CN1161660A - Encapsulated active material and method for preparing same - Google Patents
Encapsulated active material and method for preparing same Download PDFInfo
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- CN1161660A CN1161660A CN 95195276 CN95195276A CN1161660A CN 1161660 A CN1161660 A CN 1161660A CN 95195276 CN95195276 CN 95195276 CN 95195276 A CN95195276 A CN 95195276A CN 1161660 A CN1161660 A CN 1161660A
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- active material
- coating material
- solvent
- microballoon
- dimethyl urea
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Abstract
An active material encapsulated in a coating material immiscible therewith is contacted with a solvent that dissolves residual active material on the surface of the coating material without dissolving the coating material. The resultant encapsulated material has improved stability as compared to the material not contacted with solvent.
Description
The present invention relates to a kind of with active material be encapsulated in its not miscible protectiveness coating material in the method and the active material of this method packing.
The dressing of active material or micro-capsule embedding are used to prevent that these materials from contacting with environment, or control their release or improve their operation.The description of existing many dressings or micro-capsule embedding techniques in the prior art.For example Somerville (United States Patent (USP) 3015128) has described a kind of centrifugal packing device, is used to produce the less relatively single capsule of a large amount of solids or liquid active substance, and described capsule has roughly all even predetermined characteristics.In one piece of patent (United States Patent (USP) 3310612) afterwards, Somerville has described a kind of high-quality capsule method and instrument of centrifugal formation 1500 micron diameters.
Johnson etc. (gas-chromatography magazine, 345, (1965)) have described a kind of method with liquid phase substance and diatomite mixture dressing bead, and this method can repeat and improve the post effect.
Harlowe (" about the problem that increases progressively of micro-capsule embedding system ", Arden House meeting, 1-2 page or leaf, 13-18 day February nineteen eighty-three) describes to soak and buries the nozzle instrument, and it can be used for producing the capsule of 1200-2500 micron; And a kind of centrifugal extruder, this machine can be produced the capsule of 500-1000 micron.
Anderson etc. (United States Patent (USP) 4764317) compile system continuously by a kind of micro-capsule that is full of liquid is provided, and have protected capsule and have reduced capsules break, thereby solved the problem that capsule breaks owing to collision mostly.
Sparks etc. (United States Patent (USP) 4675140) have described the method and the instrument of a kind of dressing or micro-capsule embedding solid particle and thickness drop, and this makes most particles by independent or difference dressing, rather than with cluster of particle form dressing; This method also provides simultaneously from coated granule separates improving one's methods of liquid coating material harmful or that do not utilize.Regulate the excess liq coating material droplet that this method can be produced excellent pre-sizing, its diameter is less than each particle of dressing.
Uratsuka (Japanese patent gazette 2-292324) has described a kind of comprising the microcapsule-type ureas hardening accelerator of softening point at 40-200 ℃ thermoplastic resin.
The dressing ball or the micro-capsule that adopt said method to form can make active material be bonded at the coating material surface, therefore do not embody the advantage of dressing or microencapsulation.
Therefore, the objective of the invention is to form the dressing ball of active material, the appearance of this ball does not contain active material.
The present invention be a kind of with active material be encapsulated in its not miscible coating material in method, the fusing point of this coating material is higher than room temperature, and this method comprises the steps: a) under being enough to melt the temperature of coating material active material to be dispersed in the coating material; B) active material that coating material is disperseed forms droplet; C), coating material is solidified with the droplet cooling; And d) make droplet with the lytic activity material but the insoluble solvent of separating the dressing material contact, to remove the active material on coating material surface.
On the other hand, the present invention relates to contain the microballoon that micro-capsule is embedded in the active material in the coating material, and microballoon coating material surface is contacted with the solvent of active material, remove this surperficial active material.
The present invention has solved dressing and microencapsulation problem in the prior art by the active material of removing the coating material surface.
Method of the present invention needed for four steps: a) under being enough to melt the temperature of coating material active material is dispersed in the coating material; B) active material that coating material is disperseed forms droplet; C), coating material is solidified with the droplet cooling; And d) make droplet with the lytic activity material but the insoluble solvent of separating the dressing material contact, to remove the active material on coating material surface.Below four steps are described in detail.
Active material is encapsulated in the first step of method is in the coating material, be enough to make the coating material fusing but do not make coating material and active material decomposes or the temperature of volatilization under form the heterogeneous mixture of active material and coating material.Selected active material and coating material are immiscible each other (unmixings).
Coating material preferred fusing point is between 40-200 ℃.Preferred coating material is the paraffins of petroleum derivation, Tissuemat E, and polyethylene-olefine copolymer comprises oxidation chloroflo, polyester, polyamide or their mixture of hydroxyl or carboxyl.Most preferred coating material is the paraffins of petroleum derivation, polyethylene-olefine copolymer, or Tissuemat E.The most preferred coating material is a Tissuemat E.The mean molecule quantity of preferably polyethylene wax is preferably 500, more preferably in 1000 to 3000 scopes, and especially preferred 2000 dalton.These waxes can exemplify Polywax
TM500, Polywax
TM1000 and Polywax
TM2000, perhaps their mixture, more preferably Polywax
TM1000 and Polywax
TM2000 75: 25 mixture (Polywax is the registration mark of Petrolite Corporation).
At room temperature, active material can be a liquid or solid, but at room temperature is solid preferably.More preferably the fusing point of active material is higher than room temperature but is lower than the decomposition or the volatilization temperature of coating material.Therefore, the fusing point of active material can be higher than, be less than or equal to the fusing point of coating material.In any case, preferably be higher than coating material and active material fusing point but under the Undec temperature of coating material and active material, active material be dispersed in the coating material in this method first step.
Active material can be any and coating material forms inhomogeneous slurry and is dissolved in the insoluble material of separating the solvent of dressing material.For example, active material can be medicine, pesticide, herbicide, aromatic, dyestuff, catalyst or the curing agent that slowly-releasing is used.
Active material is curing agent preferably, more preferably fusing point or vitrification point (T
g) hardening accelerator between 70-200 ℃.
Hardening accelerator is urea or imidazoles preferably.Preferred urea comprises 3-phenyl-1, the 1-dimethyl urea; 3-(4-chlorphenyl)-1, the 1-dimethyl urea; 3-(3, the 4-dichlorophenyl)-1, the 1-dimethyl urea; 1,1 '-(4-methyl-metaphenylene) two (3,3 '-dimethyl urea); The different methyl dimethoxy base of 3-urea-3,5,5-trimethylcyclohexyl dimethyl urea; Or 4,4 '-methylene two (phenyl dimethyl urea).Preferred urea is a 3-phenyl-1,1-dimethyl urea (PDMU).
Preferred imidazoles comprises the alkyl or aryl imidazoles, as glyoxal ethyline, and 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole, 2-ethyl imidazol(e), 2 isopropyl imidazole and 2-phenyl-4-methylimidazole; 1-cyanoethyl derivative, as the 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazole and 1-cyanoethyl-2 isopropyl imidazole; And carboxylate, as 1-cyanoethyl-2-ethyl-4-methylimidazole-trimellitic acid salt.Preferred imidazoles is a glyoxal ethyline.
Hardening accelerator can also be urea-imidazoles conjugate, and as 2-methyl-N-phenyl-1H-imidazoles-1-formamide, this conjugate can be by imidazoles and the preparation of organic polyisocyanate reactant.
As mentioned above, inhomogeneous slurry forms at elevated temperatures.To achieve the object of the present invention, the temperature of rising should be higher than room temperature and be enough to make the coating material dissolving, more preferably makes the dissolving of coating material and active material; But also should be enough low, with thermal decomposition or the volatilization that prevents coating material or active material.
The concentration of active material is preferably from 1wt.%, more preferably from 10wt.%, most preferably from 25wt.% preferably to 60wt.%, more preferably to 45wt.%, most preferably to 35wt.%, with the total weight of active material and coating material.
Second step of the inventive method needs to form droplet.Though the droplet of size all can use arbitrarily, the present invention is preferred for the active material microballoon with the coating material dispersion.To achieve the object of the present invention, microballoon is that diameter is 500 microns or littler spherolite.Preferred particle diameter can be different and different according to using, but preferably from 300 microns, more preferably from 200 microns, most preferably from 150 microns preferably to 10 microns, more preferably to 30 microns, optimum is chosen 50 microns.Similarly, term " micro-capsule embedding " and " microencapsulation " are used for describing and active material is encapsulated into coating material forms microballoon.
As mentioned above, the microballoon that forms the active material that disperses with coating material can adopt distinct methods to finish.The method of the microballoon of the active material that formation disperses with coating material is preferably under the temperature of the rising that is enough to melt coating material, more preferably is poured on the rotating disk being enough to melt the inhomogeneous slurry that under the temperature of coating material and active material the first step is formed.Rotation can be cast coating material/active material dispersion thing rotating disk aside and become microballoon, and microballoon solidifies (the 3rd step) by the air cooling effect.The type decided that the speed of rotating disk, temperature, slurry are poured into speed on the rotating disk and used instrument forms the size of microballoon.
The 4th step, will solidify droplet, preferably the solidified microsphere of the active material that will disperse with coating material compile and with the lytic activity material but the insoluble solvent of separating the dressing material contact.
Preferred solvent is a polarity, because preferred coating material is nonpolar polymer wax, preferred active material is a polarity comparatively.Preferred solvent is volatile, promptly is easy to evaporation and removes.Most preferably fusing point is lower than 100 ℃ solvent.
The example of preferred solvent comprises water; Alcohol is as methyl alcohol, ethanol and isopropyl alcohol; Ketone is as acetone and methyl ethyl ketone; Chlorohydrocarbon is as carrene; And polar non-solute, as second cyanogen.Preferred solvent is a water, methyl alcohol, ethanol, isopropyl alcohol and acetone.Most preferred solvent is acetone and methyl alcohol.
Suppose that active material and coating material volatilize in different temperatures, by being encapsulated in the active matter quality in the coating material behind thermogravimetry (TGA) the mensuration solvent wash.In the TGA method, sample is placed on the platinum dish that links to each other with microbalance, heating makes active material and coating material volatilization then.Because active material and coating material volatilize in different temperatures,, determine composition easily by measuring the function of weight with temperature.
The inventive method provides a kind of active material droplet that is encapsulated in the coating material, preferably be encapsulated in the active material microballoon in the coating material, they show long-term stability in adhesive formulation, and also show highly reactivity (" slaking as required ") under medium temperature condition.In advantageous applications, the micro-capsule that exists with the composition forms that contains epoxy resin and dicyandiamide is embedded in urea in the Tissuemat E or imidazoles and can stores the several months under 40 ℃ or lower temperature.But composition is heated to when being enough to melt the high temperature of wax, and hardening accelerator discharges, and has promoted the reaction of epoxy resin and dicyandiamide.(referring to Japanese patent gazette 2-2923324, December 3 nineteen ninety)
Embodiment 1 solvent rinsing with the PDMU micro-capsule globule of low molecular weight polyethylene wax dressing
Preparation
With 3-phenyl-1,1-dimethyl urea (PDMU) (300g) is distributed to 75/25 Polywax of fusion
TM1000/Polywax
TM2000 (Polywax
TM1000 and Polywax
TMThe mixture of 2000 75: 25 percentage by weight) (700g) in.Heat this mixture then until the PDMU fusion, the speed with per minute 500g is poured on the center of turntable with the 650rpm rotational speed that remains on 140 ℃ again.With Polywax
TMThe PDMU microballoon that disperses is pulled out away from rotating disk, is pooled in the taperer.The diameter of gained microspheres with solid (1000g) soaked 5 minutes them between the 50-300 micron in acetone (1000ml), and then with acetone rinsing 4 times (each 500ml) with Polywax
TMThe PDMU on surface.Globule is carried out the air drying, store when need are made into adhesive then.The stability of embodiment 2 solvent wash microballoons and non-packing microballoon relatively
With the ratio of per 2 parts of active materials of 100 parts of epoxy resin (PDMU) the solvent wash microballoon of embodiment 1 is mixed into D.E.R.
TMIn 331 (registration mark of Dow chemical company) liquid epoxies and be stored in 110 °F.This preparation was kept six months with fluid state.For comparing, make the preparation gelatine in 10 days that comprises non-packing PDMU.Embodiment 3 uses the adhesive of solvent wash microballoon preparation
Be prepared as follows adhesive: with Tactics
TM123 liquid-state epoxy resins (247.5g); D.E.R.TM755 liquid-state epoxy resin (247.5g); The epoxy resin of acrylic rubber modification (495g); Aluminium powder (310g, Reynolds A-200), Cab-O-Sil
TMM-5 mist attitude silica gel (50g); Byk
TMR-605 polycarboxylic acids acid amides (polycarboxylic acid amide) (15g); The solvent wash microballoon (70g) of preparation forms paste adhesive in heavy stirrer for mixing among dicyandiamide (50g) and the embodiment 1.This adhesive is added in the cold-rolled steel sampling test tube of 32 mil thick with 5 mil adhesive thickness, and 177 ℃ of slakings 30 minutes.The lap shear tensile strength of finding this adhesive greater than the T-peel strength of 2000psi and per inch length greater than 20 pounds.
(annotate: Tactics is the registration mark of Dow chemical company; Cab-O-Sil is the registration mark of Cabot company; Byk is the registration mark of BykChemie) the solvent rinsing micro-capsule of embodiment 4 preparation glyoxal ethylines and low molecular weight polyethylene wax is little
Pearl
Glyoxal ethyline (2-MI) (900g) is distributed to 75/25 Polywax of fusion
TM1000/Polywax
TM2000 (Polywax
TM1000 and Polywax
TM75: 25 percentage by weight mixtures of 2000) (525g) in.Heat this mixture then until 2-MI fusion (180 ℃), again with the speed of per minute 300g be poured into remain on 150 ℃ with 10, the center of turntable that 000rpm rotates.With Polywax
TMThe 2-MI microballoon that disperses is pulled out away from rotating disk, is pooled in the collecting chamber.Unwashed microballoon (90g) is kept in the container and compares with the microballoon of washing.
The microballoon (2500g) of diameter at the 50-300 micron soaked 5 minutes in isopropyl alcohol (3000ml), and then with acetone rinsing 4 times (each 1500ml) to remove Polywax
TMThe 2-MI on surface.To finally wash globule (about 2300g) and carry out the air drying, store when need are used for preparation then.Embodiment 5 solvent wash microballoons compare with the stability of not washing microballoon
With the ratio of 1 part of active 2-MI of per 100 parts of liquid-state epoxy resins the solvent wash microballoon of embodiment 4 is mixed into D.E.R.
TMIn 331 (registration mark of Dow chemical company) liquid-state epoxy resin and be stored in room temperature (normally 70).Make this preparation keep more than six months with fluid state.For comparing, make the preparation that comprises non-packing 2-MI and do not wash microballoon gelatine in 2 and 3 weeks respectively.
Claims (12)
- One kind with active material be encapsulated in its not miscible coating material in method, the fusing point of this coating material is higher than room temperature, this method comprises the steps: a) under being enough to melt the temperature of coating material active material to be dispersed in the coating material; B) active material that coating material is disperseed forms droplet; C), coating material is solidified with the droplet cooling; With d) make droplet with the lytic activity material but the insoluble solvent of separating the dressing material contact, to remove the active material on coating material surface.
- 2. the process of claim 1 wherein that a) step is under being enough to melt the temperature of active material active material to be dispersed in the coating material; And b), c) and d) droplet in the step is a microballoon.
- 3. claim 1 or 2 method, wherein coating material is the paraffins of petroleum derivation, Tissuemat E, polyethylene-olefine copolymer wax comprises oxidation chloroflo, polyester or the polyamide of hydroxyl or carboxyl.
- 4. each method of claim 1-3, active material wherein is urea or the imidazoles of fusing point between 70-200 ℃.
- 5. each method of claim 1-4, solvent wherein is that fusing point is lower than 100 ℃ water, alcohol or ketone.
- 6. each method of claim 1-5, active material wherein is a 3-phenyl-1, the 1-dimethyl urea; 3-(4-chlorphenyl)-1, the 1-dimethyl urea; 3-(3, the 4-dichlorophenyl)-1, the 1-dimethyl urea; 1,1 '-(4-methyl-metaphenylene) two (3,3 '-dimethyl urea); The different methyl dimethoxy base of 3-urea-3,5,5-trimethylcyclohexyl dimethyl urea; Or 4,4 '-methylene two (phenyl dimethyl urea); 2-methyl-N-phenyl-1H-imidazoles-1-formamide or glyoxal ethyline.
- 7. each method of claim 1-6, hardening accelerator wherein is a 3-phenyl-1,1-dimethyl urea or glyoxal ethyline.
- 8. each method of claim 1-7, wherein coating material is the Tissuemat E of molecular weight between 1000-2000 dalton.
- 9. each method of claim 1-8, solvent wherein is water, acetone, methyl alcohol, ethanol or isopropyl alcohol.
- 10. each method of claim 1-9, solvent wherein is an acetone.
- 11. a microballoon that contains active material that is encapsulated in the coating material contacts the coating material of this microballoon surface with the solvent of active material, make it not contain active material.
- 12. the microballoon of claim 11, active material wherein are 3-phenyl-1,1-dimethyl urea or glyoxal ethyline, coating material are the Tissuemat E of molecular weight between 1000-2000 dalton.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95195276 CN1161660A (en) | 1994-09-26 | 1995-09-11 | Encapsulated active material and method for preparing same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/311,818 | 1994-09-26 | ||
| CN 95195276 CN1161660A (en) | 1994-09-26 | 1995-09-11 | Encapsulated active material and method for preparing same |
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| Publication Number | Publication Date |
|---|---|
| CN1161660A true CN1161660A (en) | 1997-10-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95195276 Pending CN1161660A (en) | 1994-09-26 | 1995-09-11 | Encapsulated active material and method for preparing same |
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| Country | Link |
|---|---|
| CN (1) | CN1161660A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109069907A (en) * | 2016-04-27 | 2018-12-21 | 尤尼克斯株式会社 | String group, ordinate string and horizontal line string |
-
1995
- 1995-09-11 CN CN 95195276 patent/CN1161660A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109069907A (en) * | 2016-04-27 | 2018-12-21 | 尤尼克斯株式会社 | String group, ordinate string and horizontal line string |
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