, in which one disperse phase A is dispersed in a continuous phase B.
- the immiscible phases are ones which spontaneously form different phases upon mixing.
- an emulsion i.e. a two-phase system, in which both the phase A and also the phase B are liquid phases, is produced in the centrifugal reactor with rotating packing in the presence of an interface-active substance.
- a phase A comprising a water-immiscible organic solvent and a starting material A
- an aqueous phase B comprising a starting material B
- a phase A is used which in turn is itself an emulsion of a water-immiscible organic solvent in water.
- the reactive starting substance A here is present in the organic phase.
- the preemulsification takes place in the presence of an interface-active substance.
- the emulsion of phase A and phase B can be of the oil-in-water emulsion type or of the water-in-oil emulsion (W/O) type.
- the substance to be encapsulated can be a hydrophilic or a hydrophobic substance.
- a hydrophilic substance to be encapsulated a water-in-oil emulsion is produced.
- an oil-in-water emulsion (O/W) is produced.
- the method according to the invention is used for encapsulating hydrophobic substances.
- the emulsion type can be adjusted via the selection of the interface- active substance.
- the emulsion type can be adjusted via the quantitative ratio of continuous phase to disperse phase.
- water-immiscible organic solvents are those solvents which spontaneously form a separate phase upon contact with water under standard conditions (at 20°C and a pressure of 0.1 MPa).
- Suitable water-immiscible organic solvents are in particular synthetic or natural aromatic or nonaromatic hydrocarbons, and also synthetic or natural oils. Suitable oils are: vegetable and animal oils, silicone oils, paraffins, triglycerides or oily monomers.
- Aromatic solvents such as benzene or toluene are also suitable. Likewise of suitability are aliphatic hydrocarbons such as Cs-Cso-alkanes.
- the capsule wall obtained by interfacial reaction is a polycondensate.
- Suitable polycondensates are preferably polyureas, polyurethanes, melamine-formaldehyde condensates, polyamides or polycarbonates.
- Suitable polycondensates are preferably polyureas, polyurethanes or a polycarbonate, in particular polyureas.
- polyureas or polyurethanes as wall material for the microcapsules.
- a di- or polyfunctional isocyanate is used as starting material A.
- a di- or polyfunctional compound from the group of amines, hydroxylamines or alcohols is used as starting material B.
- starting material A are, in particular, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1 ,4-phenylene diisocyanate or hexamethylene diisocyanate or mixtures thereof.
- starting material B for producing polyureas are primarily C2-C6-alkylene- diamines, in particular 1 ,6-hexamethylenediamine, or alkylenetriamines such as diethylene- triamine.
- triamines is particularly advisable if relatively high degrees of crosslinking of the capsule wall and less permeable wall material is desired.
- polycondensates can be obtained by reaction of phosgene or acid dichlorides such as sebacoyl dichloride, terephthaloyl dichloride or phthaloyl dichloride with di- or polyfunctional amines, hydroxylamines or alcohols.
- phosgene or acid dichlorides such as sebacoyl dichloride, terephthaloyl dichloride or phthaloyl dichloride
- the encapsulation takes place in the presence of at least one interface-active substance.
- Suitable interface-active substances are surfactants or emulsifiers.
- Anionic, cationic or nonionic emulsifiers for O/W and W/O emulsions can be used.
- Suitable emulsifiers for W/O emulsions can be sorbitan fatty acid esters, for example Span® types, also polysorbates, fatty acid esters of glycerol, polyglycerol esters, fatty acid esters of ethylene glycol, polyethylene glycols, amine alkoxylates (for example Quadrol®), copolymers or block copolymers of polyalkylene oxides, polyoxamines or polyisobutene-polyamine polymers (for example Glissopal®) suitable as emulsifiers.
- sorbitan fatty acid esters for example Span® types
- polysorbates also polysorbates, fatty acid esters of glycerol, polyglycerol esters, fatty acid esters of ethylene glycol, polyethylene glycols, amine alkoxylates (for example Quadrol®), copolymers or block copolymers of polyalkylene oxides, polyoxamines or polyisobut
- Suitable emulsifiers for O/W emulsions are, for example, sorbitan esters, glycerides, polyglyceryl esters or lignosulfonates. Further suitable W/0 or O/W emulsifiers are described in ⁇ . ⁇ . Fiedler, Lexikon der Hilfsstoffe [Lexicon of auxiliaries], keyword: HLB values, p. 77-82, vol. 1 , 4th edition, Editio Cantor Verlag Aulendorf).
- the emulsifiers can be used in amounts of from 0.5 to 10% by weight, based on the disperse phase.
- the amount of the disperse phase, based on the total amount of the emulsion can be 5 to 60% by weight.
- Centrifugal reactors which can be used are all devices of this type known per se which are equipped with a rotating packing. According to the invention, the centrifugal reactors are operated continuously.
- the centrifugal reactor can be operated at pressures of from 0.1 MPa to 3 MPa.
- the centrifugal accelerations are in the range from 500 to 2000 g, preferably 800 to 1500 g [m/s 2 ].
- the temperature in the centrifugal reactor can be in the range from 0 to 150°C, preferably 5 to 70°C.
- the parameters are applied cumulatively, i.e. the interfacial reaction can be carried out at pressures of from 0.1 MPa to 3 MPa and centrifugal accelerations of from 500 to 2000 g and at temperatures of from 0 to 150°C.
- the preferred ranges in each case are freely combinable with one another.
- the flow rates in the centrifugal reactor can be 1 l/min to 1000 l/min.
- the rotating packing used can be, for example, a fabric mesh which consists of metal, ceramic or a textile fabric.
- the fabric meshes can have mesh widths in the range from 0.5 to 10 mm.
- the method according to the invention is suitable for producing microcapsules which comprise a biologically active substance as substance to be encapsulated.
- Suitable biologically active substances are pharmaceutical or cosmetic substances or agrochemicals.
- the method is also suitable for encapsulating inorganic substances such as calcium nitrate or iron oxide for use as concrete ingredients.
- inorganic or organic pigments can be microencapsulated.
- Solvesso 200 aromatic solvent - light oil, boiling range 220-290°C
- Lupranat® M20S 4,4'-diphenylmethane diisocyanate
- hexamethylenediamine Packing material textile fabric, mesh width 2 mm
- Spray lances 5 bores with a diameter of 1 mm
- Diameter of the reactor drum 160 mm
- Diameter of the rotating packing 107 mm
- initial charge 1 The components in initial charge 1 were preemulsified using an oblique-blade stirrer or an Ultra-Turrax. The substances from both initial-charge containers were then sprayed at the same time onto the rotating packing via the spray lances. In the packing, a fine- emulsification of the drops and the formation of the capsules took place as a result of the reaction between isocyanate and amine. Following the capsule formation, the suspension was stirred gently for 3.5 h at 55°C in order to completely cure the capsules formed. The microcapsules obtained had average particle sizes (d(0.5), volume-average) of 2.05 pm.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Method for encapsulating substances, where the capsule walls are obtained by interfacial reaction, wherein the interfacial reaction is carried out in a centrifugal reactor with rotating packing.
Description
Method for encapsulating substances with formation of the capsule shell by interfacial reaction in the centrifugal reactor
Description
The present invention relates to a method for encapsulating substances by interfacial reaction with formation of the capsule shell in a centrifugal reactor with rotating packing.
The encapsulation of substances by means of reactions at an interface is known per se.
Here, a core material, the disperse phase, is dispersed in a continuous phase. By bringing the two liquid, mutually immiscible phases into contact with one another, which in each case comprise the wall-forming reactive starting materials, the chemical reaction results at the interface of the emulsion droplets, with the formation of polymeric capsule walls.
For example, WO 03/101606 describes the encapsulation of hydrophobic organic substances in polyurea microcapsules by interfacial polymerization, during which an aqueous phase comprising di- or polyamines and a water-immiscible phase comprising di- or polyisocyanates are brought into contact. US 2007/0220686 describes the microencapsulation of pigments in polyurea or polyurethane microcapsules by interfacial polymerization.
US 6,338,838 describes the production of encapsulated light protection compositions, where the outer capsule shell is likewise produced by interfacial polymerization.
WO 2009/091726 describes the microencapsulation of hydrophobic cosmetic substances by means of interfacial polymerization of isocyanates and amines with the formation of polyureas.
All of these products are obtained by batch processes. However, the product properties with regard to uniform product quality, such as, for example, encapsulation rates, particle size distribution or stability against agglomeration, are unsatisfactory. It is a further disadvantage that the up-scaling of such batch processes is not possible indefinitely and, moreover, there is the disadvantage of the discontinuous process. Centrifugal reactors with a rotating packing are likewise known per se.
Thus, US 7,537,644 B2 describes the use of such a reactor type for the degassing of liquids. This document refers to numerous publications relating to other uses of this reactor type, for example the use for producing nanoparticles from calcium carbonate. The object of the present invention was to find a method for encapsulating substances which helps to overcome the described disadvantages, and leads, in a simple manner and with good yields, to encapsulated products with good properties.
Accordingly, a method has been found for encapsulating substances where the capsule walls are obtained by reactions at interfaces, wherein the interfacial reaction is carried out in a centrifugal reactor with rotating packing.
The interfacial reaction takes place in a disperse system of at least two immiscible phases, in which one disperse phase A is dispersed in a continuous phase B. The immiscible phases are ones which spontaneously form different phases upon mixing. According to one embodiment of the invention, an emulsion, i.e. a two-phase system, in which both the phase A and also the phase B are liquid phases, is produced in the centrifugal reactor with rotating packing in the presence of an interface-active substance.
According to one embodiment of the invention, a phase A, comprising a water-immiscible organic solvent and a starting material A, and an aqueous phase B, comprising a starting material B, are converted into an emulsion in the presence of at least one surface-active substance and the substance to be encapsulated, where the formation of the capsule wall takes place at the interface of the emulsion droplets by chemical reaction of the starting materials A and B.
According to a further embodiment, a phase A is used which in turn is itself an emulsion of a water-immiscible organic solvent in water. The reactive starting substance A here is present in the organic phase. The preemulsification takes place in the presence of an interface-active substance.
According to the invention, the emulsion of phase A and phase B can be of the oil-in-water emulsion type or of the water-in-oil emulsion (W/O) type. Accordingly, the substance to be encapsulated can be a hydrophilic or a hydrophobic substance. In the case of the embodiment of a hydrophilic substance to be encapsulated, a water-in-oil emulsion is produced. In the case of the embodiment of a hydrophobic substance to be encapsulated, an oil-in-water emulsion (O/W) is produced. Preferably, the method according to the invention is used for encapsulating hydrophobic substances. The emulsion type can be adjusted via the selection of the interface- active substance. Furthermore, the emulsion type can be adjusted via the quantitative ratio of continuous phase to disperse phase.
A combination of said measures can also be used for controlling the emulsion type. Irrespective of the selected embodiment, water-immiscible organic solvents are those solvents which spontaneously form a separate phase upon contact with water under standard conditions (at 20°C and a pressure of 0.1 MPa).
Suitable water-immiscible organic solvents are in particular synthetic or natural aromatic or nonaromatic hydrocarbons, and also synthetic or natural oils. Suitable oils are: vegetable and animal oils, silicone oils, paraffins, triglycerides or oily monomers.
Aromatic solvents such as benzene or toluene are also suitable. Likewise of suitability are aliphatic hydrocarbons such as Cs-Cso-alkanes.
According to one embodiment of the invention, the capsule wall obtained by interfacial reaction is a polycondensate. Suitable polycondensates are preferably polyureas, polyurethanes, melamine-formaldehyde condensates, polyamides or polycarbonates. Suitable polycondensates are preferably polyureas, polyurethanes or a polycarbonate, in particular polyureas.
Particular preference is given to the production of polyureas or polyurethanes as wall material for the microcapsules. Here, a di- or polyfunctional isocyanate is used as starting material A. A di- or polyfunctional compound from the group of amines, hydroxylamines or alcohols is used as starting material B.
Of suitability as starting material A are, in particular, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1 ,4-phenylene diisocyanate or hexamethylene diisocyanate or mixtures thereof.
Of suitability as starting material B for producing polyureas are primarily C2-C6-alkylene- diamines, in particular 1 ,6-hexamethylenediamine, or alkylenetriamines such as diethylene- triamine. The use of triamines is particularly advisable if relatively high degrees of crosslinking of the capsule wall and less permeable wall material is desired.
Furthermore, polycondensates can be obtained by reaction of phosgene or acid dichlorides such as sebacoyl dichloride, terephthaloyl dichloride or phthaloyl dichloride with di- or polyfunctional amines, hydroxylamines or alcohols.
According to all embodiments, the encapsulation takes place in the presence of at least one interface-active substance. Suitable interface-active substances are surfactants or emulsifiers. Anionic, cationic or nonionic emulsifiers for O/W and W/O emulsions can be used. Suitable emulsifiers for W/O emulsions can be sorbitan fatty acid esters, for example Span® types, also polysorbates, fatty acid esters of glycerol, polyglycerol esters, fatty acid esters of ethylene glycol, polyethylene glycols, amine alkoxylates (for example Quadrol®), copolymers or block copolymers of polyalkylene oxides, polyoxamines or polyisobutene-polyamine polymers (for example Glissopal®) suitable as emulsifiers. Suitable emulsifiers for O/W emulsions are, for example, sorbitan esters, glycerides, polyglyceryl esters or lignosulfonates.
Further suitable W/0 or O/W emulsifiers are described in Ή.Ρ. Fiedler, Lexikon der Hilfsstoffe [Lexicon of auxiliaries], keyword: HLB values, p. 77-82, vol. 1 , 4th edition, Editio Cantor Verlag Aulendorf). The emulsifiers can be used in amounts of from 0.5 to 10% by weight, based on the disperse phase. The amount of the disperse phase, based on the total amount of the emulsion, can be 5 to 60% by weight.
Centrifugal reactors which can be used are all devices of this type known per se which are equipped with a rotating packing. According to the invention, the centrifugal reactors are operated continuously.
The ranges specified below for the process parameters are used for all specified embodiments. The centrifugal reactor can be operated at pressures of from 0.1 MPa to 3 MPa.
The centrifugal accelerations are in the range from 500 to 2000 g, preferably 800 to 1500 g [m/s2].
The temperature in the centrifugal reactor can be in the range from 0 to 150°C, preferably 5 to 70°C.
The parameters are applied cumulatively, i.e. the interfacial reaction can be carried out at pressures of from 0.1 MPa to 3 MPa and centrifugal accelerations of from 500 to 2000 g and at temperatures of from 0 to 150°C. The preferred ranges in each case are freely combinable with one another.
The flow rates in the centrifugal reactor can be 1 l/min to 1000 l/min.
The rotating packing used can be, for example, a fabric mesh which consists of metal, ceramic or a textile fabric. The fabric meshes can have mesh widths in the range from 0.5 to 10 mm.
The method according to the invention is suitable for producing microcapsules which comprise a biologically active substance as substance to be encapsulated. Suitable biologically active substances are pharmaceutical or cosmetic substances or agrochemicals.
Furthermore, the method is also suitable for encapsulating inorganic substances such as calcium nitrate or iron oxide for use as concrete ingredients. Likewise, inorganic or organic pigments can be microencapsulated.
Example
Preparation of microcapsules in an O/W emulsion
Composition:
Data in % by weight, based on the total amount of initial charge 1 and 2
Initial charge 1
19.5% by weight of Solvesso 200 (aromatic solvent - light oil, boiling range 220-290°C) 12% by weight of Lupranat® M20S (4,4'-diphenylmethane diisocyanate)
40% by weight of water
1.63% by weight of lignosulfonic acid
1.87% by weight of Atlas G5000 (nonionic surfactant, HLB 17, polyalkylene oxide block copolymer)
Initial charge 2
24.5% by weight of water
0.5% by weight of hexamethylenediamine Packing material: textile fabric, mesh width 2 mm
Spray lances: 5 bores with a diameter of 1 mm
Speed of the rotating packing: 5000 rpm
Diameter of the reactor drum: 160 mm
Diameter of the rotating packing: 107 mm
Packing density: 56 mm
Flow rate in the region of 0.8 l/h
The components in initial charge 1 were preemulsified using an oblique-blade stirrer or an Ultra-Turrax. The substances from both initial-charge containers were then sprayed at the same time onto the rotating packing via the spray lances. In the packing, a fine- emulsification of the drops and the formation of the capsules took place as a result of the reaction between isocyanate and amine. Following the capsule formation, the suspension was stirred gently for 3.5 h at 55°C in order to completely cure the capsules formed. The microcapsules obtained had average particle sizes (d(0.5), volume-average) of 2.05 pm.
Claims
1 . A method for encapsulating substances, where the capsule walls are obtained by
interfacial reaction, wherein the interfacial reaction is carried out in a centrifugal reactor with rotating packing.
2. The method according to claim 1 , wherein a phase A, comprising a water-immiscible organic solvent and a starting material A, and an aqueous phase B, comprising a starting material B, are converted into an emulsion in the presence of at least one surface-active substance and the substance to be encapsulated, where the formation of the capsule wall takes place at the interface of the emulsion droplets by chemical reaction of the starting materials A and B.
3. The method according to either of claims 1 and 2, wherein a fabric mesh is used as rotating packing.
4. The method according to any one of claims 1 to 3, wherein the packing is rotated with a centrifugal acceleration of from 500 g to 5000 g.
5. The method according to any one of claims 1 to 4, wherein the centrifugal reactor is operated at pressures of from 0.1 to 3 MPa.
6. The method according to any one of claims 1 to 5, wherein the flow rate in the
centrifugal reactor is 1 l/min to 1000 l/min.
7. The method according to any one of claims 1 to 6, wherein the temperature in the
centrifugal reactor is in the range from 0 to 100°C.
8. The method according to any one of claims 2 to 7, wherein the emulsion of phase A and phase B is an oil-in-water emulsion or a water-in-oil emulsion.
9. The method according to any one of claims 1 to 8, wherein the substance to be
encapsulated is a hydrophilic or a hydrophobic substance.
10. The method according to any one of claims 2 to 9, wherein the phase A is an emulsion of a water-immiscible organic solvent in water.
1 1 . The method according to any one of claims 2 to 10, wherein an aromatic solvent or a light oil is used as organic solvent of phase A.
12. The method according to any one of claims 1 to 1 1 , wherein the capsule wall obtained by interfacial reaction is a polycondensate.
Gd/Ya 13.08.2012
13. The method according to any one of claims 1 to 12, wherein the capsule wall obtained by interfacial reaction consists of a polyurea, a polyurethane, a polyamide or a polycarbonate.
14. The method according to any one of claims 2 to 13, wherein a di- or polyfunctional isocyanate is used as starting material A.
15. The method according to any one of claims 2 to 14, wherein a di- or polyfunctional compound from the group of amines, hydroxylamines or alcohols is used as starting material B.
16. The method according to any one of claims 2 to 15, wherein diphenylmethane
diisocyanate, polymeric diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1 ,4-phenylene diisocyanate or hexamethylene diisocyanate is used as starting material A.
17. The method according to any one of claims 2 to 16, wherein C2-C6-alkylenediamines are used as starting material B.
18. The method according to any one of claims 2 to 17, wherein at least one surfactant or emulsifier is used as interface-active substance.
19. The method according to any one of claims 2 to 17, wherein a lignosulfonic acid or polyalkylene oxide block copolymers or mixtures thereof are used as interface-active substance.
20. The method according to any one of claims 1 to 17, wherein construction chemicals are used as substances to be encapsulated.
21 . The method according to any one of claims 1 to 18, wherein a biologically active
substance is used as substance to be encapsulated.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12824551.1A EP2744486A4 (en) | 2011-08-16 | 2012-08-16 | Method for encapsulating substances with formation of the capsule shell by interfacial reaction in the centrifugal reactor |
| CN201280038948.5A CN103732219A (en) | 2011-08-16 | 2012-08-16 | Method for encapsulating substances with formation of capsule shell by interfacial reaction in centrifugal reactor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11177665A EP2559481A1 (en) | 2011-08-16 | 2011-08-16 | Method for encapsulating substances by forming the capsule using interfacial reaction in a centrifugal reactor |
| EP11177665.4 | 2011-08-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013024452A1 true WO2013024452A1 (en) | 2013-02-21 |
Family
ID=44674274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2012/054172 WO2013024452A1 (en) | 2011-08-16 | 2012-08-16 | Method for encapsulating substances with formation of the capsule shell by interfacial reaction in the centrifugal reactor |
Country Status (3)
| Country | Link |
|---|---|
| EP (2) | EP2559481A1 (en) |
| CN (1) | CN103732219A (en) |
| WO (1) | WO2013024452A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109110831A (en) * | 2017-06-23 | 2019-01-01 | 兰州山水环保科技有限责任公司 | A kind of efficient centrifugal reactor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105386149A (en) * | 2015-10-26 | 2016-03-09 | 安徽泛博纺织科技有限公司 | Colored polyester filament yarns with skin-core structure improved by adding special master batch and preparing method |
| CN112159144B (en) * | 2020-09-24 | 2022-04-22 | 金华市公路与运输管理中心 | Permeable microcapsule for asphalt concrete pavement and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5441840A (en) * | 1992-12-02 | 1995-08-15 | Fuji Xerox Co., Ltd. | Capsule toner and process for producing the same |
| WO2003101606A1 (en) * | 2002-05-31 | 2003-12-11 | Mcmaster University | Method of encapsulating hydrophobic organic molecules in polyurea capsules |
| US20060115604A1 (en) * | 2004-12-01 | 2006-06-01 | Fuji Xerox Co., Ltd. | Liquid crystal microcapsule, method for producing the same, and liquid crystal display device using the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO20002309L (en) | 1999-05-12 | 2000-11-13 | Hoffmann La Roche | Photo-stable cosmetic light-shielding compositions |
| US7537644B2 (en) | 2003-10-24 | 2009-05-26 | Gastran Systems | Method for degassing a liquid |
| US8680212B2 (en) | 2006-03-24 | 2014-03-25 | L'oreal | Composite dyestuff of microcapsule type and cosmetic use thereof |
| US20110059144A1 (en) | 2008-01-16 | 2011-03-10 | Fletcher Robert B | Encapsulated hydrophobic actives via interfacial polymerization |
| CN101549273B (en) * | 2009-03-30 | 2011-06-15 | 浙江新和成股份有限公司 | Method of preparing nano-dispersed high-all-trans-carotenoid microcapsules |
| CN102106345A (en) * | 2009-12-28 | 2011-06-29 | 联合国南通农药剂型开发中心 | Avermectin microcapsule suspending agent and preparation method thereof |
-
2011
- 2011-08-16 EP EP11177665A patent/EP2559481A1/en not_active Withdrawn
-
2012
- 2012-08-16 WO PCT/IB2012/054172 patent/WO2013024452A1/en active Application Filing
- 2012-08-16 EP EP12824551.1A patent/EP2744486A4/en not_active Withdrawn
- 2012-08-16 CN CN201280038948.5A patent/CN103732219A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5441840A (en) * | 1992-12-02 | 1995-08-15 | Fuji Xerox Co., Ltd. | Capsule toner and process for producing the same |
| WO2003101606A1 (en) * | 2002-05-31 | 2003-12-11 | Mcmaster University | Method of encapsulating hydrophobic organic molecules in polyurea capsules |
| US20060115604A1 (en) * | 2004-12-01 | 2006-06-01 | Fuji Xerox Co., Ltd. | Liquid crystal microcapsule, method for producing the same, and liquid crystal display device using the same |
Non-Patent Citations (3)
| Title |
|---|
| ABKARIAN, M. ET AL.: "Continuous droplet interface crossing encapsulation (cDICE) for high throughput monodisperse vesicle design", SOFT MATTER., vol. 7, no. 10, 15 April 2011 (2011-04-15), pages 4610 - 4614, XP055124394 * |
| ROSENBAUER E. ET AL.: "Surface-Active Monomer as a Stabilizer for Polyurea Nanocapsules Synthesized via Interfacial Polyaddition in Inverse Miniemulsion", LANGMUIR, vol. 25, no. 20, 20 July 2009 (2009-07-20), pages 12084 - 12091, XP055124395 * |
| See also references of EP2744486A4 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109110831A (en) * | 2017-06-23 | 2019-01-01 | 兰州山水环保科技有限责任公司 | A kind of efficient centrifugal reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2559481A1 (en) | 2013-02-20 |
| EP2744486A1 (en) | 2014-06-25 |
| CN103732219A (en) | 2014-04-16 |
| EP2744486A4 (en) | 2015-05-06 |
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